DE102018203111A1 - Isothiazolinone-free preservation of detergents - Google Patents

Abstract

The invention relates to liquid aqueous cleaning compositions comprising: a) at least one surfactant; b) at least one salt of sorbic acid or mixtures thereof; c) at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropan-2-ol, 3-phenoxypropane-1,2-diol, benzyloxymethanol or mixtures thereof; d) optionally additives and additives; and e) water, the sum of a) to e) being 100% by weight. Also included are a process for preparing the aforesaid compositions and the use of a mixture of at least one salt of sorbic acid or mixtures thereof and at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropane-2 ol, 3-phenoxypropane-1,2-diol, benzyloxymethanol or mixtures thereof, for increasing the storage stability of liquid aqueous cleaning agents.

Description

The invention relates to liquid aqueous cleaning compositions comprising: a) at least one surfactant; b) at least one salt of sorbic acid or mixtures thereof; c) at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropan-2-ol, 3-phenoxypropane-1,2-diol, benzyloxymethanol or mixtures thereof; d) optionally additives and additives; and e) water, the sum of a) to e) being 100% by weight. Also included are a process for preparing the aforesaid compositions and the use of a mixture of at least one salt of sorbic acid or mixtures thereof and at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropane-2 ol, 3-phenoxypropane-1,2-diol, benzyloxymethanol or mixtures thereof, for increasing the storage stability of liquid aqueous cleaning agents.

Liquid aqueous detergents, in particular hand dishwashing detergents, are generally preserved with isothiazolinone or derivatives thereof, in particular methylisothiazolinone (MIT), benzisothiazolinone (BIT) or octylisothazolinone (OIT), as a preservative. These preservatives are in public criticism, as they may have sensitizing properties. However, they are highly effective active ingredients and therefore not easy to replace. Thus, there is a need for an alternative preservative or preservative system which is capable of providing similar good preservative properties, particularly shelf life, of the composition containing it, and which is also more tolerable or less hazardous to health.

Surprisingly, the inventors of the present invention have found that this is achieved by using a mixture of at least one salt of sorbic acid or mixtures thereof; and at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropan-2-ol, 3-phenoxypropane-1,2-diol, benzyloxymethanol or mixtures thereof. As a result, aqueous cleaning agents are obtained which, among other things, meet the requirements of ECARF or DAAB.

1. a) mindestens ein(em) Tensid;
2. b) mindestens ein(em) Salz der Sorbinsäure oder Mischungen davon;
3. c) mindestens eine(r) Verbindung ausgewählt aus Benzylalkohol, 2-Phenylethylalkohl, 2-Phenoxyethanol, 3-Phenoxypropanol, 1-Phenoxypropan-2-ol, 3-Phenoxypropan-1,2-diol, Benzyloxymethanol oder Mischungen davon;
4. d) gegebenenfalls Additive(n) und Zusatzstoffe(n); und
5. e) Wasser, welches auf 100 Gew.-% addiert wird, wobei die Summe von a) bis e) 100 Gew.-% ergibt.

A first subject of this application are therefore liquid aqueous cleaning agents, hereinafter also referred to as agents according to the invention, comprising or consisting of:

1. a) at least one (em) surfactant;
2. b) at least one salt of sorbic acid or mixtures thereof;
3. c) at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropan-2-ol, 3-phenoxypropane-1,2-diol, benzyloxymethanol or mixtures thereof;
4. d) optionally additives and additives; and
5. e) water, which is added to 100 wt .-%, wherein the sum of a) to e) 100 wt .-% results.

Preferred embodiments are set forth in the dependent claims.

The composition according to the invention can be used for cleaning hard surfaces and for manual dishwashing.

Whenever alkaline earth metals are mentioned below as counter ions for monovalent anions, this means that the alkaline earth metal is only present in half the amount of substance that is sufficient for charge equalization, such as the anion.

Substances which also serve as ingredients of cosmetic products are hereinafter referred to as appropriate according to the German translation of the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed only after Linnaeus in Latin. So-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The translated INCI names can be found in the International Cosmetic Ingredient Dictionary and Handbook, Seventh Edition (1997), published by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101, 17 ^th Street, Suite 300, Washington, DC 20036, USA, and contains more than 9,000 INCI names, as well as references to more than 37,000 trade names and technical names, including related distributors, from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, for example, "polymeric ethers," and one or more functions, for example, "surfactants-detergents," which in turn will be further explained. These may also be referred to below.

The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service

Unless explicitly stated otherwise, stated amounts in percent by weight (% by weight) refer to the entire liquid aqueous cleaning agent. These percentages refer to active contents.

The water content of the aqueous composition according to the invention is usually 15 to 98% by weight, preferably 20 to 95% by weight, in particular 30 to 90% by weight.

In various embodiments of the invention, the agent according to the invention is free from isothiazolinone and its derivatives, in particular methylisothiazolinone (MIT), benzisothiazolinone (BIT) or octylisothazolinone (OIT). "Free from" as used in this context means that the corresponding ingredient is not used intentionally, preferably the concentration in the agent is below 0.5 wt%, more preferably below 0.1 wt% more preferably less than 0.01% by weight, most preferably less than 0.001% by weight, based on the total weight of the composition.

surfactants

The composition according to the invention contains surfactants in a total amount of usually 3 to 50% by weight, preferably 5 to 35% by weight, in particular 7 to 15% by weight. In a preferred embodiment, the liquid aqueous cleaning agent of the present invention comprises anionic and / or amphoteric surfactants. In a more preferred embodiment, the liquid aqueous cleaning agent of the present invention comprises at least one amphoteric surfactant selected from betaines, sulfobetaines or a mixture thereof. In a further more preferred embodiment, the liquid aqueous cleaning agent of the present invention comprises at least one anionic surfactant selected from alkyl ether sulfates, secondary alkanesulfonates, fatty alcohol sulfates, monoglyceride sulfates, ester sulfonates, ligninsulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates, fatty acid sarcosinates, ether carboxylic acids, alkyl ( ether) phosphates and gemini surfactants or a mixture thereof, preferably an alkyl ether sulfate, more preferably sodium lauryl ether sulfate. In an even more preferred embodiment, it comprises at least one amphoteric surfactant and at least one anionic surfactant, more preferably selected from the specific surfactants mentioned above.

In a further preferred embodiment, the agent according to the invention may contain a surfactant combination of alkyl ether sulfate, secondary alkyl sulfonate and betaine, in further preferred forms may additionally contain alkyl polyglycosides. The anionic surfactants are usually in situ as the alkali metal, alkaline earth metal and / or mono-, di- or trialkanolammonium salt and / or else in the form of theirs with the corresponding alkali metal hydroxide, alkaline earth metal hydroxide and / or mono-, di- or trialkanolamine to be neutralized corresponding acid used. Preferred alkali metals here are potassium and in particular sodium, alkaline earth metals calcium and in particular magnesium, and alkanolamines mono-, di- or triethanolamine. Particularly preferred are the sodium salts.

Anionic surfactants

Suitable anionic surfactants are especially the alkyl ether sulfates and secondary alkanesulfonates. However, it is also possible to use aliphatic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates. Also suitable anionic surfactants are anionic Gemini surfactants having a Diphenyloxid basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings according to the formula ^- O ₃ S (C ₆ H ₃ R) O (C ₆ H ₃ R ') SO ₃ ^- in which R is an alkyl radical having, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax® Dry Hydrotropic Powder with C ₁₆ -alkyl radical (s)) INCI: sodium hexyldiphenyl ether sulfonate, disodium decylphenyl ether disulfonate, disodium laurylphenyl ether disulfonate, Dinatriumcetylphenyletherdisulfonat) and fluorinated anionic surfactants, in particular perfluorinated alkylsulfonates such as ammonium C _9/10 -Perfluoroalkylsulfonat (Fluorad FC 120) and Perfluorooctanesulfonic acid potassium salt (Fluorad® FC 95). The composition according to the invention may contain anionic surfactants in amounts of 1 to 30% by weight, preferably 5 to 15% by weight, in particular 7 to 10% by weight.

alkyl ether

Alkyl ether sulfates (fatty alcohol ether sulfates, INCI: alkyl ether sulfates) are products of sulfation reactions on alkoxylated alcohols. In this context, the person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols, ie with aliphatic straight-chain or one or more branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably straight-chain, acyclic, saturated, alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16 and particularly preferably 12 to 14 carbon atoms. In general, from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, a complex mixture of addition products of different degrees of ethoxylation (n = 1 to 30, preferably 1 to 20, especially 1 to 10, particularly preferably 2 to 4). Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Very particularly preferred for the purposes of the present invention are low-ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 2 EO, such as Na-C _12-14 fatty alcohol + 2EO sulfate. A particularly preferred compound is sodium dodecylpoly (oxyethylene) sulfate with 3 EO.

In a preferred embodiment, the composition according to the invention contains one or more alkyl ether sulfates in an amount of 1 to 30% by weight, preferably 5 to 15% by weight, in particular 7 to 10% by weight.

alkylsulfonates

The alkyl sulfonates (INCI: sulfonic acids) usually have an aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical having 6 to 22, preferably 9 to 20, in particular 11 to 18 and particularly preferably 14 to 17 carbon atoms.

Accordingly, suitable alkyl sulfonates are the saturated alkanesulfonates, the unsaturated olefin sulfonates and the ether sulfonates which are derived formally from the alkoxylated alcohols on which the alkyl ether sulfates are based, in which terminal ether sulfonates (n-ether sulfonates) having a sulfonate function bound to the polyether chain and internal radicals Ethersulfonate (i-ether sulfonates) with associated with the alkyl radical sulfonate function. Preference according to the invention is given to the alkanesulfonates, in particular alkanesulfonates having a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na-C13-17-alkane.

The agent according to the invention contains one or more sec. Alkyl sulfonates in an amount of 1 to 30% by weight, preferably 5 to 15% by weight, in particular 7 to 10% by weight.

alkylbenzenesulfonates

Further preferred anionic surfactants are alkylbenzenesulfonates, ABS for short, especially linear alkylbenzenesulfonates (LAS). These usually have the benzene ring in addition to a sulfonic acid or sulfonate also an aliphatic straight-chain or mono- or poly-branched, acyclic, saturated or mono- or polyunsaturated alkyl side chain with 6 to 22, preferably 8 to 20, especially 10 to 16 and particularly preferably 12 up to 14 carbon atoms. Alkylbenzenesulfonates are used in the composition according to the invention preferably in amounts of 1 to 30% by weight, preferably 5 to 15% by weight, in particular 7 to 10% by weight.

alkyl sulfates

Alkyl sulfates (fatty alcohol sulfates, FAS) are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C _12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C _10-20 oxo alcohols and those Half-ester secondary alcohols of these chain lengths are preferred. Also preferred are alkyl sulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Particularly preferred are the C _10-16 alkyl sulfates, in particular the C _12-14 alkyl sulfates. Furthermore It is also possible to use alkyl sulfates having mono- or polysubstituted alkyl chains or cyclic alkyl radicals. The composition according to the invention may contain one or more alkyl sulfates in amounts of preferably 0.1 to 10% by weight, more preferably 0.5 to 6% by weight, in particular 1 to 3% by weight.

Anionic sulfosuccinic acid surfactants

Particularly preferred further anionic surfactants are the anionic sulfosuccinic acid surfactants sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates. The sulfosuccinates are the salts of the monoesters and diesters of sulfosuccinic acid HOOCCH (SO ₃ H) CH ₂ COOH, while the sulfosuccinamates are the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides are the salts of the diamides of sulfosuccinic acid. The salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium, potassium or ammonium salts. or ammonium salts, most preferably sodium salts.

In the sulfosuccinates, one or both carboxyl groups of the sulfosuccinic acid is preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols having 4 to 22, preferably 6 to 20, in particular 8 to 18 , more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified. Particularly preferred are the esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols, in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4. The monoesters are preferred in the context of the present invention over the diesters. A particularly preferred sulfosuccinate is sulfosuccinic acid lauryl polyglycol ester di-sodium salt (lauryl EO sulfosuccinate, di-Na salt), which is commercially available, for example, as Tego® sulfosuccinate (Evonik Tego Chemie GmbH) having a sulfosuccinate content of 30% by weight.

In the sulfosuccinamates or sulfosuccinamides, one or both form carboxyl groups of the sulfosuccinic acid preferably with a primary or secondary amine having one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals having 4 to 22 , preferably 6 to 20, in particular 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms carries, a carboxylic acid amide. Particular preference is given to unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals. Further suitable are, for example, in the WO 2008/046778 A1 disclosed sulfosuccinamates and sulfosuccinamides, to which reference is explicitly made. Yet another suitable sulfosuccinamate is disodium C _18-20 alkoxypropylene sulfosuccinamate.

Preferred anionic sulfosuccinic acid surfactants are imidosuccinate, monosodium sulfosuccinic di-isobutyl ester (Monawet® MB 45), monosodium sulfosuccinic acid di-octyl ester (Monawet® MO-84 R2W, Rewopol® SB DO 75), mono-sodium sulfosuccinic di-tridecyl ester (Monawet® MT 70), fatty alcohol polyglycol sulfosuccinate Na-NH ₄ salt (sulfosuccinate S-2), di-Na-sulfosuccinic acid mono C _12/14 -3EO ester (Texapon® SB-3), diisooctyl sodium sulfosuccinate (Texin® DOS 75) and di-Na-sulfosuccinic acid mono-C _12/18 ester (Texin® 128-P), in particular the mono-Na-sulfosuccinic acid di-octyl ester. In a particular embodiment, the agent according to the invention contains as anionic sulfosuccinic acid surfactants one or more sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or sulfosuccinamates, in particular sulfosuccinates, in an amount of usually 0.001 to 5% by weight, preferably 0.01 to 4 % By weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2% by weight, very preferably 0.5 to 1.5% by weight, for example 1% by weight.

Other suitable anionic surfactants are in particular anionic gemini surfactants with a diphenyl oxide base structure 2 sulfonate groups and an alkyl group on one or both benzene rings of the formula ^- O ₃ S (C ₆ H ₃ R) O (C ₆ H ₃ R ') SO ₃ ^- in which R is an alkyl radical having, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax® Dry Hydrotropic Powder with C ₁₆ -alkyl radical (s), INCI: sodium hexyldiphenyl ether sulfonate, disodium decylphenyl ether bisulfonate, disodium lauryl phenyl ether bisulfonate, Disodium cetylphenyl ether disulfonates) and the fluorinated anionic surfactants ammonium C _9/10 perfluoroalkylsulfonate (Fluorad® FC 120), perfluorooctanesulfonic acid potassium salt (Fluorad® FC 95) and the sulfosuccinic acid surfactants imidosuccinate, monosodium sulfosuccinic acid di-isobutyl ester (Monawet® MB 45), monosodium sulfosuccinic acid di-octyl ester (Monawet® MO 84 R2W, Rewopol® SB DO 75), monosodium sulfosuccinic acid di-tridecyl ester (Monawet® MT 70), Fatty alcohol polyglycol sulfosuccinate Na-NH ₄ salt (sulfosuccinate S-2), di-Na sulfosuccinic acid mono C _12/14 -3EO ester (Texapon® SB-3), diisooctyl sodium sulfosuccinate (Texin® DOS 75) and Di-Na Sulfosuccinic acid mono-C _12/18 ester (Texin® 128 P).

Amphoteric surfactants

Betaine

Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazoliumbetaines, the sulfobetaines (INCI: sultaines) and the phosphobetaines and preferably satisfy formula I, R ¹ - [CO-X- (CH ₂ ) _n ] _x -N ⁺ (R ² ) (R ³ ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] yY ^- (I), in
R ¹ is a saturated or unsaturated C _6-22 alkyl, preferably C _8-18 alkyl group, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group,
X is NH, NR ⁴ with the C _1-4 -alkyl radical R ⁴ , O or S,
n is a number from 1 to 10, preferably 2 to 5, in particular 3,
x is 0 or 1, preferably 1,
R ² , R ^{3 are} independently a C _1-4 alkyl radical, optionally hydroxy-substituted, such as. B. a hydroxyethyl radical, but especially a methyl radical,
m is a number from 1 to 4, in particular 1, 2 or 3,
y is 0 or 1 and
Y is -COO, -SO ₃ , -OPO (OR ⁵ ) O or -P (O) (OR ⁵ ) O, wherein R ^{5 is} hydrogen H or C _1-4 alkyl.

The alkyl and alkylamido betaines, betaines of the formula I having a carboxylate group (Y ^- = COO ^- ) are also called carbobetaines.

Preferred betaines are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id),
R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO- (Ia)
R ¹ -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (Ib)
R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (IC)
R ¹ -CO-NH- (CH ₂ ) ₃ -N '(CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (Id) in which R ^{1 has} the same meaning as in formula I.

Particularly preferred betaines are the carbo-betaines, in particular the carbo-betaines of the formula (Ia) and (Ib), most preferably the alkylamido-betaines of the formula (Ib).

Examples of suitable betaines and sulfobetaines are, for example, in WO 2008/046778 A1 which is incorporated by reference. A preferred betaine is, for example, cocoamidopropyl betaine or betaine, which is commercially available under the trade name Tego® Natural Betaine from Evonik.

The agent according to the invention may contain one or more betaines in an amount of preferably 0.1 to 15% by weight, more preferably 1 to 10% by weight, in particular 2 to 5% by weight. In a preferred embodiment, the agent according to the invention may contain a surfactant combination of a) alkyl ether sulfate, b) secondary alkanesulfonate and c) betaine, said surfactants preferably being in a ratio a) b) c) of 5: 2: 1 to 3: 1: 1 are available.

Other amphoteric surfactants

The amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the betaines are preferred within the scope of the teaching according to the invention.

alkylamidoalkylamines

The alkylamidoalkylamines (INCI: alkylamido alkylamines) are amphoteric surfactants of the formula (III), R ⁹ -CO-NR ¹⁰ - (CH ₂ ) _i -N (R ¹¹ ) - (CH ₂ CH ₂ O) _j (CH ₂ ) _k - [CH (OH)] _I -CH ₂ -Z-OM (III) in which
R ⁹ is a saturated or unsaturated C _6-22 alkyl, preferably C _8-18 alkyl group, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group,
R ^{10 is} a hydrogen atom H or a C _1-4 -alkyl radical, preferably H,
i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
R ^{11 is} a hydrogen atom H or CH ₂ COOM,
j is a number from 1 to 4, preferably 1 or 2, in particular 1,
k is a number from 0 to 4, preferably 0 or 1,
I 0 or 1, where k = 1, if I = 1,
Z is CO, SO ₂ , OPO (OR ¹² ) or P (O) (OR ¹² ) wherein R ^{12 is} C _1-4 alkyl or M (defined as follows), and
M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.

Preferred representatives satisfy the formulas IIIa to IIId,
R ⁹ -CO-NH- (CH ₂ ) ₂ -N (R ¹¹ ) -CH ₂ CH ₂ O-CH ₂ -COOM (IIIa)
R ⁹ -CO-NH- (CH ₂ ) ₂ -N (R ¹¹ ) -CH ₂ CH ₂ O-CH ₂ CH ₂ COOM (IIIb)
R ⁹ -CO-NH- (CH ₂ ) ₂ -N (R ¹¹ ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -SO ₃ M (IIIC)
R'-CO-NH- (CH ₂ ) ₂ -N (R ¹¹ ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -OPO ₃ HM (IIId) in which R ¹¹ and M have the same meaning as in formula (III).

Exemplary suitable alkylamidoalkylamines are, for example, those in WO 2008/046778 A1 which is explicitly referred to.

Also suitable amphoteric surfactants are in particular Natriumcarboxyethylkokosphosphoethylimidazolin (Phosphoteric® TC-6), C _8/10 amidopropylbetaine (INCI: Capryl / Capramidopropyl Betaine, Tego® Betaine 810), N-2-hydroxyethyl-N-carboxymethylfettsäureamidoethylamin-Na (Rewoteric® AMV ) and N-capryl / caprin-amidoethyl-N-ethyl ether propionate-Na (Rewoteric® AMVSF) and the betaine 3- (3-cocoamido-propyl) -dimethylammonium-2-hydroxypropanesulfonate (INCI: Sultaine, Rewoteric® AM CAS) and the Alkylamidoalkylamine N- [N '(N "-2-hydroxyethyl-N" -carboxyethylaminoethyl] -acetic acid-N, N-dimethyl-N-coco-ammoniumbetaine Rewoteric® QAM 50).

Alkyl substituted amino acids

Alkyl-substituted amino acids which are preferred according to the invention are monoalkyl-substituted amino acids of the formula (IV)
R ^{13 is} -NH-CH (R ¹⁴ ) - (CH ₂ ) _U -COOM '(IV) in which
R ¹³ is a saturated or unsaturated C _6-22 alkyl, preferably C _8-18 alkyl group, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group, R ¹⁴ is a hydrogen atom H or a C _{1 -4-} alkyl radical, preferably H,
u is a number from 0 to 4, preferably 0 or 1, in particular 1, and
M 'is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine,
alkyl-substituted imino acids according to formula (V),
R ¹⁵ -N - [(CH ₂ ) _V -COOM "] ₂ (V) in which
R ¹⁵ is a saturated or unsaturated C _6-22 alkyl, preferably C _8-18 alkyl group, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group,
v is a number from 1 to 5, preferably 2 or 3, in particular 2, and
M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M "in the two carboxy groups may have the same or two different meanings, eg hydrogen and sodium or twice sodium, is
and mono- or dialkyl-substituted natural amino acids according to formula (VI), R ¹⁶ -N (R ¹⁷ ) -CH (R ¹⁸ ) -COOM "'(VI) in which
R ¹⁶ is a saturated or unsaturated C _6-22 alkyl, preferably C _8-18 alkyl group, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group, R ¹⁷ represents a hydrogen atom or a C _{1- 4-} alkyl radical, optionally hydroxyl or amine-substituted, for example a methyl, ethyl, hydroxyethyl or Aminpropylrest,
R ^{18 is} the radical of one of the 20 natural α-amino acids H ₂ NCH (R ¹⁸ ) COOH, and M '"is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.

Particularly preferred alkyl-substituted amino acids are the aminopropionates according to formula (IVa), R ¹³ -NH-CH ₂ CH ₂ COOM '(IVa), in which R ¹³ and M' have the same meaning as in formula (IV).

Exemplary suitable alkyl-substituted amino acids are described in U.S. Pat WO 2008/046778 A1 which is explicitly incorporated by reference.

Acylated amino acids

Acylated amino acids are amino acids, in particular the 20 natural α-amino acids which carry on the amino nitrogen the acyl radical R ¹⁹ CO of a saturated or unsaturated fatty acid R ¹⁹ COOH, where R ^{19 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 Alkyl, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical. The acylated amino acids can also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt. Exemplary acylated amino acids are the acyl derivatives summarized under INCI under Acids, for example sodium cocoylglutamate, lauroylglutamic acid, capryloylglycine or myristoylmethylalanine.

Amphotensidkombinationen

In a particular embodiment of the invention, a combination of two or more different amphoteric surfactants, in particular a binary Amphotensidkombination is used. The amphoteric surfactant combination preferably contains at least one betaine, in particular at least one alkylamidobetaine, more preferably cocoamidopropylbetaine. Furthermore, the amphoteric surfactant combination preferably contains at least one amphoteric surfactant from the group comprising sodium carboxyethyl cocosphoethylimidazoline (Phosphoteric® TC6), C _8/10 amidopropyl betaine (INCI: caprylic / capramidopropyl betaine, Tego® Betaine 810), N-2-hydroxyethyl-N-carboxymethyl- fatty acid amido-ethylamine-Na (Rewoteric® AMV) and N-capryl / caprinamidoethyl-N-ethyl ether-propionate-Na (Rewoteric® AMVSF) as well as the betaine 3- (3-cocoamido-propyl) -dimethylammonium-2-hydroxypropanesulfonate (INCI: Sultaine, Rewoteric® AM CAS) and the alkylamidoalkylamine N- [N '(N "-2-hydroxyethyl-N" -carboxyethylaminoethyl) -acetic acid amido] -N, N-dimethyl-N-coco-ammoniumbetaine (Rewoteric® QAM 50), in particular together with cocoamidopropylbetaine.

In a further particular embodiment, the agent according to the invention contains one or more amphoteric surfactants in an amount of more than 0.1% by weight and less than 8% by weight, preferably less than 5% by weight, less than 3% by weight. ,

Nonionic surfactants

The composition according to the invention may additionally contain one or more nonionic surfactants, usually in an amount of from 0.1 to 15% by weight, preferably from 0.25 to 10% by weight, in particular from 0.5 to 6% by weight.

Nonionic surfactants in the context of the invention are alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, endgroup-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also suitable are block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers. Important classes of nonionic surfactants according to the invention are furthermore the amine oxides and the sugar surfactants, in particular the alkyl polyglucosides, as well as the biosurfactants (glycolipids).

Fettalkoholpolyglykolether

Among fatty alcohol polyglycol ethers, saturated or unsaturated C are according to the invention with ethylene (EO) and / or propylene oxide (PO) alkoxylated, branched or unbranched, to understand _10-22 alcohols with a degree of alkoxylation up to 30, preferably ethoxylated C _10-18 fatty alcohols with a Degree of ethoxylation of less than 30, preferably with a degree of ethoxylation of 1 to 20, in particular from 1 to 12, more preferably from 1 to 8, most preferably from 2 to 5, for example C _12-14 fatty alcohol ethoxylates with 2, 3 or 4 EO or a mixture of the C _12-14 fatty alcohol ethoxylates with 3 and 4 EO in the weight ratio of 1 to 1 or isotridecyl alcohol ethoxylate with 5, 8 or 12 EO.

amine oxides

The amine oxides suitable in accordance with the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy formula II,
R ⁶ R ⁷ R ⁸ N ⁺ -O ^- (II)
R ⁶ - [CO-NH- (CH ₂ ) _W ] _Z -N + (R ⁷ ) (R ⁸ ) -O ^- (II) in which
R ⁶ is a saturated or unsaturated C _6-22 alkyl, preferably C _8-18 alkyl group, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group, one in the alkylamidoamine oxides via Carbonylamidoalkylengruppe -CO-NH- (CH ₂ ) _z - and in the Alkoxyalkylaminoxiden via an oxaalkylene group -O- (CH ₂ ) _Z - bound to the nitrogen atom N, wherein z is in each case a number from 1 to 10, preferably 2 to 5 , in particular 3, R ⁷ , R ⁸ independently of one another is a C _1-4 -alkyl radical, optionally hydroxy-substituted, such as. B. is a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are in the WO 2008/046778 A1 which is explicitly referred to. A preferred amine oxide is, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide)

sugar surfactants

Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerolamides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides. Preferred sugar surfactants within the scope of the teaching according to the invention are the alkyl polyglycosides and the sugar amides and their derivatives, in particular their ethers and esters. The ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxyl groups, for example C _1-22 -alcohols or glycols such as ethylene and / or propylene glycol, where the sugar hydroxy group also comprises polyethylene glycol. and / or can carry polypropylene glycol. The esters are the reaction products of one or more, preferably one, sugar hydroxy group with a carboxylic acid, especially a C6-22 fatty acid.

sugar amides

Particularly preferred sugar amides satisfy the formula R'C (O) N (R ") [Z], in which R 'is a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, having 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R "is a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferred 8 to 14 carbon atoms, a C _1-5 alkyl radical, in particular a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or n-pentyl radical, or hydrogen and Z is a sugar radical ie a monosaccharide residue. Particularly preferred sugar amides are the amides of glucose, the glucamides, for example lauroyl-methylglucamide.

Alkylpolyglykoside

The alkylpolyglycosides (APG) are particularly preferred sugar surfactants within the scope of the teaching according to the invention and preferably satisfy the general formula R'O (AO) _a [G] _x in which R 'is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar residue and x for a number from 1 to 10 and AO for an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a represent the average degree of alkoxylation of 0 to 20. In this case, the group (AO) _{a may} also contain different alkyleneoxy units, for example ethyleneoxy or propyleneoxy units, in which case a is the average total degree of alkoxylation, ie the sum of degree of ethoxylation and degree of propoxylation. Unless otherwise stated below, the alkyl radicals R 'of the APG are linear unsaturated radicals having the specified number of carbon atoms.

APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry. The index number x indicates the degree of oligomerization (DP degree), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10. While x in a given compound always has to be an integer, and above all the values x = 1 to 6, the value x for a given alkyl glycoside is an analytically determined arithmetic size, which is usually a fractional number. Preferably, alkyl glycosides having a mean degree of oligomerization x of 1.1 to 3.0 are used. From an application point of view, those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred. The glycosidic sugar used is preferably xylose, but especially glucose. The alkyl or alkenyl radical R 'can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, such as those obtained during the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from ROELEN's oxosynthesis.

Preferably, however, the alkyl or alkenyl radical R 'is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Furthermore, elaidyl alcohol, Petroselylalkohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures may be mentioned.

Particularly preferred APG are not alkoxylated (a = 0) and satisfy the formula RO [G] _x , in which R is as previously described for a linear or branched, saturated or unsaturated alkyl radical having 4 to 22 carbon atoms, [G] for a glycosidically linked sugar radical, preferably glucose residue, and x is a number from 1 to 10, preferably 1.1 to 3, in particular 1.2 to 1.6. Accordingly, preferred alkyl polyglycosides are, for example, C _8-10 and C _12-14 alkyl polyglucoside having a DP degree of 1.4 or 1.5, especially C _8-10 alkyl-1,5-glucoside and C _12-14 alkyl-1,4-glucoside.

A likewise particularly suitable class of nonionic surfactants are so-called biosurfactants, which are glycolipids of microbial origin, for example sophorolipids, rhamnolipids, glucoselipids, cellobioselipids or trehaloselipids. Glycolipids in the narrower sense are compounds in which one or more monosaccharide units are glycosidically linked to a lipid moiety. They belong to the biosurfactants, which are surfactants of microbial origin, which can be produced on the basis of vegetable oil or sugar substrates. For example, sophorolipids are produced by fermentation using yeasts such as Candida bombicola (also known as Torulopsis bombicola), Yarrowia lipolytica, Candida apicola (Torulopsis apicola) and Candida bogoriensis by growing them on sugars, hydrocarbons, vegetable oils or mixtures thereof. The sophorolipid available from Soliance under the trade name Sopholiance S is obtained, for example, by fermentation of Candida bombicola on rapeseed oil methyl ester and glucose. On the other hand, rhamnolipids are obtained from bacteria of the genus Pseudomonas, in particular from Pseudomonas aeruginosa, preferably when grown on hydrophobic substrates such as n-alkanes or vegetable oils. Other glycolipids, such as glucoselipids, cellobioselipids or trehaloselipids, are produced by other microorganisms on different substrates. Preferably used glycolipid biosurfactants are selected from the group comprising sophorolipids, rhamnolipids, glucoselipids, cellobioselipids, trehaloselipids and mixtures thereof, particularly preferably sophorolipids and / or rhamnolipids are used.

Further suitable nonionic surfactants are, in particular, C ₁₀ -dimethylamine oxide (Ammonyx® DO), C _10-14 -fatty alcohol + 1.2PO + 6,4EO (Dehydol® 980), C _12/14 -fatty alcohol + 6EO (Dehydol® LS6), C ₈ fatty alcohol + 1.2PO + 9EO (Dehydol® O10), C _16/20 guerbet alcohol + 8EO, n-butyl-capped (Dehypon® G2084), mixture of several n-butyl-closed nonionic surfactants and C _8/10 -APG (Dehypon® Ke 2555), C _8/10 fatty alcohol + 1PO + 22EO- (2-hydroxydecyl) ether (Dehypon® Ke 3447), C _12/14 fatty alcohol + 5EO + 4PO (Dehypon® LS 54 G ), C _12/14 fatty alcohol + 5EO + 3PO, methyl-capped (Dehypon® LS 531), C _12/14 fatty alcohol + 10EO, n-butyl-capped (Dehypon® LS 104 L), C ₁₁ -oxoalcohol + 8EO ( Genapol® UD 088), C ₁₃ oxo alcohol + 8EO (Genapol® X 089), C _13/15 fatty alcohol EO adduct, n-butyl capped (Plurafac® LF 221) and alkoxylated fatty alcohol (Tegotens® EC11).

Other suitable ingredients may be included in the detergent of the invention and are referred to as additives in the present invention.

Water-soluble salts

The cleaning agent according to the invention may further comprise one or more water-soluble salts which serve, for example, for adjusting the viscosity. It may be inorganic and / or organic salts, in a preferred embodiment, the agent contains at least one inorganic salt.

Inorganic salts which can be used according to the invention are preferably selected from the group consisting of colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or transition metals, furthermore ammonium salts used. Particularly preferred are halides and sulfates of the alkali metals, preferably the inorganic salt is therefore selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof.

The organic salts which can be used according to the invention are, in particular, colorless water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and / or transition metal salts of the carboxylic acids. Preferably, the salts are selected from the group comprising formate, acetate, Propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof. A particularly preferred salt is the skin-friendly known lactate, which both counteract the drying of the skin and can prevent skin irritation and additionally has an antibacterial activity.

solvent

In one embodiment, the agent according to the invention may advantageously additionally comprise one or more water-soluble organic solvents, usually in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, in particular 2 to 15% by weight, more preferably 3 to 12% by weight, most preferably 4 to 8% by weight. In a further preferred embodiment, the agent according to the invention is free of organic solvents.

The solvent is used in the context of the teaching of the invention as needed in particular as a hydrotrope, viscosity regulator and / or cold stabilizer. It acts solubilizing, especially for surfactants and electrolyte as well as perfume and dye and thus contributes to their incorporation, prevents the formation of liquid-crystalline phases and has a share in the formation of clear products. The viscosity of the agent according to the invention decreases with increasing amount of solvent. However, too much solvent can cause excessive viscosity drop. Finally, as the amount of solvent increases, the clouding and clearing point of the composition according to the invention decreases.

Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C _1-20 -hydrocarbons, preferably C _2-15 -hydrocarbons, having at least one hydroxy group and optionally one or more ether functions COC, ie the carbon atom chain interrupting oxygen atoms. Preferred solvents are the - optionally unilaterally etherified with a C _1-6 alkanol - C _2-6 alkylene glycols and poly-C _2-3 alkylene glycol having an average of 1 to 9 identical or different, preferably the same, alkylene glycol groups per molecule as well C _1-6 -alcohols, preferably ethanol, n-propanol or isopropanol, especially ethanol. Exemplary solvents are in the WO 2008/046778 A1 which is incorporated by reference.

Particularly preferred solvents are the unilaterally etherified with a C _1-6 alkanol poly-C _2-3 alkylene glycol having an average of 1 to 9, preferably 2 to 3, ethylene or propylene glycol, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether). Preferably, the solvent is selected from the group comprising methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol and mixtures thereof. The most preferred solvents are the C _2-3 alcohols ethanol, n-propanol and / or iso-propanol, especially ethanol.

As a solubilizer, in particular for perfume and dyes, for example, alkanolamines and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical can be used in addition to the solvents described above.

Other additives

In addition to the components mentioned so far, the compositions according to the invention may contain further additives. These include, for example, other surfactants, microcapsules, additives for improving the drainage and drying behavior, for adjusting the viscosity, for stabilization and other customary in manual dishwashing detergents and additives, such as UV stabilizers, perfume, pearlescing agents, dyes, corrosion inhibitors, preservatives, organic Salts, disinfectants, enzymes and pH adjusters.

Cationic surfactants

The composition according to the invention may additionally contain one or more cationic surfactants (cationic surfactants, INCI: quaternary ammonium compounds), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3% by weight %, more preferably 0.2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight. Preferred cationic surfactants are the quaternary surface-active compounds, in particular having an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or whose antimicrobial effect, which may already be present due to other ingredients, can be improved. Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV, INCI: Quaternary Ammonium Compounds) according to the general formula (R ') (R ") (R"') ( ^R'V ) N ⁺ X ^- , in which R 'to R ^{'v are} identical or different C _1-22 -alkyl radicals, C _7-28 -aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic inclusion as in pyridine, even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or Imidazoliniumverbindung , form, represent and X are halide ions, sulfate ions, hydroxide ions or similar anions. For optimum antimicrobial activity, preferably at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms. QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines having three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAVs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C ₁₂ -alkylammonium chloride, CAS No. 58390-78-6), Benzoxonium chloride (benzyl-dodecyl-bis- (2-hydroxyethyl) -ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No 57-09-0), benzetonium chloride (N, N-dimethyl-N-) [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No 121-54-0), dialkyldimethylammonium chloride such as di-n-decyldimethylammonium chloride (CAS No 7173- 51-5-5), didecyldimethylammonium bromide (CAS No 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No 123-03-5) and thiazoline iodide (CAS No 15764-48-1) and mixtures thereof , Preferred QUATS are the benzalkonium chlorides containing _C8-18 alkyl groups, particularly C _{12- 14} alkyl benzyldimethylammonium chloride. A particularly preferred QAV is coco-pentaethoxymethylammonium methosulfate (INCI PEG-5 Cocomonium Methosulfate, Rewoquat® CPEM).

Further suitable cationic surfactants are, in particular, cationic surfactants which are compatible with anionic surfactants, such as quaternary ammonium compounds, for example cocospentaethoxymethylammonium methosulfate (INCI: PEG-5 Cocomonium Methosulfate, Rewoquat® CPEM). Polymers suitable as additives are in particular maleic acid-acrylic acid copolymer Na salt (Sokalan® CP 5), modified polyacrylic acid Na salt (Sokalan® CP 10), modified polycarboxylate Na salt (Sokalan® HP 25), polyalkylene oxide, modified heptamethyltrisiloxane (Silwet® L77), polyalkylene oxide, modified heptamethyltrisiloxane (Silwet® L-7608) and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide segments (polyether blocks)), preferably water-soluble linear polyethersiloxanes with terminal polyether blocks such as Tegopren® 5840, Tegopren® 5843, Tegopren ® 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878.

In order to avoid possible incompatibilities of the cationic surfactants with the anionic surfactants according to the invention anionic surfactant-compatible and / or cationic surfactant is preferably used or omitted in a particular embodiment of the invention entirely on cationic surfactants.

The skin feel positively affecting agents

The agent according to the invention may contain one or more active ingredients which have a positive effect on the skin. These are understood as meaning those raw materials which bring about a sensory effect, ie a positive skin feel, such as smoother skin or a lower feeling of dryness on the skin, as well as active ingredients with positive biological effects such as skin calming or skin protection. For example, soothing, soothing, smoothing, anti-inflammatory or antioxidant plant extracts and vitamins, as well as bisabolol, allantoin, nourishing wax dispersions, nourishing polymers and other care and conditioning agents used in cosmetic compositions and mixtures may serve as skin-influencing active ingredients ,

The sensory, the skin feel positive influencing agents in the context of this invention, the effect of which is usually already quite short term and after one or a few applications palpable, can be divided mainly into two groups, the quaternary polymers and the skin affine refatting agents. The quaternary polymers may be synthetic or natural or modified natural polymers. Thus, for example, quaternized protein hydrolysates or partial hydrolysates, such as the quaternized wheat protein hydrolyzate sold by BASF under the trade name Gluadin® WQ, can be used to improve the feel on the skin. As further quaternary polymers here are an acrylamide-diallyldimethylammonium chloride copolymer (INCI: Polyquaternium-7), as it is sold for example by BASF under the trade name Polyquart® 701 / NA, or a Copolymer of hydroxyethyl cellulose and diallyldimethylammonium chloride units (INCI: Polyquaternium-4), such as Celquat® L200 (Akzo Nobel), called. Other copolymers synthesized from several monomers are also suitable active agents, such as those from subunits of AMPS (2-acrylamido-2-methylpropanesulfonic acid), MAPTAC (3- [methacrylamidopropyl] trimethylammonium chloride), DMAPMA (N- [3-dimethylamino] propylmethacrylamide) and acrylamide composite copolymers (INCI Polyquaternium-43), which can be obtained, for example, under the trade name Bozequat® 4000 from Clariant. A suitable quaternary polymer is also a diquaternary polydimethylsiloxane, as commercially available, for example, from Evonik under the tradename Tegopren® 6922. Derivatives of hydroxyethylcellulose, for example, hydrophobized cationic hydroxyethylcellulose, such as that available under the trade name Softcat Polymer® from Dow Amerchol, or also the reaction products of quaternary ammonium salts of hydroxyethylcellulose with trimethylammonium-substituted epoxides (2-hydroxyethylcellulose-2- [2-hydroxy-3- (trimethylammonio ) propoxy] ethyl 2-hydroxy-3- (trimethylammonio) propyl ether chloride, INCI: Polyquaternium-10), available, for example, under the trade names Jellner® QH300 (Daicel) or Ucare® Polymer (Dow Amerchol) are also suitable. The usable modified natural polymers further include cationically modified polysaccharides and in particular cationically modified polygalactomannans. Quaternized guar gum flour, which is available, for example, from BASF under the trade name Cosmedia® Guar C 261 N or from Hercules Aqualon under the trade name N-Hance®, may be mentioned here in particular.

Among the skin-affine moisturizing agents are, for example, nourishing wax dispersions. As such, all wax dispersions used in skin care and hair care / conditioning cosmetic preparations can be used. Representative here is the dispersion of (INCI) glycol distearate, coco-glucoside, glyceryl oleate and glyceryl stearate available under the trade name Lamesoft® TM Benz from BASF. A mixture of alkylpolyglycoside and fatty acid partial esters of glycerol, for example the plantatex® LLE offered by BASF, can also be used according to the invention. In addition, according to the invention it is also possible to use further care and conditioning agents used in cosmetic agents, such as the conditioner marketed by Evonik under the trade name Amilan® GST 40, which is a mixture of a C _12-14 fatty alcohol polyglycol ether with 3 ethylene oxide ( EO) units (INCI: Laureth-3) and a mixed ester of fatty acids and diacetyltartaric acid with glycerol. Further suitable skin-affinity jerk-greasing active ingredients are mixtures of longer-chain alcohols and ethers, for example the mixture of dicapryl ether and lauryl alcohol available under the trade name Cetiol® LDO from BASF. Polymers such as polypropylene terephthalate sold under the trade name Aristoflex® PEA / PEA 70 by Clariant, or long-chain glycols, such as the polyglycol 35000S from Clariant, a polyethylene glycol (INCI: PEG-800), can also be used as sensory agents in the context of this invention , Protein hydrolysates or partial hydrolysates can also be used in agents according to the invention, for example collagen partial hydrolysates or also vegetable protein partial hydrolysates and protein hydrolyzate-fatty acid condensates. Also suitable are amino acids and amino acid derivatives such as creatine, the z. B. under the trade name Tego® Cosmo C 100 from Evonik is available.

The sensory active substances are preferably present in amounts of from 0.01 to 8% by weight, preferably from 0.1 to 5% by weight, in particular from 1 to 3% by weight.

In addition to one or more sensory agents, the agent according to the invention in a preferred embodiment additionally contains one or more active substances with positive biological effects. These include, for example, plant extracts and vitamins, but also bisabolol, allantoin or A.H.A. complexes. Preferred plant extracts are preferably selected from the group comprising calendula extract (Calendula officinalis), green tea extract, almond extract, arnica extract (Amica montana), hops extract (Humulus lupulus), balm extract (Melissa officinalis), gentian extract (Gentiana lutea), chamomile extract (Matricaria chamomilla). , Henna extract (Lawsonia inermis) and mixtures thereof. This marigold and green tea extract especially anti-inflammatory and able to calm the skin, the almond extract also has a smoothing and regenerating effect, the arnica extract, the anti-inflammatory effect is used, and the other plant extracts mentioned are able to soothe the skin in general and protect. Other usable skin-care extracts include, for example, aloe vera, witch hazel extract or algae extracts. However, most preferred are the extracts of marigold and green tea. The plant extracts are preferably used in amounts of 0.01 to 20% by weight, more preferably 0.1 to 5% by weight.

Particularly preferred vitamins are selected from the group comprising vitamin A (retinol), vitamin B5 (panthenol), vitamin C (ascorbic acid), vitamin E (tocopherol) and mixtures thereof. The Vitamins A, C and E act as antioxidants, vitamin A and vitamin E can further counteract skin aging, and panthenol (vitamin B5) has an anti-inflammatory and calming effect. But other vitamins, such as vitamins B2 (riboflavin) and B12 (cobalamins) or vitamin H (biotin) can be used according to the invention. However, vitamin B5 and / or vitamin E are particularly preferably used. In accordance with the invention, vitamins are preferably present in amounts of 0.01 to 5% by weight, preferably 0.1 to 3% by weight.

Perfumes and perfumes

In a preferred embodiment, the agent according to the invention contains perfumes and / or fragrances. It is possible to use all perfumes and / or fragrances known to the person skilled in the art, with the proviso that they essentially do not adversely affect the properties of the cleaning agent.

microcapsules

It may be desirable to maintain the skin feel positive influencing agents or other sensitive agents, such as perfumes, spatially separated from the actual agent until use. An elegant method for incorporating such sensitive, chemically or physically incompatible or volatile ingredients is the use of microcapsules in which these ingredients are stored stable and transport stable and from which they are released to or during use mechanically, chemically, thermally or enzymatically , In a preferred embodiment, therefore, one or more of the skin feel positively affecting agents and / or perfumes and / or fragrances is wholly or partially incorporated into microcapsules.

Microcapsules are finely dispersed liquid or solid phases coated with film-forming polymers, in the preparation of which the polymers precipitate on the material to be enveloped (active ingredient) after emulsification and coacervation or interfacial polymerization. In this case, the active ingredient is shell-shaped enveloped by a solid membrane (microcapsule in the strict sense) or enclosed by a matrix (microsphere or sphere). In the following, the term microcapsule is used in a summarized sense for both variants. Such capsules are usually microscopically small (<50 microns) and are sometimes referred to as nanocapsules or nanospheres, they can be dried like powder. However, larger capsules or pearls visible to the naked eye (> 0.5 mm) filled with active ingredients can also be produced. These provide, incorporated into the hand dishwashing agent according to the invention, an additional visual appeal when the capsules are suspended stable distributed on average, which can be realized by the selection of suitable surfactants and thickening agents and the setting of a suitable viscosity.

As microcapsules, it is possible to use all surfactant-stable capsules and capsule materials or spheres and spheroidal materials available on the market, such as, for example, Primasphere® (chitosan and agar or carboxymethylcellulose) and Primasponge® (alginate, chitosan, agar) from BASF, Hallcrest Microcapsules® (gelatin, gum arabic) from Hallcrest, Inc. (US), Coletica Thalaspheres® (marine collagen) Company Coletica (FR), Lipotec Millicapseln® (alginic acid, agar-agar) from Lipotec SA (ES), Induchem Unispheres® (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose) and Unicerin® C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose) from Induchem AG (CH), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids) and Softspheres® (modified Agar-agar) from Kobo (US) and Kuhs Probiol Nanospheres (phospholipids) from Kuhs (DE) and others. The microcapsules may have any shape in the production-related framework, but they are preferably egg-shaped or ellipsoidal or in particular approximately spherical. Depending on the active ingredient and application, the diameter along its greatest spatial extent may be between 100 nm (not visually recognizable as a capsule) and 10 mm. The preferred diameter is in the range between 0.1 mm and 7 mm, particularly preferred are microcapsules with a diameter between 0.4 mm and 5 mm. To improve the appearance, dyes, color pigments or pearlescent components can also be added.

The release of the active ingredient from the microcapsules can be done mechanically both by grinding the microcapsules during the cleaning process as well as by breaking up by means of a suitable metering device. Other options are the release of the active ingredient by changing the temperature (introduction into warm rinsing water), by shifting the pH, changing the electrolyte content, etc.

If microcapsules are used, their content is usually from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, in particular from 0.2 to 3% by weight and most preferably from 0.3 to 2% by weight -%, wherein the agent according to the invention can contain only similar microcapsules or mixtures of different types of microcapsules

Polymers and builders

To further improve the drainage and / or drying behavior, the composition according to the invention may comprise one or more additives from the group of polymers and builders (builders), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight -%, in particular 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight.

Builders suitable as additives are, in particular, polyaspartic acid sodium salt, ethylenediaminetriacetate cocoalkylacetamide (Rewopol® CHT 12), methylglycinediacetic acid tri-Na salt (Trilon® ES 9964) and acetophosphonic acid (Turpinal® SL).

viscosity

The preferred viscosity for the composition of the invention is 20 ° C and a shear rate of 30 min ^-1 - measured by a viscometer type Brookfield LV DV II and spindle 31 - in the range of 10 to 5000 mPa s, preferably 50 to 2000 mPa s , in particular 500 to 1500 mPa s, particularly preferably 600 to 1000 mPa s. The viscosity of the composition according to the invention can be increased - in particular with a low surfactant content of the composition - by thickening agents and / or - especially with a high surfactant content of the composition - can be reduced by the water-soluble inorganic salts contained and by solvents.

thickener

For thickening, the composition according to the invention may additionally contain one or more polymeric thickeners

For the purposes of the present invention, polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homo- and copolymerates of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other customary thickening polymers. Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, eg. B. propoxylated guar, and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, may be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g. Hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.

A preferred polymeric thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 * 10 ⁶ and is available, for example, from Kelco under the trade name Keltrol®, eg as a cream-colored powder Keltrol® T (transparent) or as white granules Keltrol® RD (Readily Dispersable). Another preferred polymeric thickening agent is the microbial heteropolysaccharide gellan gum, which is formed under aerobic conditions, for example, from Auromonas elodea and especially from Sphingomonas paucimobilis strains. For example, Gellan Gum can be obtained under the trade name Kelcogel® in various qualities from Kelco

Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI: Carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are i.a. Carbopol® 940 (molecular weight about 4,000,000 g / mol), Carbopol® 941 (molecular weight about 1,250,000 g / mol) or Carbopol® 934 (molecular weight approx 3,000,000 g / mol).

However, particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably those formed with C _1-4 -alkanols, for example the copolymers of methacrylic acid, Butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from the company Dow under the trade names Aculyn® and Acusol®, for example, the anionic non- associative polymers Aculyn® 33 (crosslinked), Acusol® 810 and Acusol® 830 (CAS 25852-37-3), (ii) crosslinked high molecular weight acrylic acid copolymers to which, for example, the copolymers of C ₁₀ crosslinked with an allyl ether of sucrose or of pentaerythritol. ₃₀ alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with C _1-4 alkanols, esters (INCI: acrylates s / C _10-30 alkyl acrylate crosspolymer) and which are obtainable, for example, from the company Lubrizol under the trade name Carbopol®, for example the hydrophobicized Carbopol® ETD2623 and Carbopol® 1382 (INCI Acrylates / C _10-30 alkyl acrylates Crosspolymer) and Carbopol® AQUA 30 (formerly Carbopol® EX 473).

The content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, more preferably between 0.5 and 6% by weight, in particular between 1 and 5% by weight and most preferably between 1, 5 and 4% by weight, for example between 2 and 2.5% by weight.

In a preferred embodiment of the invention, however, the agent is free of polymeric thickeners.

Dicarboxylic acids (salts)

To stabilize the agent according to the invention, in particular at high surfactant content, one or more dicarboxylic acids and / or their salts may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as described e.g. available under the trade name Sokalan® DSC. The use is advantageously carried out in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1.3 to 6% by weight and particularly preferably 2 to 4% by weight.

A change in the dicarboxylic acid (salt) content can - especially in amounts above 2% by weight - contribute to a clear solution of the ingredients. Also, within certain limits, influencing the viscosity of the mixture by this means is possible. Furthermore, this component influences the solubility of the mixture. This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30% by weight. However, if it is possible to dispense with their use, the agent according to the invention is preferably free from dicarboxylic acid (salts).

Other additives

In addition, one or more further customary additives, in particular in hand dishwashing detergents and hard surface cleaners, in particular UV stabilizers, perfume, pearlescing agents (INCI: Opacifying Agents, for example glycol distearate, for example Cutina® AGS from BASF, or this containing mixtures, for example the Euperlane® from BASF, or else styrene-acrylate copolymers, for example Acusol OP 301 or Opulyn 301 from Dow), dyes, corrosion inhibitors, preservatives (for example the technical 2-bromo called Bronopol 2-nitropropane-1,3-diol (CAS 52-51-7), which is commercially available, for example, as Myacide® BT from BASF, organic salts, disinfectants, enzymes and pH adjusters, in quantities of usually no more be contained as 5% by weight.

PH value

The pH of the agent according to the invention can be adjusted by means of customary pH regulators, for example acids, such as mineral acids or citric acid and / or alkalis, such as sodium or potassium hydroxide, with a range of from 4 to 8, preferably 4, especially if the desired hand tolerance is desired. 5 to 7, especially 5 to 6, is preferred.

For adjusting and / or stabilizing the pH, the composition according to the invention may contain one or more buffer substances, usually in amounts of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, in particular 0.01 to 2% by weight. , particularly preferably 0.05 to 1% by weight, most preferably 0.1 to 0.5% by weight, for example 0.2% by weight. Preference is given to buffer substances which at the same time complexing agent or even chelating agents are. Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate 2 * H ₂ O and tripotassium citrate H ₂ O.

manufacturing

The composition according to the invention can be prepared by stirring the individual components together in any order. The order of attachment is not critical to the preparation of the agent. Preferably, in this case water, surfactants, active ingredients and optionally further of the aforementioned ingredients are stirred together. If perfume and / or dye are used, then their addition to the resulting solution. Subsequently, the pH is adjusted as described above.

use

The composition according to the invention can be used for cleaning hard surfaces, in particular for manual cleaning of dishes. For use, the agent according to the invention can be metered from a commercially available bottle for washing. In addition, the composition according to the invention can also be applied in the form of a foam either directly on the surface to be cleaned or on a sponge, a cloth, a brush or another, optionally moistened, cleaning aid. For foam generation is particularly suitable a manually activated foam dispenser, in particular selected from the group comprising aerosol spray dispenser, even pressure-building spray dispenser, pump spray dispenser and trigger spray dispensers, in particular pump foam dispenser, as for example from the company Airspray, the company Taplast, the company Keltec or the Daiwa Can Company. In addition to trigger bottles, pump spray dispensers and trigger spray dispensers with a polyethylene, polypropylene or polyethylene terephthalate container are also suitable. Such trigger bottles are offered for example by the company Afa-Polytec. The spray head is preferably equipped with a foam nozzle. In addition, the agent may also be filled with the addition of a suitable propellant (eg n-butane, a propane / butane mixture, carbon dioxide, nitrogen or a CO ₂ / N ₂ mixture) into a corresponding aerosol spray bottle. However, such a spray dispenser is less preferred. If the agent is to be dosed as a foam, it is necessary in any case to set a suitable viscosity so that the agent can be conveyed through the spray dispenser.

All embodiments described herein for the agents are also applicable to the methods and uses according to the invention and vice versa. The following examples are illustrative of the invention without being limited thereto.

EXAMPLES

Example 1: Composition

Table 1 components example 1 Comparative Example 1 Anionic surfactant SLES * 7.14 7.14 Amphoteric surfactant betaine 2.86 2.86 potassium sorbate 0.2 / 2-phenoxyethanol 0.9 / Acticide MBR (MIT / BIT) / 0.1 pearlizing 0.1 0.1 citric acid 0,035 0,035 sodium chloride 1.17 1.17 Perfume 0.18 0.18 water to 100% by weight to 100% by weight All% data are based on wt .-% of active substance, wherein water is made up to 100 wt .-%. The pH of these compositions is 5.5. * SLES = sodium lauryl ether sulfate.

The storage stability was determined in a so-called challenge test (Preservative Challenge Test). In this case, the product sample to be examined for its microbiological stability is inoculated with defined organisms and a count of the living microorganisms is carried out at defined time intervals. The defined organisms are those standard bacteria (bacteria and fungi) that are used according to various international standards, as well as additional strains that are relevant in the context of microbiologically sensitive products. The compatibility of the different strains with each other had already been confirmed in earlier investigations. The mixture of bacteria and fungi is added to the product sample and then the germ reduction is determined over time. For this purpose, the germ count in the product sample, for example, 0, 7, 14, 21 and 28 days, if necessary, also checked 35 days after inoculation. A reduction in the number of germs by four to five log ₁₀ levels is sought.

Both the example and the comparative example showed comparably good values in the challenge test after storage. The example shows that compositions according to the invention have similar good stabilizing properties, in particular storage stability, as systems containing isothiazolinone-based preservatives.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2008/046778 A1 [0025, 0032, 0037, 0041, 0049, 0064]

Claims (11)

Liquid aqueous cleaning agent comprising: a) at least one surfactant; b) at least one salt of sorbic acid or mixtures thereof; c) at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropan-2-ol, 3-phenoxypropane-1,2-diol, benzyloxymethanol or mixtures thereof; d) optionally additives; and e) water, which is added to 100 wt .-%, wherein the sum of a) to e) 100 wt .-% results. Liquid aqueous cleaning agent according to Claim 1 wherein the at least one surfactant comprises a) anionic and / or amphoteric surfactants. Liquid aqueous cleaning agent according to Claim 2 wherein the at least one surfactant a) comprises at least one amphoteric surfactant selected from betaines, sulfobetaines or a mixture thereof. Liquid aqueous cleaning agent according to Claim 2 or 3 in which the at least one surfactant comprises a) at least one anionic surfactant selected from alkyl ether sulfates, secondary alkanesulfonates, fatty alcohol sulfates, monoglyceride sulfates, ester sulfonates, ligninsulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates, fatty acid sarcosinates, ether carboxylic acids, alkyl (ether) phosphates and gemini Surfactants or a mixture thereof, preferably an alkyl ether sulfate, more preferably sodium lauryl ether sulfate. Liquid aqueous cleaning agent according to any one of Claims 1 to 4 in which at least one salt of sorbic acid is selected from sodium sorbate, potassium sorbate, calcium sorbate or mixtures thereof, preferably potassium sorbate. Liquid aqueous cleaning agent according to any one of Claims 1 to 5 wherein the at least one compound c) comprises 2-phenoxyethanol. Liquid aqueous cleaning agent according to any one of Claims 1 to 6 wherein the at least one additive d) is selected from perfumes, perfumes, water-soluble salts, acids, pearlescers, enzymes, corrosion inhibitors, pH adjusters or mixtures thereof. Liquid aqueous cleaning agent according to any one of Claims 1 to 7 wherein 3 to 50 wt%, preferably 5 to 35 wt%, more preferably 7 to 15 wt% a); 0.01 to 1.0 wt%, preferably 0.05 to 0.75 wt%, more preferably 0.1 to 0.5 wt% b); 0.05 to 3 wt%, preferably 0.1 to 2.5 wt%, more preferably 0.2 to 1.5 wt% c); 0 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 2.5 to 5% by weight of d); and e) adding water to 100% by weight, wherein the weight% relates to the total weight of the liquid aqueous cleaning agent. Liquid aqueous cleaning agent according to any one of Claims 1 to 8th wherein the pH of the liquid aqueous cleaning agent is 4 to 8, preferably 4.5 to 7, more preferably 5 to 6. Process for the preparation of a liquid aqueous cleaning agent according to one of the Claims 1 to 9 comprising the steps of: i) mixing components a), b), c), e) and optionally d); and ii) adjusting the desired pH by adding pH adjusters and optionally buffering agents. Using a mixture of at least one salt of sorbic acid or mixtures thereof; and at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropan-2-ol, 3-phenoxypropane-1,2-diol, benzyloxymethanol or mixtures thereof, for increasing the storage stability of liquid aqueous cleaning agents.