WO2015078743A1

WO2015078743A1 - Longer-lasting hand dishwashing detergent

Info

Publication number: WO2015078743A1
Application number: PCT/EP2014/075010
Authority: WO
Inventors: Detlef Buisker; Ulrich Pegelow
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2013-11-28
Filing date: 2014-11-19
Publication date: 2015-06-04
Also published as: DE102013224454A1

Abstract

A surfactant-containing and salt-containing cleaning agent for hard surfaces in which the salt/surfactant concentration ratio ranges from 0.001 to 0.8 lasts longer during the use thereof.

Description

Hand dishwashing detergent with improved range

The present invention relates to a liquid detergent, especially an aqueous detergent for hard surfaces. The cleaning agent is preferably used for manual dishwashing.

Liquid aqueous hand dishwashing detergents are used in countless households. In the usual manual application, they are diluted in water and in the thus prepared aqueous solution, the soiled dishes by means of an auxiliary agent (usually a sponge or cloth) is cleaned by mechanical force. However, such hand dishwashing detergents have only a limited range, since they are usually quickly rinsed out of the cloth or sponge. The amount of soiled surface that can be cleaned with a certain amount of hand dishwashing detergent is thus severely limited. Extending the range of liquid hand dishwashing detergents is the goal of more diverse

Developments in this field of technology.

Thus, an improvement in the range of a hand detergent in the sponge, for example, be achieved by an increased surfactant concentration in the detergent. This approach is disadvantageous not least because of the associated higher costs. In addition, higher surfactant concentrations are an additional burden on the environment.

In an alternative approach, larger amounts of salts are used. A disadvantage of higher salt amounts, however, is the associated higher viscosity of the cleaning agent and its tendency to opacification and possibly phase separation.

The invention is therefore based on the object to provide a liquid detergent, especially for hard surfaces, which has an improved range, and in which at least one disadvantage of the prior art is at least reduced.

It has surprisingly been found that this object is achieved by a liquid cleaning agent comprising at least one surfactant and a salt, wherein the salt is present in an amount of from 0.01 to 1.3% by weight (in each case inclusive) and the agent has a salt Surfactant index (ST index) from 0.001 to 0.8. The ST index is the ratio between the salt concentration in the detergent and the surfactant concentration in the detergent. This is the undiluted cleaning agent.

The use of such a low salt concentration leads to an increase in the viscosity of the detergent diluted with water. The increase in viscosity increases the shelf life of the product in the cloth or sponge, thus achieving the desired increase in reach. The durability of the cleaning agent (or so-called "sponge load") can be used as a relative proportion of the surfactant remaining in the sponge to that originally applied to the sponge

Amount of surfactant are detected. One methodology for determining durability is in WO

2010/097316 A1. Preferably, the durability of the invention

Detergent according to this test at least 50%, preferably at least 60%, most preferably at 75%.

The improved range of the cleaning agent according to the invention can also be expressed by the so-called. Teller index. This is the ratio between the number of plates and the amount of surfactant required to clean these plates. The TK index of the cleaning agents according to the invention is advantageously between 1 and 8, preferably between 2 and 5, very particularly between 3 and 5.

Further advantages of the cleaning agents according to the invention are that the product itself, ie in the undiluted form, retains a low viscosity. This is preferably from 10 to 10000 mPa.s, more preferably from 600 to 6000 mPa.s, most preferably from 1000 to 5000 mPa.s (Brookfield LV DV II, spindle 25, 20 ° C., shear rate 30 min ^-1 ). , Furthermore, the cleaning agents according to the invention show a good cold turbidity behavior with at the same time transparent aesthetics.

In an advantageous embodiment, the salt content is from 0.1 to 1.1% by weight, preferably from 0.1 to 0.8% by weight, in particular from 0.1 to 0.5% by weight (in each case based on the cleaning agent ).

In a preferred embodiment of the invention, the ST index is in the range of 0.01 to 0.5, more preferably in the range of 0.01 to 0.06.

Salts which can be used according to the invention are, in particular, water-soluble salts, especially inorganic salts, which are preferably selected from the group comprising colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or the transition metals and mixtures thereof, particularly preferably from the group of

Halides and sulfates of the alkali metals and mixtures thereof, in particular from the group of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof. Particularly preferred is sodium chloride.

Likewise, water-soluble organic salts can be used according to the invention, namely, for example, formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and

Mixtures thereof. For the purposes of the present invention, liquid cleaning agents are understood as meaning those which are flowable under normal conditions of use and whose viscosities can vary within a wide range. The liquid preparations also include gelatinous or pasty agents, which may optionally have additional thickening agents known from the prior art. In a further preferred embodiment of the invention, the liquid agents are based on water. In particular, the cleaning agents according to the invention are hand dishwashing detergents.

A hand dishwashing detergent (synonym: manual dishwashing detergent) in the context of the present invention is a liquid detergent or cleaning agent particularly adapted for use in manual dishwashing. Hand dishwashing detergents are therefore particularly suitable for removing dirt from hard surfaces, have a good

Foaming power and also a special skin compatibility.

Advantageously, the detergent according to the present invention is preferably designed as a hand dishwashing detergent, which has a foaming capacity of at least 250 mL, measured according to the DIN method 53 902, Part 2 (Ross-Miles test), preferably of at least 300 mL. This advantageous foaming behavior is typically due to the fact that the hand dishwashing detergent preferably contains at least 5% by weight of an anionic surfactant, based on the total hand dishwashing detergent. The total content of surfactant may, however, be significantly higher (see below).

To ensure good skin compatibility, the pH value is one

Hand dishwashing detergent preferably in the range of (inclusive) 4 to 9. Preferred are pH values between pH 5 and pH 8.5 (inclusive), most preferred is a pH of 5.5 to 8.0 (inclusive). Also, hand dishwashing detergents preferably do not contain bleaching agents, e.g. Sodium percarbonate and sodium borate. The

Skin compatibility can be assessed as irritation potential according to OECD method no. 404 determine. It is preferably at most 65%.

The cleaning agents according to the invention usually contain as further constituents surfactants, especially anionic surfactants, nonionic surfactants, amphoteric surfactants, betaines and optionally cationic surfactants. The total amount of the surfactants in the compositions according to the invention can vary within a broad range and, for example, be from 5 to 70% by weight, preferably from 10 to 55% by weight and in particular from 15 to 50% by weight.

The anionic surfactants are usually in situ as alkali metal, alkaline earth metal and / or mono-, di- or Trialkanolammoniumsalz and / or in the form of their with the corresponding alkali metal hydroxide, alkaline earth metal hydroxide and / or mono-, di- or trialkanolamine neutralizing corresponding acid used. Preference is given here as alkali metals potassium and especially sodium, as alkaline earth metals calcium and magnesium in particular, and as alkanolamines mono-, di- or triethanolamine. Particularly preferred are the

Sodium salts. Even if in manual dishwashing detergents anionic surfactants in the form of their

Calcium salts are used according to the invention, the agents additionally contain calcium lactate, preferably in the amounts indicated above.

Particularly preferred anionic surfactants used in manual dishwashing detergents include alkyl ether sulfates and alkyl sulfonates.

Alkyl ether sulfates (fatty alcohol ether sulfates, INCI alkyl ether sulfates) are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally means, 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 mono- or poly-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 lower ethoxylated

Fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 2 EO, such as Na-Ci2-i4-fatty alcohol + 2EO sulfate.

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 1 1 to 18 and more preferably 14 to 17

Carbon atoms on.

Accordingly, suitable alkyl sulfonates are the saturated alkanesulfonates, the unsaturated olefin esters 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 sulfonate groups bonded to the polyether chain are used. Function and internal ether sulfonates (i-ether sulfonates) with the alkyl-linked sulfonate function distinguishes.

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 C 13-7 alkanesulfonate (INCI Sodium C14-17 alkyl lake sulfonates). A preferred manual dishwashing detergent contains one or more secondary alkyl sulfonates in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, especially 4 to 8% by weight.

Further possible anionic surfactants which can be used are known to the person skilled in the art from the relevant prior art for detergents or cleaners. These include in particular 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.

Suitable further anionic surfactants are anionic gemini surfactants with a di- phenyl oxide base structure 2 sulfonate groups and an alkyl group on one or both benzene rings of the formula O3S (C6H3R) 0 (C6H3R ') S03 ^~, with in which R is an alkyl radical for example 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax® Dry

Hydrotrope powder with Ci6-alkyl radical (s); INCI Sodium Hexyldiphenyl Ether Sulfonate, Disodium Decyl Phenyl Ether Disulfonate, Disodium Lauryl Phenyl Ether Disulfonate, Disodium Cetyl Phenyl Ether Disulfonate).

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 mono- 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

Trialkanolammoniumsalze, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, more preferably sodium 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

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 with a

Degree of alkoxylation from 1 to 20, preferably 1 to 15, in particular 1 to 10, particularly 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 Sulfobernsteinsäurelaurylpolyglykolester-di-sodium salt (EO lauryl sulfosuccinate, disodium salt; INCI Disodium Laureth Sulfosuccinate), for example, as Tego ^® sulfosuccinate F 30

(Goldschmidt) having a sulfosuccinate content of 30% by weight is commercially available.

In the sulfosuccinamates or sulfosuccinamides form or form both carboxyl groups of sulfosuccinic 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, especially 8 to 18, more preferably 10 to 16, most preferably 12 to 14

Carbon atoms, 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.

Also suitable are, for example, the following sulfosuccinates and sulfosuccinamates designated according to INCI, which are described in more detail in the International Cosmetic Ingredient Dictionary and Handbook: Ammonium Dinonyl Sulfosuccinates, Ammonium Lauryl Sulfosuccinates, Diamonium Dimethicone Copolyol Sulfosuccinates, Diammonium Lauramido-MEA Sulfosuccinates, Diammonium Lauryl Sulfosuccinates, Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Dioctyl Sodium Sulfosuccinate, Disodium Cetearyl Sulfosuccinate, Disodium Cocamido MEA Sulfo-succinate, Disodium Cocamido MIPA Sulfosuccinates, disodium cocamido PEG-3

Sulfosuccinates, disodium coco-glucosides sulfosuccinates, disodium cocoyl butyl gluceth-10 sulfosuccinates, disodium C12-15 pareth sulfosuccinates, disodium deceth-5 sulfosuccinates, disodium deceth-6 sulfosuccinates, disodium dihydroxyethyl sulfosuccinyl undecylenates, disodium dimethicone copolyol sulfosuccinates, disodium hydrogenated cottonseed glycerides sulfosuccinates, Disodium isodecyl sulfosuccinate, disodium isostearamido MEA sulfosuccinate, disodium isostearamido MIPA sulfosuccinate, disodium isostearyl sulfosuccinate, disodium laneth-5 sulfosuccinate, disodium lauramido MEA sulfosuccinate, disodium lauramido PEG-2 sulfosuccinate, disodium lauramido PEG-5 sulfosuccinate, disodium laureth-6 Sulfosuccinates, disodium laureth-9 sulfosuccinates, disodium laureth-12 sulfosuccinates, disodium lauryl sulfosuccinates, disodium myristamido MEA sulfosuccinates, disodium nonoxynol-10 sulfosuccinates, disodium oleamido MEA sulfosuccinates, disodium oleamido MIPA sulfosuccinates, disodium oleamido PEG-2 Su lfosuccinate, disodium oleth-3 sulfosuccinate, disodium oleyl sulfosuccinate, disodium palmitamido PEG-2 sulfosuccinate, disodium palmitoleeamido PEG-2 sulfosuccinate, disodium PEG-4 cocamido MIPA sulfo-succinate, disodium PEG-5 lauryl citrate sulfosuccinate, disodium PEG-8 palm glycerides Sulfosuccinates, disodium ricinoleamido MEA sulfosuccinates, disodium sitostereth-14 sulfosuccinates, disodium stearamido MEA sulfosuccinates, disodium stearyl sulfosuccinamates, disodium stearyl sulfosuccinates, disodium tallamido MEA sulfosuccinates, disodium tallowamido MEA sulfo-succinates, disodium tallow sulfosuccinamates, disodium tridecyl sulfosuccinates , Disodium undecylenamido MEA sulfosuccinates, Disodium Undecylenamido PEG-2 Sulfosuccinate, Disodium Wheat Germamido MEA Sulphosuccinate, Disodium Wheat Germamido PEG-2 Sulfosuccinate, Di-TEA-Oleamido PEG-2 Sulfosuccinate, Ditridecyl Sodium Sulfosuccinate, Sodium Bisglycol Ricinosulfosuccinate, Sodium / - MEA Laureth-2 Sulfosuccinate and tetrasodium dicarboxyethyl stearyl sulfosuccinamate. Yet another suitable sulfosuccinamate is disodium C 16-18 alkoxypropylene sulfosuccinamate.

Preferred anionic sulfosuccinic are imidosuccinate, mono-Na-sulfosuccinic acid diisobutyl ester (Monawet MB ^® 45), mono-Na-sulfosuccinic acid di-octyl ester (Monawet MO-84 ^® R2W, Rewopol SB ^® DO 75), mono- Na-sulfosuccinic acid di-tridecyl (Monawet ^® MT 70) Fettalkoholpolyglykolsulfosuccinat-Na-NH ₄ salt (sulfosuccinate S-2), di-sodium sulfosuccinic acid mono-Ci2 / i4-3EO ester (Texapon ^® SB -3), Natruimsulfobernsteinsäurediiso- octyl (Texin DOS 75 ^®) and di-Na-sulfosuccinic mono-Ci2 / i8-ester (Texin 128-P ^®), in particular with the inventive ternary surfactant with respect to the drain and / or drying behavior synergistically cooperating mono-Na-sulfosuccinic di-octyl esters.

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 wt .-%, in particular 0, 1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 part by weight. %.

In a preferred embodiment of the present invention, the proportion of anionic surfactant 5 to 20 wt .-%, particularly preferably 8 to 16 wt .-%, based on the total weight of the detergent, in particular the hand dishwashing detergent. In a particularly preferred embodiment, the cleaning agent according to the invention contains 12% by weight of anionic surfactant. Preferably, the anionic surfactant is a

Fatty alcohol ether. Preferred fatty alcohol ether sulfates are described above.

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.

Suitable betaines which are mainly used in manual dishwashing detergents are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy formula I,

R - [CO-X- (CH 2) n] x N ⁺ (R ² ) (R ³ ) - (CH ₂ ) m - [CH (OH) -CH ₂ ] y Y- (I) a saturated or unsaturated C6-22-alkyl radical, preferably Cs -is-alkyl radical, in particular a saturated Cio-16-alkyl radical, for example a saturated one

Ci2-14 radical,

NH, NR ⁴ with the Ci- ₄ alkyl R ^4, O or S,

a number from 1 to 10, preferably 2 to 5, in particular 3,

0 or 1, preferably 1,

independently of one another a C 1-4 -alkyl radical, optionally hydroxy-substituted, such as e.g. a hydroxyethyl radical, but especially a methyl radical,

a number from 1 to 4, in particular 1, 2 or 3,

0 or 1 and

COO, SOs, OPO (OR ⁵ ) 0 or P (0) (OR ⁵ ) 0, wherein R ^{5 is} a hydrogen atom H or a d ^ -alkyl radical.

The alkyl and alkyl amido betaines of the formula I with 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 -N ⁺ (CH ₃₎ 2 CH ₂ COO- (la) R -CO-NH- (CH 2) 3 N ⁺ (CH ₃₎ 2 CH ₂ COO- (Ib) R -N ⁺ (CH3) 2-CH ₂ CH (OH) CH ₂ S03- (Ic) R -CO-NH- (CH ₂₎ 3 N ⁺ (CH 3) 2 CH 2 CH (OH) CH ₂ S03- (Id) in which R has the same Meaning as in formula I has.

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 the following named according to INCI

Compounds: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, Betaine, Canolamidopropyl Betaine, Caprylic / Capramidopropyl Betaine, Carnitine, Cetyl Betaine, Cocamido Betaine, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco Betaine, Coco-Hydroxy-sultaine, Coco / Oleamidopropyl Betaine, Coco-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine , Isopropylamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysultaine, Oleyl Betaine, Olivamidopropyl Betaine, Palmamidopropyl Betaine,

Palmitamidopropyl Betaine, Palmitoyl Carnitine, Palm Kernel Amidopropyl Betaine, Polytetra- fluoroethylenes acetoxypropyl betaines, ricinoleamidopropyl betaines, sesamidopropyl betaines, soyamidopropyl betaines, stearamidopropyl betaines, stearyl betaines, tallowamidopropyl betaines, tallowamidopropyl hydroxysultaines, tallow betaines, tallow dihydroxyethyl betaines, undecylenamidopropyl betaines and wheat germamidopropyl betaines. A preferred betaine is, for example, cocamidopropyl betaine (cocoamidopropylbetaine).

The alkylamidoalkylamines (INCI alkylamido alkylamines) are amphoteric surfactants of the formula (III)

R9_ -NR ¹⁰ _CO - (CH2) iN (R) - (CH2CH2O) j- (CH2) k- [CH (OH)] _l -CH 2 Z-OM (III) in which R is a saturated or unsaturated ^C6-9 22-alkyl radical, preferably Cs -is-alkyl radical, in particular a saturated Cio-16-alkyl radical, for example a saturated

Ci2-14 radical,

R ^{0 is} a hydrogen atom H or a C 1-6 -alkyl radical, preferably H,

i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,

R is a hydrogen atom H or CH 2 COOM (to M s.u.),

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, SO2, OPO (OR ¹² ) or P (0) (OR ¹² ), where R ^{2 is} a

or M (see below), and

M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine.

Preferred representatives satisfy the formulas IIIa to IIId,

R9_cO-NH- (CH ₂₎ ₂ -N (R) -CH2CH20-CH2-COOM (IIIa)

R9_cO-NH- (CH ₂₎ ₂ -N (R) -CH2CH20-CH2CH2-COOM (IIIb)

R9_cO-NH- (CH ₂₎ ₂ -N (R) -CH2CH20-CH 2 CH (OH) CH2-S03M (IIIc)

R ^{9 is} -CO-NH- (CH ₂ ) ₂ -N (R) -CH ₂ CH ₂ O -CH ₂ CH (OH) CH ₂ -O-OP 3 HM (IIId) in which R and M have the same meaning as in formula (III).

Exemplary alkylamido alkylamines are the following compounds named according to INCI: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Caprylo- amphodiacetates, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhy- droxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate , Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphoacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloampho- acetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryloamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoam- phopropionate, Sodium lauroamphoacetate, sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoam- phacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium pionate Tallamphopro-, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Amphopropionate Undecyleno-, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride Phosphate.

Preferred alkyl-substituted amino acids (INCI alkyl-substituted amino acids) according to the invention are monoalkyl-substituted amino acids according to formula (IV),

R ³ -NH-CH (R ⁴ HCH ₂ ) u-COOM '(IV) in the R ^{3 is} a saturated or unsaturated C6-22-alkyl radical, preferably Cs-is-alkyl radical, in particular a saturated Cio-16-alkyl radical, for example a saturated one

Ci2-14 radical,

R ^{4 is} a hydrogen atom H or a d ^ -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, e.g. protonated mono-, di- or triethanolamine, is alkyl-substituted imino acids according to formula (V),

R ⁵ -N - [(CH ₂ ) v -COOM "] ₂ (V) in the R ^{5 is} a saturated or unsaturated C 6-22-alkyl radical, preferably Cs-is-alkyl radical, in particular a saturated Cio-16-alkyl radical, for example a saturated one

Ci2-14 radical,

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 different meanings, e.g. Is hydrogen and sodium or twice sodium, and mono- or dialkyl-substituted natural amino acids according to formula (VI),

R ⁶ -N (R ⁷ ) -CH (R ⁸ ) -COOM "'(VI) in the R ^{6 is} a saturated or unsaturated C6-22-alkyl radical, preferably Cs-is-alkyl radical, in particular a saturated Cio-16-alkyl radical, for example a saturated

Ci2-14 radical,

R ^{7 is} a hydrogen atom or a C 1-4 -alkyl radical, optionally hydroxyl- or amine-substituted, eg a methyl, ethyl, hydroxyethyl or aminopropyl radical,

R ^{8 is} the residue of one of the 20 natural amino acids H ₂ NCH (R ⁸ ) 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 ³ -NH-CH ₂ CH ₂ COOM '(IVa) in which R ³ and M' have the same meaning as in formula (IV).

Illustrative alkyl substituted amino acids are the following INCI compounds: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Copropylediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycines, myristaminopropionic acid, sodium C12-15 alkoxypropyl iminodipropionates, sodium cocaminopropionates, sodium lauraminopropionates, sodium lauriminodipropionates, sodium lauroyl methylaminopropionates, TEA lauraminopropionates, and TEA myristaminopropionates.

Acylated amino acids are amino acids, in particular the 20 natural α-amino acids which carry on the amino nitrogen the acyl radical R ⁹ CO of a saturated or unsaturated fatty acid R ⁹ COOH, where R ^{9 is} a saturated or unsaturated C 6-22 -alkyl radical, preferably Cs-is-alkyl radical , in particular a saturated Cio-16-alkyl radical, for example a saturated C 12-14 -alkyl radical. The acylated amino acids may also be used as alkali metal salt, alkaline earth metal salt or

Alkanolammonium salt, e.g. Mono-, di- or Triethanolammoniumsalz be used.

Exemplary acylated amino acids are the acyl derivatives grouped according to INCI under Amino Acids, e.g. Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine or Myristoyl Methylalanine.

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. Further, the amphoteric surfactants preferably contains at least one amphoteric surfactant is selected from the group comprising Natriumcarboxyethylkokosphosphoethylimidazolin (Phosphoteric ^® TC- 6) C8 / io amidopropyl betaine (INCI caprylic / Capramidopropyl Betaine, Betaine Tego ^® 810), N-2-hydroxyethyl-N-carboxymethyl fettsäureamido-ethylamine-Na (Rewoteric ^® AMV) and N- caprylic / capric amidoethyl-N-ethyl-propionate-Na (Rewoteric AMVSF ^®) and the betaine 3- (3-cocoamido-propyl) dimethylammonium-2-hydroxypropane ( INCI sultaines; Rewoteric AM CAS ^®) and the Alkylamidoalkylamin N- [N '(N "-2-hydroxyethyl-N" -carboxyethylaminoethyl) - essigsäureamido] -N, N-dimethyl-N-coco-ammonium betaine (Rewoteric QAM ^® 50) , in particular together with cocoamidopropylbetaine.

In a preferred embodiment, the composition according to the invention comprises one or more amphoteric surfactants, in particular betaines, in an amount of from 0.5 to 15% by weight, preferably from 1 to 10% by weight, in particular from 2 to 8% by weight. In a most preferred embodiment, the agent contains 4% by weight of amphoteric surfactants (especially betaine). Preferred betaines have been described above. A most preferred betaine is cocoamidopropyl betaine.

In a preferred embodiment, the agent according to the invention comprises at least one anionic surfactant and at least one amphoteric surfactant, these surfactants preferably being present in a mass ratio of 10: 1 to 1: 5, preferably 5: 1 to 2: 1, more preferably 4: 1 ,

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols, for example C 12-14 alcohols containing 3 EO, 7 EO or 4 EO, C ₉ include n-alcohol with 7 EO, Cis-is alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci2-is alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as

Mixtures of Ci2-i4-alcohol with 3 EO and Ci2-is-alcohol with 7 EO. The specified

Levels of ethoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Especially The hand dishwashing detergent preferably contains a C 12-18 fatty alcohol with 7 EO or a C 13-15 oxo alcohol with 7 EO as nonionic surfactant.

In a further preferred embodiment of the liquid cleaning agent, in particular of the hand dishwashing detergent, a nonionic surfactant, preferably a fatty alcohol polyglycol ether, is preferably present as further surfactant, preferably in amounts of 0.001 to 10% by weight, particularly preferably 0.01 to 6% by weight. , more preferably 0, 1 to 4 wt .-%, in particular 0.2 to 2 wt .-%, in each case based on the entire hand dishwashing detergent.

These nonionic surfactants are good in combination with an amine oxide

Cleaning performance on fat-contaminated hard surfaces, such as crockery, on.

Nonionic surfactants in the context of the invention are alkoxylates, but also alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and

Fatty acid. 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.

The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyl dimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy formula II,

_R6R 7 _R 8 _{N +} _Q-

(II)

R6_ [C0-NH (CH ₂₎ w] z N ⁺ (R ⁷⁾ (R ⁸⁾ -0- (II) in which R ⁶ is a saturated or unsaturated C 6-22 alkyl radical, preferably Cs -is-alkyl radical, ^'special a saturated Cio-16-alkyl radical, for example a saturated

C 12-14 -alkyl radical which is bonded to the nitrogen atom N in the alkylamidoamine oxides via a carbonylamidoalkylene group -CO-NH- (CH 2) z- and in the alkoxyalkylamine oxides via an oxalkylene group -O- (CH 2) z -, where each z is a number from 1 to 10, preferably 2 to 5, in particular 3, R ⁷ , R ⁸ independently of one another Ci-4-alkyl radical, optionally hydroxy-substituted such as a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are the following compounds named according to INCI:

Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidines Oxide, Dihydroxyethyl C8-10 Alkoxypropylamine Oxide, Dihydroxyethyl C9-1 1 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 alkoxypropylamines oxides, dihydroxyethyl cocamines oxides, dihydroxyethyl lauramines Oxides, Dihydroxyethyl Stearamines Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C12-15 Alkoxypropylamine Oxide, Isostearamidopropylamine Oxide, Isostearamidopropyl Morpholine Oxide, Lauramidopropylamine Oxide, Lauramine Oxide, Methyl Morpholine Oxide, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxides, myristamidopropylamine oxides, myristamine oxides, myristyl / cetyl amine oxides, oleamidopropylamine oxides, oleamine oxides, olivamidopropylamine oxides, palmitamidopropylamine oxides, palmitamines oxides, peg-3 lauramine oxides, potassium dihydroxyethyl cocamine oxides phosphates, potassium trisphosphonomethylamine oxides, sesamidopropylamine oxides, soyamidopropylamine oxides , Stearamidopropylamine oxides, stearamine oxides, tallowamidopropylamine oxides, tallowamine oxides,

Undecylenamidopropylamine oxides and Wheat germamidopropylamine oxides. Preferred amine oxides are, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide), but also N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-dihydroxyethylamine oxide,

Myristylcetyldimethylamine oxide or lauryldimethylamine oxide.

The content of amine oxide in the agent according to the invention is preferably 1 to 15% by weight and preferably 2 to 10% by weight, in each case based on the total agent.

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-22 alcohols or glycols such as ethylene and / or propylene glycol, where the sugar hydroxy group also comprises polyethylene glycol. and or

Polypropylene glycol can carry. The esters are the reaction products of one or more, preferably one, sugar hydroxy group with a carboxylic acid, in particular a C6-22 fatty acid.

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 Ci-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 residue ie a mono saccharide residue, stand. Particularly preferred sugar amides are the amides of glucose, the glucamides, for example lauroyl-methyl-glucamide.

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 for the middle one

Alkoxylierungsgrad from 0 to 20 are. In this case, the group (AO) _{a may} also contain different alkyleneoxy, for example ethyleneoxy or propyleneoxy, where it is at a to the average Gesamtalkoxylierungsgrad, ie the sum of ethoxylation and

Propoxylierungsgrad, acts. Unless otherwise stated below, the alkyl radicals R 'of the APG are linear unsaturated radicals having the stated 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), i. the distribution of mono- 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 can assume the values x = 1 to 6, the value x is for a specific alkyl glycoside an analytically determined arithmetical variable, which usually represents 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 are obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelene'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. Also to be mentioned are elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.

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] is a glycosidically linked sugar moiety, preferably glucose residue, and x is a number from 1 to 10, preferably 1, 1 to 3, in particular 1, 2 to 1, 6.

Correspondingly preferred alkylpolyglycosides are, for example, cocoa- and C 12-14 -alkylpolyglucoside having a DP degree of 1, 4 or 1.5, in particular cocoalkyl-1, 5-glucoside and C 12-14 -alkyl -1, 4-glucoside.

The composition according to the invention may additionally contain one or more cationic surfactants (cation 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 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 wt .-%.

Preferred cationic surfactants are the quaternary surface-active compounds, in particular with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary

Surface-active compounds with antimicrobial effect, the agent can be designed with an antimicrobial effect or its possibly existing due to other ingredients already existing antimicrobial effect can be improved.

Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV, INCI Quaternary Ammonium Compounds) according to the general formula (R ^l ) (R ") (R ^m ) (R ^lv ) N ⁺ X ^" , in which R 'to R ^{IV are the} same or various Ci-22-alkyl radicals, C7-28 aralkyl radicals or heterocyclic radicals, wherein 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

Imidazolinium compound, 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 are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced. 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 QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyldimethyl-C 12 -alkylammonium chloride, CAS no. 58390-78-6), benzoxonium chloride (benzyldodecyl-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] benzylammonium chloride, CAS no. 121-54-0), dialkyldimethylammonium chlorides 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 QACs are the benzalkonium chlorides having Cs-ds-alkyl radicals, in particular C 12 -C 14 -alkyl-benzyldimethylammonium chloride. A particularly preferred QAV is the Kokospentaethoxy- methylammonium methosulfate (INCI PEG-5 Cocomonium Methosulfate, Rewoquat ^® CPEM).

In order to avoid possible incompatibilities of the cationic surfactants with the anionic surfactants, it is possible to use anionic surfactant-compatible and / or as little as cationic surfactant or, in a particular embodiment of the invention, to dispense entirely with cationic surfactants.

Advantageously, in one embodiment of the invention in the agent according to the invention, no builder substances are present which have calcium-precipitating properties.

Accordingly, an agent is preferred which contains in particular no carbonate-containing salts.

On the other hand, the use of other builder substances, preferably water-soluble builder substances, may be advantageous.

Organic builder substances which may be present in hand dishwashing detergents are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids,

Nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as

Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

However, preference is given to soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol in the liquid

Hand dishwashing detergents used.

The water content of the preferred liquid and aqueous hand dishwashing detergent is usually from 15 to 90% by weight, preferably from 20 to 85% by weight, in particular from 30 to 80% by weight. The composition of the invention may additionally contain one or more water-soluble organic solvents, usually in an amount of 0.1 to 30 wt .-%, preferably 1 to 20 wt .-%, in particular 2 to 15 wt .-%, particularly preferably 3 to 12 wt .-%, most preferably 4 to 8 wt .-%.

The solvent is used in the context of the teaching of the invention as needed in particular as a hydrotrope, viscosity regulator and / or additional cold stabilizer. It acts solubilizing in particular 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.

A particularly preferred and with respect to the stabilization of the enzymatic

Hand dishwashing detergent particularly effective organic solvent is the glycerol and the 1, 2-propylene glycol.

With regard to the manual application of the agents according to the invention, however, the use of organic solvents is dispensed with in a preferred embodiment.

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.

In addition to the components mentioned so far, the compositions according to the invention may contain further ingredients. These include, for example, other surfactants, additives for improving the flow 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 (INCI Opacifying Agents, such as glycol distearate, eg Cutina ^® AGS of the Fa. Cognis, or mixtures comprising, for example, the Euperlane ^® from. Cognis), dyes, corrosion inhibitors, preservatives (for example, the technical also known as Bronopol 2-bromo-2-nitropropane-1, 3-diol (CAS 52-51- 7), for example, as Myacide ^® BT or as

Boots Bronopol BT of the company Boots), organic salts,

Disinfectants, enzymes, pH adjusters and skin feel-improving or nourishing additives (eg dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein Partial hydrolyzates, protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes), which may be contained in amounts of usually not more than 5 wt .-%.

To further improve the running and / or drying behavior, the agent according to the invention may contain one or more additives from the group of surfactants, polymers and builders (builders), usually in an amount of 0.001 to 5% by weight, preferably 0, 01 to 4 wt .-%, in particular 0, 1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 part by weight. %, wherein as described above on calcium-precipitating builders is largely dispensed with.

Polymers suitable as additives are especially 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 ^® L-77), polyalkylene oxide-modified heptamethyltrisiloxane (Silwet ^® L-7608), and poly-ethersiloxane (copolymers of polydimethylsiloxanes having ethylene oxide / propylene oxide segments (polyether )), preferably water-soluble linear polyether having terminal polyether as Tegopren ^® 5840, Tegopren ^® 5843, Tegopren ^® 5847, Tegopren ^® 5851, Tegopren ^® 5863 or Tegopren ^® 5878th

As additives suitable builders are, in particular polyaspartic acid-Na-salt, Ethylendiamintriacetatkokosalkylacetamid (Rewopol ^® CHT 12), methylglycine-tri-sodium salt (Trilon ES ^® 9964) and acetophosphonic (Turpinal SL ^®). Blends with surfactant or polymeric additives show in the case of Monawet MO-84 ^® R2W, Tegopren ^® 5843 and Tegopren 5863 ^® synergism. However, the use of Tegopren grades 5843 and 5863 is less preferred when applied to hard surfaces of glass, especially glassware, since these

Apply silicone surfactants to glass. In a particular embodiment of the invention, the additives mentioned are dispensed with.

The viscosity preferred for the liquid agent according to the invention is 20 ° C. and a shear rate of 30 min ^-1 - measured with a Brookfield LV DV II viscometer and spindle 25 - in the range of 10 to 10,000 mPa · s, preferably 600 to 6,000 mPa-s, in particular 1000 to 5000 mPa.s. The viscosity of the composition according to the invention can be increased by thickening agents and / or reduced by solvents.

For the purposes of the present invention, polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homopolymers and copolymers 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, guaran,

Tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, e.g. propoxylated guar, as well as 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, hydroxypropylmethyl 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 for example, by Fa. Kelco under the trade name Keltrol ^®, eg as cream-colored powder Keltrol ^® T (transparent) or as white granules Keltrol ^® RD (Readily Dispersable).

Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are i.a. from the Fa.

BFGoodrich under the trade name Carbopol ^®, for example Carbopol ^® 940 (molecular weight approximately 4,000,000), Carbopol ^® 941 (molecular weight approximately 1,250,000) or Carbopol ^® 934

(Molecular weight about 3,000,000).

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 ester, preferably formed with C 1-4 alkanols (INCI acrylates copolymer), to which approx 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 obtainable for example from Messrs. Rohm & Haas under the trade names Aculyn ^® and Acusol ^® such as 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 including such as the crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of Cio-30-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with Ci-4-alkanols, esters (INCI Acrylates / C 10 -30 alkyl acrylate crosspolymer) and the example of the Fa.

BFGoodrich are available under the trade name Carbopol ^®, eg hydrophobic the

Carbopol ^® and ETD2623 Carbopol ^® 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and Carbopol AQUA ^® 30 (formerly Carbopol ^® EX 473).

The content of polymeric thickener is usually not more than 8 wt .-%, preferably between 0.1 and 7 wt .-%, particularly preferably between 0.5 and 6 wt .-%. In other embodiments, the proportion may also be between 1 and 5 wt .-%, preferably between 1, 5 and 4 wt .-%, particularly preferably between 2 and 2.5 wt .-%.

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

To stabilize the composition of the invention, particularly at high surfactant content, one or more dicarboxylic acids and / or salts thereof may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, for example as available under the trade name Sokalan ^® DSC is. The use is advantageously carried out in amounts of 0.1 to 8 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1, 3 to 6 wt .-% and particularly preferably 2 to 4 wt .-%.

A change in the dicarboxylic acid (salt) content can - especially in amounts above 2 wt .-% - 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 wt .-%.

However, if it is possible to dispense with their use, the agent according to the invention is preferably free from dicarboxylic acid (salts).

As antibacterial component agents according to the invention may also contain elemental silver and / or a silver compound.

Lactic acid also has the advantage that, like benzoic acid or else salicylic acid as pH regulator and / or buffer substance, it can support or enhance the antibacterial action of the silver and / or the silver compound. However, the pH of the liquid agent according to the invention can also 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, wherein - in particular with the desired skin and hand tolerance - a range of 4 to 9, preferably 5 to 8.5 and in particular 5.5 to 8.0, is preferred. To adjust and / or stabilize the pH, the

agents according to the invention contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight, preferably from 0.005 to 3% by weight,

in particular 0.01 to 2 wt .-%, particularly preferably 0.05 to 1 wt .-%, most preferably 0, 1 to 0.5 wt .-%, for example 0.2 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (INCI chelating agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium conduction rates, for example trisodium citrate-2H2O and tripotassium citrate H20.

A liquid agent may further contain hydrotropes. This is

Solubilizers. Suitable hydrotropes are, for example, urea, butyl glycol or aliphatic short-chain anionic or amphoteric solubilizers.

In a preferred embodiment of the invention, the liquid cleaning agent contains a surfactant content of 5 to 20 wt .-%, preferably 8 to 16 wt .-%, based on the total weight of the composition and 0.2 to 0.7 wt .-% of an inorganic salt. The surfactant fraction preferably consists of a fatty alcohol ether sulfate and a betaine, preferably in a mass ratio of 5: 1 to 2: 1. The betaine is preferably cocoamidopropyldimethylamine oxide. In these embodiments, the ST index is preferably in the range of 0.01 and 0.06.

In a further preferred embodiment, the agent according to the invention contains 12% by weight of a fatty alcohol ether sulfate, 4% by weight of cocoamidopropyldimethylamine oxide, 0.5% by weight of a thickener, 0.6% by weight of an organic acid and 0.3% by weight. -% sodium chloride.

Preferably, the agent consists of these components (remainder water).

In one embodiment, the liquid cleaning agent according to the invention for cleaning hard surfaces, so in particular for cleaning soiled dishes, 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 be applied. To generate foam in a special way is a manually activated

Spray dispensers, in particular selected from the group comprising aerosol spray dispensers, pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump foam dispensers, such as those offered by Airspray, Taplast, Keltec or Daiwa Can Company. In addition to trigger bottles, pump spray dispensers and trigger spray dispensers with a polyethylene container are also suitable. Polypropylene or polyethylene terephthalate. 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 can also be filled with the addition of a suitable propellant (eg n-butane, a propane / butane mixture, carbon dioxide, nitrogen or a C02 / N2 mixture) in a corresponding aerosol spray bottle. However, such a spray dispenser is less preferred.

Accordingly, the agent according to the invention in the form of a product of the agent according to the invention and a spray or foam dispenser, in particular

Pump foam dispenser, be placed on the market.

For manual cleaning of a hard surface, the inventive liquid

Detergent either directly, that is undiluted, for example, by means of a sponge, applied to the surface to be cleaned and then removed with water again.

Alternatively, the hand dishwashing detergent according to the invention can first be applied with water

Dilute concentrations of 1: 1 to 1: 1000 and then the resulting cleaning solution with the surface to be cleaned in contact.

In the following, the present invention will be described in more detail by examples. However, these examples are by no means limitative of the subject matter of the present invention and are merely illustrative to those skilled in the art.

Examples

Two formulations were prepared, the respective compositions of which are shown in the table below. The quantities are in wt .-%

Active substance. E1 is a detergent according to the invention, while V1 is a comparative formulation.

The hand dishwashing detergents thus obtained were stable, pourable and readily dosed and had good cleaning, drainage and drying behavior.

The hand dishwashing detergent formulation E1 of the invention was advantageous in terms of its range, i. It showed an advantageous ratio between the number of cleaned plates and the required amount of starting hand dishwashing detergent. This is reflected in the TK index (number of cleaned plates per wt .-% surfactant in the detergent). This good TK value could be achieved with a much lower salt concentration at the same time, as can be seen from the ST index (salt concentration ratio in the product / surfactant concentration).

The range of Handgeschirrmittel is also expressed in the so-called. Durability of the agent in the sponge ("sponge load"). This is determined by default with the following method (see also exemplary embodiment in WO 2010/097316 A1):

A sponge is rinsed four times with water. Subsequently, 5 g of the detergent to be tested are applied. Then the sponge is pressed once with a defined force, so that the agent is distributed in the sponge. Then, add 100 ml of water evenly over the sponge and collect the passing liquid. The amount of surfactants dissolved in the detergent-loaded sponge contained in this liquid is determined analytically and the difference to the previously calculated determined surfactant content of the applied detergent determined. This then results in the amount of surfactant remaining in the sponge.

The proportion of surfactants remaining in the sponge is a measure of the longer shelf life of the detergent.

In addition, the cleaning agents according to the invention had improved cold turbidity with a simultaneously more transparent aesthetics and a lower viscosity.

Claims

claims

1. Liquid cleaning agent, in particular for hard surfaces, containing at least one surfactant and at least one salt, characterized by a ratio of

Salt concentration to surfactant concentration (ST index) from 0.001 to 0.8 and a ratio of the number of purified plates per wt .-% surfactant in the detergent (TK index) from 1 to 8.

2. Liquid detergent according to claim 1, characterized by an ST index of 0.01 to 0.5.

3. Liquid detergent according to claim 1 or claim 2, characterized by a salt content of 0, 1 to 0.5 wt .-%.

4. Liquid detergent according to one of the preceding claims characterized by a TK index of 2 to 5.

5. Liquid detergent according to one of the preceding claims characterized by a surfactant content of 5 to 70 wt .-%, preferably 10 to 55 wt .-%, in particular

15 to 50 wt .-%.

6. Liquid detergent according to one of the preceding claims, characterized by a surfactant combination with at least one anionic surfactant and at least one amphoteric surfactant.

7. Liquid detergent according to claim 4, characterized in that it contains at least one fatty alcohol ether sulfate and at least one betaine.

8. Liquid detergent according to one of claims 5 or 6, characterized by a mass ratio of anionic surfactant to amphoteric surfactant of 10: 1 to 1; 5, preferably 5: 1 to 2: 1, particularly preferably 4: 1.

9. Liquid detergent according to one of claims 5 to 7, characterized by a content of anionic surfactant from 5 to 20 wt .-%, particularly preferably from 8 to

16% by weight.

10. Liquid detergent according to one of claims 5 to 8, characterized by a content of betaine of 0.5 to 15 wt .-%, preferably from 1 to 10 wt .-%, in particular from 2 to 8 wt .-%.

1 1. A liquid detergent according to any one of the preceding claims, wherein the salt is selected from the group consisting of: halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates, oxides of alkali metals, alkaline earth metals, aluminum or transition metals , Formates, acetates,

Propionates, citrates, malates, tartrates, succinates, malonates, oxalates, lactates and

Mixtures thereof.

12. A liquid cleaning agent according to any one of the preceding claims, wherein the salt is selected from the group consisting of: halides, sulfates of the alkali metals, sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof, in particular sodium chloride.

13. Use of a liquid cleaning agent according to at least one of

previous claims for manual dishwashing.

14. A method for cleaning hard surfaces, in particular for the manual cleaning of dishes, comprising the use of a liquid cleaning agent according to any one of claims 1 to 12.