WO2001030958A1

WO2001030958A1 - Aqueous multiple phase detergent

Info

Publication number: WO2001030958A1
Application number: PCT/EP2000/010195
Authority: WO
Inventors: Georg Meine; Brigitte Giesen; Dagmar Zaika; Marion Wortmann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-10-26
Filing date: 2000-10-17
Publication date: 2001-05-03
Also published as: CA2324336A1; AU1139201A; DE19951635A1; AR026230A1

Abstract

The invention relates to an aqueous multiple phase detergent containing a tenside, especially a manual dishwashing detergent, comprising at least two continuous phases. The detergent has at least one lower, aqueous phase I and an upper, aqueous phase II which is not miscible with the first, and can be temporarily converted into an emulsion by shaking. Said detergent contains more than 2 wt. % of at least one organic solvent, can be used for cleaning hard surfaces, especially crockery, and is produced by directly mixing the raw materials, then re-mixing them and finally, allowing the product to stand in order to separate the temporary emulsion.

Description

"Aqueous multi-phase cleaning agent"

The invention relates to aqueous multi-phase liquid detergents, in particular hand dishwashing detergents, which can be temporarily emulsified by shaking, their use for cleaning hard surfaces, in particular dishes, and a process for their production.

Conventional liquid aqueous cleaning agents, in particular hand dishwashing detergents, are usually present as homogeneous, stable solutions or dispersions. However, the use of certain, in particular hydrophobic, components in such agents to improve the cleaning performance or the skin-care properties can result in this homogeneity being lost and inhomogeneous, optically unappealing agents being obtained, the acceptance of which can be rated as low by the consumer. In addition, the stable incorporation of large quantities of perfume oils is extremely problematic. In conventional dishwashing detergents or cleaning agents, the stable incorporation of small amounts of hydrophobic components or perfume oils is only possible using solubilizers and / or emulsifiers.

European patent application 116 422 describes a liquid hair or body shampoo with two aqueous phases which are temporarily dispersible in one another by shaking. The upper phase contains 8 to 25% by weight, based on the total composition, of at least one surfactant and the lower phase contains at least 6% by weight, based on the total composition, of dissolved sodium hexametaphosphate of the formula I,

ONa ONa ONa

I I

NaO-P-O- -P I-O- -P-Ona (I)

I I I O 0 o

(π-2) in which n stands for an average of approximately 12. Additional builder salts can optionally be contained in the lower phase.

From the German laid-open documents 195 01 184, 195 01 187 and 195 01 188 (Henkel KGaA), hair treatment agents in the form of a 2-phase system are known which have an oil phase and a water phase, the oil phase being based on silicone oil or paraffin oil. The two phases can be mixed briefly by mechanical action.

The object of the present invention was to provide a cleaning agent, in particular dishwashing agent, which, in spite of a given inhomogeneity of the agent, which is caused, for example, by the use of hydrophobic components to improve the cleaning performance or the skin-care properties, a defined one and has an acceptable external appearance and application form for the consumer. In addition, it is desirable to provide a cleaning agent, in particular dishwashing agent, which at the same time has a high cleaning performance.

Further tasks result from the description below.

The invention relates to an aqueous, liquid, multi-phase surfactant-containing cleaning agent with at least two continuous phases, which has at least one lower aqueous phase I and one upper aqueous phase II and which can be temporarily converted into an emulsion by shaking, and which has more than 2% by weight. contains at least one organic solvent.

The invention also relates to the use of an agent according to the invention for cleaning hard surfaces, in particular dishes. The agent according to the invention is preferably used for the manual cleaning of hard surfaces, in particular for the manual cleaning of dishes.

Unless expressly stated otherwise, the use of a salt is possible within the scope of the present invention, as is the use of the corresponding acid / base pair of the salt, even if this is in the present case. the teaching is not always explicitly formulated. In this sense, sodium citrate and the combination of citric acid / sodium hydroxide are equivalent alternatives.

If it is provided according to the invention that a specific component can be used for different purposes, its use is deliberately repeated below, if necessary. This applies, for example, to citric acid, which can be used both as an acid for pH adjustment and as a phase separation aid and builder.

The agents according to the invention are distinguished by a high cleaning performance, in particular on soils that are fatty and bleachable, for example from tea, with diluted and undiluted use. The transfer to a temporary emulsion remains reversible even after frequent shaking.

In the context of the present invention, temporary is understood to mean that 90% of the demixing of the emulsion formed by shaking into the separate phases takes place at temperatures of about 20 ° C. to about 40 ° C. within 2 minutes to 10 hours and the last 2 % of the separation take place within a further 15 minutes to 50 hours.

Furthermore, the agents enable the stable incorporation of components which can only be stably incorporated into single-phase aqueous solutions or stable emulsions or microemulsions by using solubilizers or emulsifiers. The aforementioned components include, in particular, the hydrophobic components and perfume oils described below. In addition, the multi-phase, in particular two-phase, effect an improvement in the chemical stability of the agent by the separation of ingredients into separate phases.

Substances that also serve as ingredients in cosmetic products are referred to below in accordance with the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds have an INCI name in English, herbal ingredients are excluded. borrowed according to Linne in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCl names can be found in the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), issued by The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA, and includes more than 9,000 INCl names and references to more than 37,000 trade names and technical names of the associated distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns the ingredients one or more chemical classes, such as Polymer Ethers, and one or more functions, such as Suractants - Cleansing Agents, to which reference may also be made below.

Organic solvents

According to the invention, the agent contains at least one organic solvent. The organic solvent content according to the invention is more than 2% by weight and usually not more than 30% by weight, preferably 3 to 25% by weight, in particular 5 to 20% by weight, particularly preferably 7 to 15% by weight. -%, for example 10% by weight.

Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C _1-20 hydrocarbons, preferably C ₂ . ₁₅ -hydrocarbons, with one or more hydroxyl groups, preferably a hydroxyl group, and possibly one or more ether functions COC, ie oxygen atoms interrupting the carbon atom chain.

Preferred solvents are the C _1-6 alcohols, in particular ethanol, n-propanol or / so-propanol, as well as the C _2-6 alkylene glycols and poly-C _2, which are etherified on one side with a C 1-4 alkanol. _3- alkylene glycol ethers with an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule, in particular the poly-C ₂ etherified on one side with a C ₆ alkanol. _3- alkylene glycol ether with an average of 1 to 9, preferably 2 to 3, ethylene or propylene glycol groups, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).

Exemplary solvents are the following compounds named according to INCI: Alcohol (ethanol), buteth-3, butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyl octanol, diethylene glycol, dimethoxydiglycol , Dimethyl Ether, Dipropylene Glycol, Ethoxydiglycol, Ethoxyethanol, Ethyl Hexanediol, Glycol, Hexanediol, 1, 2,6-Hexanetriol, Hexyl Alcohol, Hexylene Glycol, Isobutoxypropanol, Isopentyl-diol, Isopropyl Alcohol (/ so-Propanol), 3-Methoxybutanol , Methoxydiglycol, methoxyethanol, methoxyisopropanol, methoxymethylbutanol, methoxy PEG-10, methylal, methyl alcohol, methyl hexyl ether, methyl propanediol, neopentyl glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 methyl ether, pentylene glycol, PPG-7, PPG-2-buteth-3, PPG-2 butyl ether, PPG-3 butyl ether, PPG-2 methyl ether, PPG-3 methyl ether, PPG-2 propyl ether , Propanediol, propyl alcohol (n-propanol), propylene glycol, propylene glycol butyl ether, propylene e Glycol propyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.

With aliphatic or aromatic alcohols, for example methanol, ethanol, n-propanol, π-butanol, tert-butanol or phenol, or carboxylic acids, for example acetic or carbonic acid, etherified or esterified monomers or homo- or heteropolymers, in particular monomers and Homodi- and trimeric, C ₂ -C ₄ -alkylene glycols are sold, for example, under the trade name Dowanof by Dow Chemical and those under the trade names Arcosol ^ and Arconate ^® by Arco Chemical, such as those listed below with their INCI - Names according to the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA), e.g. butoxydiglycol (DowanoP DB), methoxydiglycol (DowanoP DM), PPG-2 methyl ether (Dowanof * DPM), PPG- 2 methyl ether acetates (Dowanof DPMA), PPG-2 butyl ether (Dowanol DPnB), PPG-2 propyl ether (DowanoP DPnP), butoxyethanol (Dowanof "EB), phenoxyethanol (DowanoP EPh), methoxyisopropanol (DowanoP PM), PPG-1 methyl ether acetate e (DowanoP PMA), butoxyisopropanol (DowanoP PnB), propylene glycol propyl ether (Dowanof PnP), Phenoxyisopropanol (DowanoP PPh), PPG-3 methyl ether (Dowanof * TPM) and PPG-3 butyl ether (Dowanof * TPnB) as well as ethoxyisopropanol (Arcosol ^ PE), tert-butoxyisopropanol (Arcosol ^ PTB), PPG-2 tetτ-butyl Ether (Arcosol ^ DPTB) and propylene carbonate (Arconate ⁹ PC), of which butoxyisopropanol (dipropylene glycol n-butyl ether, Dowanof PnB) and in particular PPG-2 methyl ether (dipropylene glycol methyl ether, Dowanof DPM) are preferred.

In a particularly preferred embodiment, the agent according to the invention contains one or more organic solvents from the group consisting of ethanol, isopropanol, n-propanol, dipropylene glycol methyl ether and butoxyisopropanol (1,2-propylene glycol-n-butyl ether), preferably ethanol, isopropanol, n-propanol and / or dipropylene glycol methyl ether, in particular isopropanol and / or n-propanol.

In a further particularly preferred embodiment, the agent according to the invention contains ethanol and n-propanol as organic solvents, preferably in an amount of at least 10% by weight together, particularly preferably of at least 12% by weight together.

phases

In the simplest case, an agent according to the invention consists of a lower continuous phase, which consists of the entire phase I, and an upper continuous phase, which consists of the entire phase II. However, one or more continuous phases of an agent according to the invention can also contain parts of another phase in emulsified form, so that in such an agent, for example, phase I is partly present as continuous phase I, which is the lower continuous phase of the agent, and one another part is emulsified as discontinuous phase I in the upper continuous phase II. The same applies to phase II and other continuous phases.

In a preferred embodiment of the invention, the continuous phases I and II are delimited from one another by a sharp interface. In a particular embodiment of the invention, one or both of the continuous phases I and II contain parts, preferably 0.1 to 25% by volume, in particular 0.2 to 15% by volume, based on the volume of the respective continuous phase each other phase as a dispersant. The continuous phase I or II is then reduced by the volume that is distributed as a dispersant in the other phase. Agents in which phase I is emulsified in phase II in amounts of 0.1 to 25% by volume, preferably 0.2 to 15% by volume, based on the volume of phase II, are preferred.

In a further special embodiment of the invention, in addition to the continuous phases I and II, part of the two phases is present as an emulsion of one of the two phases in the other phase, this emulsion not being present due to two sharp interfaces, an upper and a lower one parts of phases I and II involved in the emulsion are delimited.

The agents according to the invention usually contain phase I and phase II in a volume ratio of 90:10 to 10:90, preferably 75:25 to 15:85, in particular 60:40 to 20:80, particularly preferably 50:50 to 25:75, most preferably 40:60 to 30:70, for example about 1: 6 (14: 86), 1: 5 (17: 83), 1: 4 (20: 80), 1: 3 (25: 75) or 1: 2 (33: 67).

surfactants

The agents according to the invention can contain one or more nonionic, anionic, amphoteric or cationic surfactants or surfactant mixtures from one, several or all of these classes of surfactants as the surfactant component. The compositions contain surfactants in amounts, based on the composition, of usually 1 to 45% by weight, preferably 5 to 40% by weight, in particular 10 to 40% by weight, particularly preferably 2 to 35% by weight, most preferably 25 to 35% by weight, for example 28 or 33% by weight. In a particular embodiment, the agents according to the invention contain more than 30% by weight of surfactants.

Anionic surfactants are particularly preferred for economic reasons and because of their range of services. Surfactants from the individual groups can be used as individual substances. It is preferred to use mixtures of To use surfactants, preferably mixtures of surfactants from several of the aforementioned groups. Particularly suitable surfactant mixtures are those composed of anionic surfactants in combination with one or more nonionic surfactants or betaine surfactants, the betaine surfactants in this connection being equated with the class of amphoteric surfactants. The joint additional use of nonionic surfactants and betaine surfactants in a mixture can also be advantageous for many applications.

Anionic surfactants

Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates as well as aliphatic and aromatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates, lignin sulfonates, lignin sulfonates, lignin sulfonates, lignin sulfonates and lignin sulfonates, lignin sulfonates, Lignin sulfonates and lignin sulfonates, Lignin sulfonates, Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid ethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C _1B fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and the half esters of secondary alcohols (secondary alkyl sulfates) of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. With regard to the use of the agent according to the invention as (hand) dishwashing detergent, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Suitable secondary alkyl sulfates contain 2- and / or 3-alkyl sulfates and optionally higher homologues (4-, 5-, 6-alkyl sulfates etc.), can be prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company available under the name DAN ^® , e.g. B. in the US patents 5,529,724 and H 1, 665 named products DAN® 214, a C ₁₄ -SAS with 99% 2- and 3-alkyl sulfate, DAN® 216, a C ₁₆ -SAS with 99% 2- and 3-alkyl sulfate, and DAN® 100 , a SAS with 62% 2- and 3-alkyl sulfate.

The fatty alcohol ether sulfates are particularly preferred in the context of the present invention. Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. _{Suitable alkoxylated} alcohols are obtained by reacting ethylene oxide with longer-chain alcohols, for example with straight-chain or branched alcohols with chain lengths from C ₇ to C _21, such as 2-methyl-branched C ₉ to C _ιr fatty alcohols. As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Mixtures of ethylene oxide and propylene oxide can also be used in the ethoxylation reaction. Low-ethoxylated fatty alcohols (0.5 to 4 mol EO, preferably 1 to 2 mol EO) are very particularly preferred in the sense of the present invention.

The alkanesulfonates, in particular the secondary alkanesulfonates, which are composed of unbranched paraffin hydrocarbons, in particular C _12, are furthermore particularly preferred in the context of the present invention. ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. A preferred secondary alkane sulfonates is as Hostapur SAS ^® 60, sold by Clariant secondary Na-C. ₁₃ ₁₇ alkanesulfonate.

While the fatty alcohol ether sulfates are usually slightly superior to the secondary alkanesulfonates in terms of cleaning performance, alkanesulfonate-containing agents generally require a smaller amount of the phase separation auxiliaries and / or builders described below.

Other suitable surfactants of the sulfonate type are alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C ₁₂ . ₁₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Alkylbenzenesulfonates in the sense of the teaching according to the invention are alkylbenzenesulfonates with straight-chain or branched, saturated or unsaturated C _f ^ -alkyl radicals, preferably C ₈ . ₁₈ alkyl radicals, in particular C _9-14 alkyl radicals, most preferably C _10-13 alkyl radicals. They are used as alkali metal and / or alkaline earth metal salts, in particular sodium, potassium, magnesium and / or calcium salts, and also as ammonium salts or mono-, di- or tri-alkanolammonium salts, preferably mono-, di- or triethanol and / or -isopropanolammonium salts, especially mono-, di- or triethanolammonium salts, but also used as alkylbenzenesulfonic acid together with the corresponding alkali metal or alkaline earth metal hydroxide and / or ammonia or mono-, di- or trialkanolamine. The esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

The anionic surfactants are in the form of their alkali metal and alkaline earth metal salts, in particular sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetraalkylammonium salts and, in the case of the sulfonates, also in the form of the acid, for example dodecylbenzenesulfonic acid, C ₁₀ -C ₁₃ alkylbenzenesulfonic acid and / or C ₁₀ -C ₁₄ alkylbenzenesulfonic acid used. When sulfonic acid is used, it is usually mixed in situ with one or more corresponding bases, for example alkali metal and alkaline earth metal hydroxides, in particular sodium, potassium and magnesium hydroxide, and ammonia or mono-, di-, tri- or tetraalkylamine, depending on what is to be set pH of the agent partially or completely - neutralized to the aforementioned salts.

The compositions contain one or more anionic surfactants in amounts, based on the composition, of 0 to 45% by weight, preferably 1 to 40% by weight, in particular 5 to 35% by weight, extremely preferably 10 to 30% by weight. %, most preferably 15 to 25% by weight, for example 20% by weight. In a particularly preferred embodiment, the agent according to the invention contains fatty alcohol polyglycol ether sulfates, preferably magnesium and / or sodium fatty alcohol polyglycol ether sulfates, as anionic surfactants. In a further preferred embodiment In the form of the surfactant, the surfactant system is essentially based on anionic surfactant (s), ie the proportion of anionic surfactant (s) is half the total amount of surfactants, preferably even more than half the total amount of surfactants.

Nonionic surfactants

Suitable nonionic surfactants are, for example, C ₆ -C ₂₂ -alkyl alcohol polyglycol ethers, alkyl polyglycosides and nitrogenous surfactants or else sulfosuccinic acid-C ₁₂ -alkyl esters or mixtures thereof, in particular the first two. The compositions according to the invention contain nonionic surfactants in amounts, based on the composition, of usually 0 to 30% by weight, preferably 0.1 to 25% by weight, in particular 1 to 20% by weight, particularly preferably 2 to 15% by weight, most preferably 3 to 10% by weight, for example 4 or 9% by weight.

Presumably, nonionic surfactants with their nonionic character advantageously contribute to the individual phases being stable over a long period of time without e.g. Form deposits, and the transfer to a temporary emulsion remains reversible even after frequent shaking.

alkyl alcohol

C ₆ -C ₂₂ alkyl alcohol polypropylene glycol / polyethylene glycol ether are preferred known nonionic surfactants. They can be represented by the formula II, R ¹ O- (CH ₂ CH (CH ₃ ) O) _p (CH ₂ CH ₂ O) _e -H , are described in which R ^{1 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 8 to 18, in particular 10 to 16, carbon atoms, p for 0 or numbers from 1 to 3 and e stands for numbers from 1 to 20.

The C ₆ -C ₂₂ alkyl alcohol polyglycol ethers of the formula II can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to oxo alcohols, to branched-chain primary alcohols obtainable by oxosynthesis or to fatty alcohols. Typical examples are polyglycol ethers of the formula II in which R ^{1 is} an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7. Preferred representatives are, for example, C- ₁₀ -C ₁₄ fatty alcohol + 1 PO + 6EO ether (p = 1, e = 6), C ₁₂ -C ₁₆ fatty alcohol + 5.5-EO (p = 0, e = 5.5), C ₁₂ -C ₁₈ fatty alcohol + 7EO ether (p = 0, e = 7) and isodecanol + 6- EO (R ¹ = isomer mixture of C ₁₀ oxo alcohol residues, p = 0, e = 6) and mixtures thereof. In particular mixtures, at least one representative of the formula II with a linear alkyl radical R ^{1 is combined} with at least one representative of the formula II with a branched alkyl radical R ¹ , for example C ₁₂ -C ₁₆ - fatty alcohol + 5.5-EO and isodecanol + 6-EO. It is further preferred here that the linear alkyl radical comprises more carbon atoms than the branched alkyl radical. C ₈ fatty alcohol + 1.2PO + 8.4EO, Cβ are particularly preferred. ₁₀ - fatty alcohol + 5EO, C _12-14 fatty alcohol + 6EO and C ₁₂ . ₁₄ fatty alcohol + 3EO and their mixtures.

Nonionic surfactants and especially alkyl alcohol polyglycol ethers cause an increase in the volume of the lower phase. This makes it possible, for example, to specifically shift the phase boundary of a two-phase cleaning agent according to the present invention upwards or downwards by using smaller or higher amounts of e.g. Fatty alcohol polyglycol ether is added.

End-capped C ₆ -C ₂₂ alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group is etherified in the formula II. The end-capped C ₆ -C ₂₂ alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry. C ₆ -C ₂₂ -Alkyl alcohol polyglycol ethers are preferably reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride. Typical examples are mixed ethers of the formula II in which R ^{1 is} an industrial fatty alcohol residue, preferably C _12/14 cocoalkyl residue, p is 0 and e is 5 to 10, which are sealed with a butyl group.

Alkylpolyglykoside

Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula III, R ² O [G] _x , in which R ^{2 is} a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] represents a glycosidically linked sugar radical and x represents a number from 1 to 10. APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry. The index number x in the general formula III indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x must always be an integer in a given compound and here before can assume all the values x = 1 to 6, the value x for an alkylglycoside is an analytically calculated quantity, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.6. Xylose, but especially glucose, is preferably used as the glycosidic sugar.

The alkyl or alkenyl radical R ² (formula III) can be derived from primary alcohols having 8 to 22, preferably 8 to 14, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from RoELEN's oxo synthesis.

However, the alkyl or alkenyl radical R ² is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures should also be mentioned.

Nitrogen-containing non-ionic surfactants

Suitable nonionic surfactants containing nitrogen are, for example

Amine oxides, polyhydroxy fatty acid amides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides, the alkyl groups with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10. Ethanolamide derivatives of alkanoic acids with 8 to 22 C atoms, preferably 12 to 16 C atoms, are preferred. The particularly suitable compounds include lauric acid, myristic acid and palmitic acid monoethanolamides.

amine oxides

The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy the formula R ¹ R ² R ³ N ⁺ -O ^" , in which R ^{1 is} a saturated or unsaturated one

in particular a saturated C _10-16 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 -0- (CH ₂ ) _z -, z in each case represents a number from 1 to 10, preferably 2 to 5, in particular 3, and R ² and R ³ independently of one another are an optionally hydroxy-substituted C _M alkyl radical, such as, for example, a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are the following compounds named according to INCI: Aimondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidine Oxide -10 Alkoxypropylamine Oxide, Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Taliowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Hydroxyethylamine Alkoxypropylamine Oxide, Isostearamidopropylamine Oxide, Isostearamidopropyl Morpholine Oxide, Lauramidopropylamine Oxide, Lauramine Oxide, Methyl Morpholine Oxide, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxide, Myristamidopropylamine Oxide, Myristamine Oxide, Myristyl / Cetyl Amine Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Sesamidopropylamine Oxide, Sesamidopropylamine Oxide, Sesamidopropylamine Oxide, Sesamidopropylamine Oxide, Sesamido Propylamine Oxide, Sesamidopropylamine Oxide, , Stearamine Oxide, Tallowamidopropylamine Oxide, Taliowamine Oxide, Undecyleneamidopropylamine Oxide and Wheat Germamidopropylamine Oxide. Preferred amine oxide (s) are, for example, cocamine oxides (N-coconut alkyl-N, N-dimethylamine oxide), dihydroxyethyl talowamine oxides (N-tallow alkyl-N, N-dihydroxyethylamine oxide) and / or cocamidopropylamine oxides (cocoamido propylamine oxide), in particular Cocamidopropylamine oxides.

polyhydroxy

Other suitable surfactants are polyhydroxy fatty acid amides of the formula III,

R ¹

I R-CO-N- [Z] (IM)

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula IV,

R ¹ -0-R ²

I

R-CO-N- [Z] (IV) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In a preferred embodiment, the agents according to the invention contain one or more nonionic surfactants, preferably alkyl polyglycosides and / or C ₆ -C ₂₂ alkyl alcohol polyglycol ethers and / or amine oxides.

Amphoteric surfactants

Suitable amphoteric surfactants (zwitterionic surfactants) are, for example, betaines, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which betaines are preferred in the context of the teaching according to the invention.

Betaine

Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazoliniumbetaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy the formula (R ^A ) (R ^B ) (R ^c ) N ⁺ CH ₂ COO ^" , in which R ^{A is} an alkyl radical which is optionally interrupted by heteroatoms or heteroatom groups and has 8 to 25, preferably 10 to 21, carbon atoms and R ^B and R ^c are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyldimethylcarboxymethylbetaines and C _ιr C ₁₇ -alkylamidopropyldimethylcarboxymethylbetaines, or formula A,

'- [CO-X- (CH ₂ ) _n ] _x -N ⁺ (R ^ll ) (R ^llll ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] Y- (A)

in which R 'is a saturated or unsaturated C _6-22 alkyl radical, preferably

in particular a saturated C _1c , ₁₆ -alkyl radical, for example a saturated C _12-14 -alkyl radical, X NH, NR ^IV with the C _1-4 -alkyl radical R ^ι , O or S, n a number from 1 to 10, preferably 2 to 5, in particular 3, x 0 or 1, preferably 1,

R ", R '" independently of one another are a C _1-4 -alkyl radical, optionally hydroxyl-substituted, such as, for example, a hydroxyethyl radical, but in particular a methyl radical, m is a number from 1 to 4, in particular 1, 2 or 3, y 0 or 1 and Y COO, S0 ₃ , OPO (OR) 0 or P (0) (OR ^v ) 0, where R is a hydrogen atom H or a C _1-4 alkyl radical.

The alkyl and alkyl amido betaines, betaines of formula A with a carboxylate group (Y ^~ = COO ^" ), are also called carbobetaines.

Preferred amphoteric surfactants are the alkylbetaines of the formula A1, the alkylamido betaines of the formula A2, the sulfobetaines of the formula A3 and the amidosulfobetaines of the formula A4,

R'-N ⁺ (CH ₃ ) ₂ -CH ₂ COO- (A1)

R'_CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO- (A2)

R'-N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ S0 ₃ - (A3) R'-CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH ( OH) CH ₂ S0 ₃ - (A4)

in which R 'has the same meaning as in formula A. Particularly preferred amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formula A1 and A2, most preferably the alkylamidobetaines of the formula A2.

Examples of suitable betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl betaine, apricotamidopropyl betaine, avocadamidopropyl betaine, Babassuamidopropyl betaine, behenamidopropyl betaine, behenyl betaine, betaine, canolamidopropyl betaine, capyl / capramidopropyl betaine, carnitine, carnitine Cocamidoethyl Betaine, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallethicine Propane , Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydro xysultaine, oleyl betaine, olivamidopropy! Betaine, Palmamidopropyl Betaine, Palmitamidopropyl Betaine, Palmitoyl Carnitine, Palm Kernelamidopropyl Betaine, Polytetrafluoroethylene Acetoxypropyl Betaine, Ricinoleamidopropyl Betaine, Sesamidopropyl Betaine, Soyamidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Betaine, and Tallowamidopropyl Betaine , Undecylenamidopropyl Betaine and Wheat Germamidopropyl Betaine. A preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine). A particularly preferred amphoteric surfactant is caprylic / capramidopropyl betaine (CAB), which is available, for example, from Th. Goldschmidt AG under the trade name Tegotens ¹¹ 'B 810.

alkylamidoalkylamines

The alkylamidoalkylamines (INCI alkylamido alkylamines) are amphoteric surfactants of the formula B Rvι_ _CO -NR ^{, l} - (CH ₂ ) N (R ^l ") - (CH ₂ CH ₂ 0) _r (CH ₂ ) _κ - [CH (OH)] _r CH ₂ -Z-OM (B)

in which R ^{vl is} a saturated or unsaturated Ce.a alkyl radical, preferably C _B-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical, R "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 ^vι "a hydrogen atom H or CH ₂ COOM (to M su), j a number from 1 to 4, preferably 1 or 2, in particular 1, k a number from 0 to 4, preferably 0 or 1,

I 0 or 1, where k = 1 if I = 1,

Z CO, S0 ₂ , OPO (OR ¹² ) or P (0) (OR ¹² ), where R ^{12 is} a C _1-4 alkyl radical or M (see below), and M is a hydrogen, an alkali metal, an alkaline earth metal or protonated alkanolamine, for example protonated mono-, di- or triethanolamine.

Preferred representatives satisfy the formulas B1 to B4,

R ^l -CO-NH- (CH ₂ ) ₂ -N (R ^VMI ) -CH ₂ CH ₂ 0-CH ₂ -COOM (B1)

R ^vl -CO-NH- (CH ₂ ) ₂ -N (R ^l ") -CH ₂ CH ₂ 0-CH ₂ CH ₂ -COOM (B2) R ^l -CO-NH- (CH ₂ ) ₂ -N ( R ^III ) -CH ₂ CH ₂ 0-CH ₂ CH (OH) CH ₂ -S0 ₃ M (B3)

R ^l -CO-NH- (CH ₂ ) ₂ -N (R ^vlll ) -CH ₂ CH ₂ 0-CH ₂ CH (OH) CH ₂ -OP0 ₃ HM (B4) in which R ^vι , R ^ι "and M have the same meaning as in formula B.

Exemplary alkylamido alkylamines are the following compounds named according to INCI: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Ca proamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloam- phodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate , Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Laurauamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2- lsodeceth-7 Carboxyamphodiacetate, disodium, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodi- propionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproam- phohydroxypropylsulfonate Stearoamphodiacetate, Sodium Caproamphopropionate, Sodium Caprylo- amphoacetates, Sodium Capryloamphohydroxypropylsulfonate, Sodium Caprylo- amphopropionates, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypro- pyisulfonate, isostearoamphopropionate Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium, Sodium lauroamphoacetate, sodium Lauroamphohydroxypropylsulfonate, Sodium lauryl roampho PG-Acetate phosphate, Sodium Lauroamphopropionate, Sodium myristic stoamphoacetate, Sodium Oleoamphoacetate, pylsulfonate Oleoamphohydroxypro- Sodium, Sodium Oleoamphopropionate , Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowa m-Phoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride Phosphate.

Alkyl substituted amino acids

Alkyl-substituted amino acids preferred according to the invention (INCI alkyl-substituted amino acids) are monoalkyl-substituted amino acids according to formula C,

R ^lx -NH-CH (R ^x ) - (CH ₂ ) _u -COOM '(C)

in the R ^ιx a saturated or unsaturated Ce ^ alkyl radical, preferably Cj β-alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,

R ^{x 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 D,

R ^xl -N - [(CH ₂ ) _v -COOM "] ₂ (D)

in which R ^{xι is} a saturated or unsaturated C _6-22 alkyl group, preferably C _8-18 alkyl group, in particular a saturated C _10- ι ₆ alkyl group, for example a saturated C _12-14 alkyl group, v is a number of 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, e.g. protonated mono-, di- or triethanolamine, where M" can have the same or two different meanings in the two carboxy groups, e.g. Can be hydrogen and sodium or twice sodium is

and mono- or dialkyl-substituted natural amino acids according to formula E, RX "_ _(R ^χ ιιι ₎ _ _{CH (R} ^χ ιv ₎ _ _COOM , H ( _E )

wherein R ^x "is a saturated or unsaturated Ce. ^ - alkyl radical, preferably C ₈ ₁₈ alkyl radical, preferably a saturated C _{1 (6} -alkyl radical, for example a saturated C _12-14 alkyl group, R ^xι." is a hydrogen atom or a C ^ alkyl, optionally hydroxy or amine substituted, for example a methyl, ethyl, hydroxyethyl or aminopropyl radical, R ^xι the rest of one of the 20 natural α-amino acids

H ₂ NCH (R ^xlv ) 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 C1,

R ^lx -NH-CH ₂ CH ₂ COOM '(C1)

in which R ^lx and M 'have the same meaning as in formula C. Exemplary alkyl-substituted amino acids are the following compounds named according to INCI: aminopropyl laurylglutamine, cocaminobutyric acid, cocaminopropionic acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, disodium lauriminodipropionionipropionionipropionionipropionionipropionionipropionionipropionate, disodium styrodinodioninodipropionate, disodium styrodinodioninodipropionic acid, , Lauryl Diethylene diaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myristaminopropate.

Acylated amino acids

Acylated amino acids are amino acids, in particular the 20 natural α-amino acids, which carry the acyl radical R ^x CO of a saturated or unsaturated fatty acid R ^x COOH on the amino nitrogen atom, where R ^{x is} a saturated or unsaturated Ce. ₂₂ -alkyl radical, preferably C ₈ . ₁₈ -alkyl radical, preferably a saturated C ₁₀ .ι ₆ alkyl radical, for example a saturated C _12-14 alkyl group. The deacylated 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 according to INCI under amino acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.

The compositions contain one or more amphoteric surfactants, preferably betaines, in particular alkylamido betaines, in amounts, based on the composition, of 0 to 15% by weight, preferably 0.1 to 10% by weight, in particular 1 to 8% by weight. %, particularly preferably from 2 to 6% by weight, extremely preferably 3 to 5% by weight, for example 4% by weight.

In a particularly preferred embodiment of the invention, the compositions comprise one or more anionic surfactants together with one or more nonionic and / or one or more amphoteric surfactants, preferably one or more anionic surfactants and one or more nonionic surfactants. de, in particular one or more anionic, one or more nonionic and one or more amphoteric surfactants.

hydrophobic components

In a particularly advantageous embodiment of the invention, the compositions contain one or more hydrophobic components. The hydrophobic components not only improve the cleaning effect against hydrophobic impurities such as greasy dirt and / or the skin-care effect, but also have a positive effect on the phase separation and its reversibility. The present invention enables a stable incorporation - especially also in larger amounts - of hydrophobic components into the two-phase or multi-phase agents, while in single-phase aqueous solutions or stable emulsions or microemulsions, hydrophobic components only by using solubilizers or emulsifiers in mostly very limited amounts can be incorporated stably.

Suitable hydrophobic components are, for example, dialkyl ethers with identical or different C ₄ to C ₁₄ alkyl radicals, in particular linear dioctyl ether; Hydrocarbons with a boiling range from 100 to 300 ° C, in particular 140 to 280 ° C, for example aliphatic hydrocarbons with a boiling range from 145 to 200 ° C, isoparaffins with a boiling range from 200 to 260 ° C; essential oils, in particular limes and the pine oil extracted from pine roots and stumps; and also mixtures of these hydrophobic components, in particular mixtures of two or three of the hydrophobic components mentioned.

Preferred mixtures of hydrophobic components are mixtures of various dialkyl ethers, of dialkyl ethers and hydrocarbons, of dialkyl ethers and essential oils, of hydrocarbons and essential oils, of dialkyl ethers and hydrocarbons and essential oils and of these mixtures.

Particularly preferred hydrophobic components are the skin-care dialkyl ethers, in particular di-n-octyl ether. The compositions contain hydrophobic components in amounts, based on the composition, of 0 to 20% by weight, preferably 0.1 to 15% by weight, in particular 1 to 12% by weight, particularly preferably 2 to 10% by weight , extremely preferably 3 to 8% by weight, for example 4 to 6% by weight, for example 5% by weight.

Phase separation auxiliaries

The agents according to the invention can contain one or more phase separation aids. Suitable phase separation aids are, for example, the alkali metal and alkaline earth metal halides, in particular chlorides and sulfates and nitrates, in particular sodium and potassium chloride and sulfate, and also ammonium chloride and sulfate or mixtures thereof. Such salts support the phase separation through the salt effect as strong electrolytes which increase the ionic strength. A particularly preferred phase separation aid are magnesium salts of the above-mentioned anions, in particular magnesium chloride, for example in the form of its hexahydrate MgCl ₂ -6H ₂ O, since the magnesium ions additionally improve the skin-friendliness and, as a non-greasy agent, the cleaning performance.

The ionic or salt-form builders described below also act as phase separation aids, so that in their presence either less or possibly no additional phase separation aids is required.

Builder

Furthermore, the agent according to the invention preferably contains one or more builders, in particular to improve the cleaning performance. Suitable builders are, for example, alkali metal citrates, gluconates, nitrilotriacetates, carbonates and bicarbonates, in particular sodium citrate, gluconate and nitrilotriacetate, as well as sodium and potassium carbonate and bicarbonate, and also alkali metal and alkaline earth metal hydroxides, especially sodium and potassium hydroxide Amines, in particular the alkanolamines mono-, di- and triethanolamine, or mixtures thereof. These also include the salts of glutaric acid, succinic acid, adipic acid, tartaric acid and benzene hexacarboxylic acid as well as aminotrimethylenephosphonic acid, hydroxyethane-1, 1-diphosphonic acid, 1- Aminoethane-1, 1 -diphosphonic acid, ethylenediamine-tetra (methylenephonic acid), diethylenetriamine-penta (methylenephosphonic acid), 2-phosphonobutane-1, 2,4-tricarboxylic acid and phosphonates. In contrast, phosphates are less suitable; For example, the pentasodium triphosphate commonly known as sodium tripolyphosphate (NaTPP) often leads to severe precipitation.

If the builder is also to act as a pH-stabilizing buffer, alkali metal and alkaline earth metal carbonates and bicarbonates, preferably sodium carbonate (soda), are preferably used, in particular together with citric acid or citrate, which may be generated in situ from citric acid and hydroxide. eg Sodium or potassium citrate, particularly preferably together with the mixture of citric acid or citrate described above.

In the context of the present invention, the citrates - unless expressly stated otherwise - are the salts of triple deprotonated citric acid. However, the mono- and dihydrogen citrates can also be used according to the invention.

The builder salts mentioned can also be used in the form of their corresponding acids or bases, which are then partially or completely neutralized depending on the pH to be set. The acids mentioned can also be used in the form of their salts, preferably their alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium salts, in particular mono-, di- or triethanolammonium salts, or mixtures thereof, in particular their sodium salts , for example citric acid in the form of its monohydrate citric acid 1 H ₂ 0 instead of citrate. The builder salts also act as phase separation aids. The complexing builders also serve in particular to ensure a clear application solution when using the agents with hard water.

Citric acid or citrates are particularly preferred builders. It is preferred - if appropriate generated in situ from citric acid and hydroxide or alkanolamine -

Citrate from the group of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium citrates, preferably mono-, di- or trietha- noiammonium citrates, or their mixtures, in particular sodium citrate and / or potassium citrate, particularly preferably monoethanol ammonium citrate, since citrates combine builder and phase separation aid properties in a particularly advantageous manner and also promote the removal of lime dirt and bleachable stains.

In a particular embodiment, the agent according to the invention contains citric acid or citrate and magnesium chloride, in particular monoethanolammonium citrate and magnesium chloride.

The compositions contain builders and / or phase separation aids in a total amount, based on the composition, of preferably 1 to 40% by weight, in particular 5 to 35% by weight, particularly preferably 10 to 31% by weight, extremely preferably 15 to 25% by weight.

perfume oils

The agent according to the invention preferably also contains one or more perfume oils since, in addition to the scent effect, they support the phase separation and improve the cleaning performance. Perfume oils in particular regularly cause problems when they are incorporated, especially in larger amounts, into single-phase aqueous solutions or stable emulsions or microemulsions. The use of solubilizers or emulsifiers can usually stabilize smaller perfume oil contents. A great advantage of the multi-phase agents according to the present invention is that a stable incorporation of the perfume oils, in particular also in larger quantities, is made possible.

The components of the suitable perfume oils described below are followed by numbers in parentheses, e.g. "(5.0)", which is exemplary information on the composition of the respective perfume oil in% by weight, based on the perfume oil. Thus, "geraniol (105.0)" means that the perfume oil Geraniol e.g. may contain o in an amount of 105.0% by weight.

A suitable perfume oil with a fresh, fruity fragrance contains, for example, Dynascone 10 (5.0), Cyclovertal (7.5), hexyl acetate (35.0), allyl heptanoate (200.0), amyl butyrate (5.0), prenylacetate (10.0), aldehyde C 14 SOG (70.0), manzanate (15.0), melusate (30.0), ortho tert-butylcyclohexyl acetate (200, 0), cinnamaldehyde (5.0), isobornyl acetate (10.0), dihydrofloriffone TD (2.5), floramate (100.0), phenylethyl alcohol (30.0), geraniol (105.0), cyclohexyl salicylate (150, 0) and citronellol (20.0).

A suitable perfume oil with a fresh, floral fragrance contains, for example, bergamot oil (250.0), lemon oil Messina (50.0), citronellal (2.0), orange oil sweet (50.0), lavender oil (50.0), Terpineol (50.0), Lilial (100.0), Phenylethyl alcohol (80.0), Citronellol (100.0), Geraniol (20.0), Benzyl acetate (60.0), Isoraldein 70 (50.0), Ylang (30.0), Ambroxan 10% in IPM (1.0), Heliotropin (47.0) and Habanolide (60.0).

A suitable perfume oil with an aromatic fragrance contains, for example, orange oil (710.0), α-pinene (130.0), ß-pinene (20.0), γ-terpinene (95.0) and Litsea Cuba oil ( 55.0).

The content of one or more perfume oils is usually 0.1 to 15% by weight, preferably 0.2 to 10% by weight, in particular 0.5 to 5% by weight, particularly preferably 1 to 2% by weight ,

enzymes

In a particular embodiment of the invention, the agent contains one or more enzymes.

Customary in detergents and cleaning agents enzymes, such as proteases (for example, BLAP 260 ^®, BLAP S 260 SLD ", BLAP S 260 ALCF, BLAP S 260 LD ^ and BLAP S are 26 (f Fa. Biozym or Durazym ^®, Savinase ^® and Alcalase ^® from Novo Nordisk), amylases (e.g. TermamyP from Novo Nordisk), cellulases (e.g. KAC 500 ^® from Kao, Celluzyme ^® from Novo Nordisk), lipases (e.g. Lipolase 100 ^® and Lipolase 100 T ^® from Novo Nordisk) and peroxidases and reductases. The nonionic surfactants in general and the alkylpolyglycosides in particular improve the storage stability of the enzyme-containing embodiment as well as the citric acid or its salts and also the hydrophobic components, in particular the - optionally etherified or esterified - mono- or polymeric C ₂ -C ₄ -alkylene glycols, e.g. those under the trade names DowanoP,

and Arconate ^® products, as well as polyethylene glycols and their derivatives. The multiphase nature of the agent according to the invention has an advantageous effect on the stability of the enzymes, which is presumably due to the enrichment of the enzymes in the above-mentioned stabilizing components and - in the sense of ionic strength - less ionic upper phase II.

The pH of the agents according to the invention can be varied over a wide range from strongly acidic to neutral to highly alkaline, preferably in a range from 1 to 12, in particular 2 to 11, depending on the particular application.

Suitable pH regulators are acids such as mineral acids, e.g. Hydrochloric acid, but especially citric acid, and on the other hand the aforementioned alkaline builders, preferably sodium hydroxide, potassium hydroxide and alkanolamines, especially monoethanolamine.

In an alkaline embodiment of the invention, the agents have a pH of more than 7 to 12, preferably 8 to 11, in particular 8 to 10.5, for example between 8 and 9, e.g. 8.3, for moderate alkalinity or over 9 to 10.5, 11 or even 12, e.g. 10, for stronger alkalinity.

In a preferred embodiment of the invention, in particular for manual dishwashing, the agents are neutral to acidic with a pH of 3 to 7, preferably 3.5 to 7, in particular 4 to 6.5, particularly preferably 4.5 to 6.5, most preferably 5 to 6, for example 5.5. To set such a pH, the agents contain at least one acid. Inorganic acids, for example the mineral acids, for example hydrochloric acid, and organic acids, for example saturated or unsaturated C _1-6 -mono-, -Di- as well as tricarboxylic acids and hydroxycarboxylic acids with one or more hydroxy groups, for example citric acid, maleic acid, formic acid and acetic acid, amidosulfuric acid, C ^ fatty acids and anionic sulfonic acids, and mixtures thereof, for example that under the trade name Sokalan ^® DCS from BASF Available succinic acid-glutaric acid-adipic acid mixture. Particularly preferred acids are citric acid, preferably used in the form of its monohydrate citric acid-1H ₂ 0, and the anionic sulfonic acids and combinations of citric acid with one or more anionic sulfonic acids, especially with alkylarene sulfonic acids. Citric acid advantageously combines acid, builder and phase separation auxiliary properties, while the anionic sulfonic acids act simultaneously as an acid and an anionic surfactant. If necessary, one or more alkalis can also be used, for example the alkali metal, alkaline earth metal and ammonium hydroxides and carbonates, and ammonia or amines, preferably sodium and potassium hydroxide and alkanolamines, monoethanolamine being particularly preferred.

To stabilize or buffer the pH, the agent according to the invention contains, in a particular embodiment, small amounts of corresponding buffer substances, in the described alkaline embodiment, for example, soda or sodium bicarbonate.

thickener

To adjust the viscosity, the agent according to the invention can contain one or more thickeners, preferably in an amount of 0.01 to 5% by weight, in particular 0.05 to 2.5% by weight, particularly preferably 0.1 to 1% by weight. -%, contain.

Suitable thickeners are organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein), organic modified natural substances (carboxymethyl cellulose and other cellulose ethers, Hydroxyethyl and propyl cellulose and the like, core meal ether), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas).

The polyacrylic and polymethacrylic compounds include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (/ Λ / C / designation according to the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA): Carbomer), which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are available from BFGoodrich, among others, under the trade name Carbopof ^® , for example Carbopof ^® 940 (molecular weight approx. 4,000,000), CarbopoP 941 (molecular weight approx. 1,250,000) or Carbopof ^® 934 (molecular weight approx. 3,000) .000). The following also include the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C _1-4 alkanols, to which, for example the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (C> 4S designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) belong and which, for example, from Rohm & Haas under the trade names Aculyn ^® and Acusol ^® are available, for example the anionic non-associative polymers Aculyn ^® 33 (crosslinked), Acusol ^® 810 and ACU sof ^® 830 (CAS 25852-37-3); (ii) crosslinked high molecular acrylic copolymers, for example the copolymers of C _10-3 o-alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple, preferably with C _{1- 4} -alkanols, esters (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and which are available, for example, from BFGoodrich under the trade name Carbopof ^® , for example the hydrophobized Carbopof ^® ETD 2623 and Carbopot ^® 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and Carbopof ^® AQUA 30 (formerly Carbopof ^® EX 473). Preferred thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guarane, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated es guar, as well as their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used as an alternative, but preferably in addition to a polysaccharide rubber, for example starches of various origins and starch derivatives, for example 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 particularly preferred polymer is the microbial anionic heteropoly saccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 to 15 * 10 ⁶ and for example available from the company. Kelco under the trade name Keltrof ^® is, for example, as a cream-colored powder Keltrof ^® T (Transparent) or as white granulate Keltrof ^® RD (Readily Dispersable).

In a preferred embodiment, the agent according to the invention is free from thickeners.

Auxiliaries and additives

In addition to the components mentioned, the agents according to the invention can contain further auxiliaries and additives as are customary in such agents. These include in particular polymers, soil release agents, solubilizers, hydrotropes (e.g. sodium cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), emulsifiers (e.g. gallus soap), gloss drying additives, cleaning enhancers, antimicrobial agents or disinfectants, antistatic agents, preservative agents (preservatives) (preservatives) , Bleaching systems and dyes as well as opacifiers or skin protection agents, as described in EP-A-522556. The amount of such additives is usually not more than 12% by weight in the cleaning agent. The lower limit of the assignment depends on the type of aid and additive and can be, for example, up to 0.001% by weight and below. The amount of auxiliaries and additives is preferably between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.

A preferred auxiliary and additive are dyes, since the phases can be colored differently by their addition, which facilitates the visual perception of the separated phases and also the tracking of the emulsion formation or separation, and thus makes the handling of the agent even easier.

Another object of the invention is a method for producing a two-phase or multi-phase cleaning agent according to one of the preceding claims by mixing directly from its components, optionally subsequent mixing and / or final standing of the agent for separating the temporary emulsion.

Components within the meaning of the present invention are all of the aforementioned substances and substances which can be contained in the cleaning agent according to the invention.

Preferably, in order to adjust the phase quantity ratios after the temporary emulsion has been separated, further portions of at least one component are added one or more times, if appropriate, the mixture is subsequently mixed and / or finally left to separate the temporary emulsion.

Furthermore, the agents according to the invention can also be produced by first producing a single-phase composition, which is preferably essentially homogeneous, and then adding further, optionally additional components which separate the agent into two or more phases. The further, optionally additional components are preferably selected from the group comprising alcohols, acids, bases and / or fatty alcohol polyglycol ethers.

In a particularly preferred embodiment of the process according to the invention, a single-phase composition comprising at least one anionic and / or nonionic and / or amphoteric surfactant and / or at least one builder and / or at least one organic solvent and / or at least one thickening agent and optionally further Manufactured additives and then added citric acid, preferably citric acid monohydrate, n-propanol, monoethanolamine, water and optionally fatty alcohol polyglycol ether to form a two-phase or multi-phase composition.

Furthermore, it is preferred first of all to prepare a single-phase composition comprising fatty alcohol polyglycol ether sulfate, fatty alcohol polyglycol ether, fatty acid alkanolamide, amine oxide, amphoteric surfactant, betaine, 1, 2-propanediol, ethanol, sodium sulfate, sodium chloride, water and optionally further additives, and then citric acid, preferably citric acid demo Add nohydrate, n-propanol, monoethanolamine, water and optionally fatty alcohol polyglycol ether to form a two-phase or multi-phase composition.

It is particularly preferred according to the invention to add at least 6% by weight of citric acid monohydrate, at least 6% by weight of n-propanol and such an amount of monoethanolamine to the intermediate single-phase composition so that the resulting composition has a pH of about 5 , 0 has.

For example, a cleaning agent or dishwashing detergent according to the invention is obtained by first of all having a single-phase composition comprising 13% by weight of fatty alcohol polyglycol ether sulfate, 15% by weight of fatty alcohol polyglycol ether, 1.5% by weight of fatty acid alkanolamide, 1.5% by weight of amine oxide, 2. 2% by weight of amphoteric surfactant / betaine, 0.1% by weight of 1,2-propanediol, 6.5% by weight of ethanol, 0.4% by weight of sodium sulfate and 0.2% by weight of sodium chloride and 55.3% by weight of water, which are then added by the subsequent addition of 7.1% by weight , based on the single-phase composition, citric acid monohydrate, 5.7% by weight, based on the single-phase composition, n-propanol, 6.0% by weight, based on the single-phase composition, monoethanolamine, and 7.1% by weight .-%, based on the single-phase composition, fatty alcohol polyglycol ether is converted into a two-phase cleaning agent.

B e is p i e l e

Agents E1 to E6 according to the invention were produced by the method according to the invention. Table 1 shows the composition in% by weight.

Table 1

Hostapur ^® SAS 60 (Clariant) ^(b) Dowanof ^® DPM ^{| c} - Dowanof ^® PnB

The detergent compositions listed in Table 1 consistently showed two clear continuous phases, changing temporarily when shaken formed an emulsion. Even after repeated shaking, separate phases formed again when left standing.

The two-phase agents E7 to E12 according to the invention were likewise produced by the method according to the invention. Table 2 shows the composition in% by weight. In addition, the respective volume fractions (T) of the lower (u) and upper phase (o) are listed in Table 2.

Table 2

Table 2 shows that the cleaning agents according to the invention were consistently obtained as two-phase compositions. The respective volume proportions of the consistently clear phases or the phase boundary can be specifically adjusted or shifted by suitable choice of the ingredients. The visual appearance does not change even after prolonged storage or standing, ie no precipitation has been observed.

The following table 3 shows the compositions V1 of a conventional hand dishwashing detergent of the prior art.

Table 3

To demonstrate the excellent cleaning ability of the cleaning agents according to the present invention, the cleaning performance of V1 and E7 were examined. The results are shown in Table 4. Table 4

The results obtained show that the two-phase hand dishwashing detergent E7 according to the invention has an excellent dishwashing capacity which is improved compared to the conventional hand dishwashing detergent V1. The emulsifying and foaming power of E7 can also be assessed as very good

Claims

P a te n ta nsp

1. Aqueous liquid multi-phase surfactant-containing cleaning agent, in particular hand dishwashing detergent, with at least two phases, which has at least one lower aqueous phase I and one upper aqueous phase II and can be temporarily converted into an emulsion by shaking, characterized in that it has more than 2 Wt .-% contains at least one organic solvent.

2. Composition according to claim 1, characterized in that it contains at least one organic solvent in an amount of more than 2 to 30 wt .-%, preferably 3 to 25 wt .-%, in particular 5 to 20 wt .-%, especially 0 preferably 7 to 15% by weight.

3. Composition according to one of claims 1 or 2, characterized in that it is one or more organic solvents from the group ethanol, isopropanol, n-propanol, dipropylene glycol methyl ether and butoxyisopropanol, in particular isopropanol and / or n-propanol and particularly preferred

15 contains a solvent mixture of ethanol and n-propanol.

4. Composition according to one of claims 1 to 3, characterized in that the continuous phases I and II are delimited from each other by a sharp interface.

5. Composition according to one of the preceding claims, characterized in that one or both of the continuous phases I and II parts, preferably 0.1 to 25% by volume, in particular 0.2 to 15% by volume, based on the Volume of the respective continuous phase, the other phase contained as dispersant.

6. Agent according to one of the preceding claims, characterized in that phase I in amounts of 0.1 to 25 vol .-%, preferably 0.2 to 15 vol .-%, based on the volume of phase II, in phase II is emulsified.

7. Agent according to one of the preceding claims, characterized in that in addition to the continuous phases I and II, part of the two phases is present as an emulsion of one of the two phases in the other phase, this emulsion having two sharp interfaces, an upper and a lower - s right, compared to the parts of phases I and not involved in the emulsion

II is delimited.

8. Composition according to one of the preceding claims, characterized in that there are phase I and phase II in a volume ratio of 90: 10 to 10: 90, preferably 75: 25 to 15: 85, in particular 60: 40 to 20: 80, 0 contains.

9. Composition according to one of the preceding claims, characterized in that it contains one or more anionic surfactants.

10. Agent according to one of the preceding claims, characterized in that it contains fatty alcohol polyglycol ether sulfates, preferably as anionic surfactants

15 wise magnesium and / or sodium fatty alcohol polyglycol ether sulfates, contains.

11. Agent according to one of the preceding claims, characterized in that it contains one or more nonionic surfactants, preferably alkyl polyglycosides C ₆ -C ₂₂ - and / or alkyl alcohol polyglycol ethers and / or amine oxides,

20 contains.

12. Composition according to one of the preceding claims, characterized in that it contains one or more amphoteric surfactants, preferably betaine.

13. Agent according to one of the preceding claims, characterized in that it additionally contains hydrophobic components from the group of dialkyl ethers

25 with identical or different C ₄ - to C ₁₄ -alkyl radicals, in particular

Dioctyl ether, which contains hydrocarbons with a boiling range from 100 to 300 ° C., in particular 140 to 280 ° C., of the essential oils, in particular limonene and pine oil, and their mixtures, in particular mixtures of two or three of the hydrophobic components mentioned.

14. Agent according to one of the preceding claims, characterized in that it additionally contains one or more phase separation aids, in particular magnesium chloride.

15. Agent according to one of the preceding claims, characterized in that it additionally contains one or more builders, preferably citric acid or citrates, in particular triethanolammonium citrate.

16. Agent according to one of the preceding claims, characterized in that it contains one or more perfume oils.

17. Agent according to one of the preceding claims, characterized in that it contains one or more enzymes.

18. A method for producing a two-phase or multi-phase cleaning agent according to one of the preceding claims by mixing directly from its components, optionally subsequent mixing and / or final standing of the agent for separating the temporary emulsion.

19. The method according to claim 18, wherein in order to adjust the phase quantity ratios after the temporary emulsion has been separated, further portions of at least one component may be added one or more times, optionally subsequently mixed and / or finally left to separate the temporary emulsion.

20. A process for the preparation of a two-phase or multi-phase agent according to any one of the preceding claims 1 to 17, wherein a single-phase composition is first produced, which is preferably essentially homogeneous and which is then added further, optionally additional components that separate the agent effect in two or more phases.

21. The method according to claim 20, wherein the further, optionally additional components are selected from the group comprising alcohols, acids, bases and / or fatty alcohol polyglycol ethers.

22. The method according to any one of claims 20 or 21, wherein first a homogeneous single-phase composition comprising at least one anionic and / or nonionic and / or amphoteric surfactant and / or at least one builder and / or at least one organic solvent and / or at least one thickener and optionally further additives are prepared and then citric acid, preferably 0 citric acid monohydrate, n-propanol, monoethanolamine, water and optionally fatty alcohol polyglycol ether are added to form a two-phase or multi-phase composition.

23. The method according to any one of claims 20 to 22, wherein first of all a homogeneous single-phase composition comprising fatty alcohol polyglycols thersulfate, fatty alcohol polyglycol ether, fatty acid alkanolamide, amine oxide, amphoteric surfactant, betaine, 1,2-propanediol, ethanol, sodium sulfate, sodium chloride, water and optionally further Additives is produced, and then citric acid, preferably citric acid monohydrate, n-propanol, monoethanolamine, water and optionally fatty alcohol

20 polyglycol ethers are added to form a two or more phase composition.

24. Use of an agent according to one of the preceding claims for cleaning hard surfaces, in particular dishes.