EP1141225A1

EP1141225A1 - Aqueous multi-phase cleaning agent

Info

Publication number: EP1141225A1
Application number: EP99964566A
Authority: EP
Inventors: Georg Meine; Ryszard Katowicz
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1998-12-23
Filing date: 1999-12-14
Publication date: 2001-10-10
Also published as: AU3038400A; CO5211009A1; TNSN99250A1; DE19859774A1; WO2000039270A1; AR021990A1; CA2292967A1

Abstract

The invention relates to an aqueous liquid multi-phase surface-active cleaning agent with at least two continuous phases which contains at least one lower aqueous phase I and one non-aqueous liquid upper phase II which is immiscible with said aqueous phase and which can be temporarily converted to an emulsion by shaking and contains citric acid and/or at least one citrate. Said cleaning agent can be used to clean hard surfaces and it is prepared directly from its starting materials by mixing them, then thoroughly agitating the mixture and leaving it to stand so that the temporary emulsion dissolves. Citric acid and/or at least one citrate is used in an aqueous liquid multi-phase surface-active cleaning agent with at least two continuous phases which comprises at least one lower aqueous phase I and one upper aqueous phase II which is immiscible with said lower phase and which can be temporarily converted to an emulsion by shaking. The invention also relates to a method of producing such a cleaning agent.

Description

"Aqueous multi-phase cleaning agent"

The invention relates to aqueous multiphase liquid surfactant-containing cleaning agents with citric acid or citrate, which can be temporarily emulsified by shaking and can be used for cleaning hard surfaces, a process for their preparation and their use for cleaning hard surfaces, and the use of citric acid or citrate in such a multi-phase cleaning agent as phase separation aid or for reducing turbidity in the area of the boundary layer between the phases and corresponding methods for producing such multi-phase cleaning agent with the aid of citric acid or citrate for separating the phases or reducing said clouding.

Universally usable cleaning agents for all hard, wet or damp wipeable surfaces in the household and business are known as so-called all-purpose cleaners and are predominantly neutral to weakly alkaline aqueous liquid products, the 1 to 30 wt .-% surfactants, 0 to 5 wt .-% builder (for example citrates, gluconates, soda, polycarboxylates) 0 to 10% by weight of hydrotropes (for example alcohols, urea), 0 to 10% by weight of water-soluble solvents (for example alcohols, glycol ethers) and optionally, among others Contain skin protection agents, dyes and fragrances. It is usually used as an approx. 1% solution in water, also undiluted for local stain removal. Ready-to-use all-purpose cleaners are also commercially available as so-called spray cleaners.

Such aqueous liquid cleaners are usually present as homogeneous, stable solutions or dispersions. However, the use of certain, in particular hydrophobic, components in such cleaning agents can result in this homogeneity being lost and inhomogeneous agents being obtained, the acceptance of which can be estimated as low by the consumer. In such cases, the alternative wording of Agents that, despite their inhomogeneity, have a defined and acceptable form of appearance and application for the consumer.

European patent application 116 422 describes a liquid hair or body shampoo with two aqueous phases which can be temporarily dispersed into one another by shaking, and both phases being miscible with water in any ratio. 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 I

NaO-P-O- -P-O- -P-ONa (D

II II II

0 0 0

(fi-2) in which n stands for an average of approximately 12. Additional builder salts can optionally be contained in the lower phase. Anionic, cationic, amphoteric and / or nonionic surfactants can be present as surfactants, preferably at least one anionic surfactant being contained.

From the German laid-open documents 195 01 184, '187 and' 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, and by mechanical action are miscible for a short time.

In the case of a two-phase agent such as that of the '422, undesirable turbidity of the individual phases in the undispersed, separated state of the phases can easily occur, in particular after shaking one or more times. Here, especially in the area of the boundary layer, streak-like cloudiness can occur, which the consumer perceives as unaesthetic and may even mistakenly be interpreted as an indication of a product that has become unusable. In addition, after one or more shakes, a renewed phase separation may be absent in part or even entirely and lead to an undefined appearance of the agent, which is judged by the consumer as negative. The object of the present invention was to provide high-performance and storage-stable means for cleaning hard surfaces in a defined inhomogeneous, easy-to-handle and acceptable form for the consumer, which does not have the problems described above.

In a first embodiment, the invention relates to an aqueous liquid multiphase 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 which is immiscible with this phase and which can be temporarily converted into an emulsion by shaking, and which contains citric acid and / or at least one citrate.

In a second embodiment, the invention relates to the use of an aqueous liquid multiphase 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 which is immiscible with this phase and which is temporarily converted into an emulsion by shaking leaves and contains citric acid and / or at least one citrate, for cleaning hard surfaces.

In a third embodiment, the invention relates to a process for producing an agent according to the invention by mixing it directly from its raw materials, then mixing it and finally standing the agent to separate the temporary emulsion.

In a fourth embodiment, the invention relates to the use of citric acid and / or at least one citrate in an aqueous liquid multiphase 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 which is immiscible with this phase and can be temporarily converted into an emulsion by shaking, as a phase separation aid and / or to reduce turbidity in the region of the boundary layer between phases I and II.

In a fifth embodiment, the invention relates to a process for the preparation of an aqueous liquid multiphase 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 which is immiscible with this phase and which is temporarily shaken into a Emulsion can be transferred to the citric acid and / or at least one citrate is used as an aid for separating the phases and / or for reducing turbidity in the area of the boundary layer between phases I and II.

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 into the phase state before shaking within a further 15 minutes to 50 hours.

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 which only gives the salt or its solution in situ with neutralization, even if the respective one Alternative is not always explicitly formulated in the present teaching. In this sense, potassium citrate and the combination of citric acid / potassium hydroxide or potassium alkylbenzenesulfonate and the combination of alkylbenzenesulfonic acid / potassium hydroxide are equivalent alternatives.

Insofar as the following statements relate to an object of the invention, they also apply to the other objects of the invention, unless expressly stated otherwise.

Citric acid or citrate advantageously combine builder and phase separation aid properties in accordance with the invention. The agents according to the invention are therefore distinguished by a high cleaning ability with diluted and undiluted use, in particular with stubborn grease soiling when used undiluted. In addition, the agents show favorable residue behavior. The individual phases on average are stable over a long period of time without e.g. Deposits formed and the transfer to a temporary emulsion remains reversible even after frequent shaking. In addition, the separation of ingredients in separate phases can promote the chemical stability of the agent.

A particular advantage of the invention is the high transparency of the continuous phases I and II and the low-opacity or even opacifying boundary layer between them. The agents according to the invention contain citric acid and / or at least one citrate in an amount of usually 0.1 to 30% by weight, preferably 1 to 20% by weight, in particular 2 to 15% by weight, extremely preferably 4 to 12% by weight .-%. The amount to be selected for a certain concentration of citrate ions depends on the type of cations in the form used, which on the one hand are the light protons of the acidic carboxyl groups and / or on the other hand are heavier metallic cations or, if appropriate, alkylated - Can act ammonium ions.

Citric acid can be used, for example, in the form of its monohydrate '1H ₂ O citric acid.

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.

A group of suitable citrates are e.g. the alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium citrates, preferably mono-, di- or triethanolammonium citrates, or mixtures thereof. Sodium citrate and potassium citrate are particularly suitable.

Potassium citrate or the use of citric acid in combination with potassium hydroxide has a particularly positive effect on the phase separation, the clarity of the phases and the sharpness, as well as the lack or opacity of the phase boundary layer.

Accordingly, a preferred agent according to the subject of the invention in its first embodiment contains potassium citrate and / or citric acid in combination with potassium hydroxide.

Accordingly, in a preferred use according to the subject of the invention in its fourth embodiment, potassium citrate and / or citric acid is used in combination with potassium hydroxide.

Accordingly, in a preferred method according to the subject of the invention, in its fifth embodiment, potassium citrate and / or citric acid is used in combination with potassium hydroxide. 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 other part than discontinuous phase I is emulsified 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 further preferred 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, the 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 particularly preferred.

In a further preferred 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 contain phase I and phase II in a volume ratio of 90:10 to 10:90, preferably 75:25 to 25:75, in particular 65:35 to 35:65.

In a particularly advantageous embodiment of the invention, the agents contain one or more hydrophobic components. Suitable hydrophobic components are, for example, dialkyl ethers with the same or different C ₄ -C ₁₄ -alkyl radicals, in particular dioctyl ether; Hydrocarbons with a boiling range of 100 to 300 ° C, in particular 140 to 280 ° C, for example aliphatic hydrocarbons with a boiling range of 145 to 200 ° C, isoparaffins with a boiling range of 200 to 260 ° C; essential oils, in particular limonene and 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. The agents contain hydrophobic components in amounts, based on the composition, of 0 to 20% by weight, preferably 0.1 to 14% by weight, in particular 0.5 to 10% by weight, most preferably 0.8 to 7 % By weight.

In addition to citric acid and / or citrate, the agents according to the invention can contain one or more further phase separation aids. Suitable further 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, sodium chloride being particularly preferred. Such salts, as strong electrolytes, support phase separation through the salt effect. The compositions contain phase separation aids in amounts, based on the composition, of 0 to 30% by weight, preferably 1 to 20% by weight, in particular 3 to 15% by weight, extremely preferably 5 to 12% by weight. These phase separation aids are used in particular when the ionic strength caused by the other ionic compounds contained does not bring about the desired phase separation.

The agents according to the invention can contain anionic, nonionic, amphoteric or cationic surfactants or surfactant mixtures from one, several or all of these surfactant classes as the surfactant component. The compositions contain surfactants in amounts, based on the composition, of 0.01 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 14% by weight, extremely preferably 3 to 10% by weight. -%.

Suitable nonionic surfactants are, for example, C ₈ -C ₁₈ -alkyl alcohol polyglycol ethers, alkyl polyglycosides and nitrogen-containing surfactants or also sulfosuccinic acid di-C 1 -C 4 -alkyl esters or mixtures thereof, in particular the first two. The funds included nonionic surfactants in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 0.5 to 14% by weight, extremely preferably 1 to 10% by weight .

C ₈ -C ₁₈ alkyl alcohol polypropylene glycol / polyethylene glycol ethers 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 8 to 18 carbon atoms, p is 0 or numbers from 1 to 3 and e is numbers from 1 to 20.

The C ₈ -C ₁₈ 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 fatty alcohols. Typical examples are polyglycol ethers of the formula II in which R represents an alkyl radical having 8 to 18 carbon atoms, p represents 0 to 2 and e represents numbers from 2 to 7. Preferred representatives are, for example, C ₁₀ -C ₁₄ fatty alcohol + 1PO + 6EO ether (p = 1, e = 6) and C ₁₂ -C ₁₈ fatty alcohol + 7EO ether (p = 0, e = 7) and mixtures thereof .

End-capped C ₈ -C ₁₈ alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group in the formula II is etherified. The end-capped C ₈ -C ₁₈ alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry. C ₈ -C ₁₈ -Alkyl alcohol polyglycol ethers are preferably reacted with alkyl halides, in particular butyl or benzyl chloride, in the presence of bases. Typical examples are mixed ethers of the formula II in which R ^{1 is} an industrial fatty alcohol radical, preferably C _12/14 cocoalkyl radical, p is 0 and e is 5 to 10, which are sealed with a butyl group.

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] is a glycosidically linked sugar radical and x stands for 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 in a given compound must always be integer and here can assume the values x = 1 to 6, the value x for a certain alkyl glycoside is an analytically calculated value, 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, preference is given to those alkyl glycosides 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 18, preferably 8 to 14, carbon atoms. Typical examples are capronalcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from ROELEN's oxosynthesis.

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, gadolinyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures are also to be mentioned.

Nitrogen-containing surfactants may be included as further nonionic surfactants, e.g. Fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides which have alkyl groups with 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10. Ethanolamide derivatives of alkanoic acids having 8 to 22 C atoms, preferably 12 to 16 C atoms, are preferred. The particularly suitable compounds include the lauric acid, myristic acid and palmitic acid monoethanolamides.

Suitable anionic surfactants are the preferred C ₈ -C ₁₈ alkyl sulfates, C ₈ -C ₁₈ alkyl ether sulfates, ie the sulfation products of the alcohol ethers of the formula II, and / or C ₈ -C ₁₈ alkyl benzene sulfonates, in particular dodecylbenzenesulfonate, but also C ₈ -C ₁₈ alkanesulfonates, C ₈ -C ₁₈ -α-olefin sulfonates, sulfonated C ₈ -C ₁₈ fatty acids, C ₈ -C ₂₂ carboxamide ether sulfates, sulfosuccinic acid mono-C _r C ₁₂ alkyl esters, C ₈ -C ₁₈ alkyl polyglycol ether carboxylates, C ₈ -C ₁₈ N acyl taurides, C ₈ -C ₁₈ N sarcosinates and C ₈ -C ₁₈ alkyl isethionates or mixtures thereof. They 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 their corresponding acid, for example dodecylbenzenesulfonic acid. When sulfonic acid is used, it is usually converted into the aforementioned salts 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 neutralized. The compositions contain anionic surfactants in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 14% by weight, extremely preferably 2 to 10% by weight. %.

When using the particularly preferred alkylbenzenesulfonic acids, in particular with a high content of sodium chloride and / or with neutralization with sodium hydroxide, clouding in the region of the boundary layer between phases I and II can occur. Citric acid or citrate already counteracts this problem according to the invention. A further improvement occurs, however, in the neutralization of the alkylbenzenesulfonic acid with potassium hydroxide, which has a particularly positive effect in this regard on the phase separation, the clarity of the phases and the sharpness, as well as low or low haze of the phase boundary layer.

Because of their foam-suppressing properties, the agents according to the invention can also contain soaps, ie alkali metal or ammonium salts of saturated or unsaturated C ₆ -C ₂₂ fatty acids. The soaps can be used in an amount of up to 5% by weight, preferably from 0.1 to 2% by weight.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ³ ) (R ⁴ ) (R ⁵ ) N ⁺ CH ₂ COO ^" , in which R ^{3 is} an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms which is optionally interrupted by heteroatoms or heteroatom groups and R ⁴ and R ^{5 are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyl-dimethylcarboxymethylbetaine and C _{ι r} C ₁₇ -alkylamidopropyl-dimethylcarboxymethylbetaine. The compositions contain amphoteric surfactants in quantities, based on the composition, from 0 to 15% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ⁶ ) (R ⁷ ) (R ⁸ ) (R ⁹ ) N ⁺ X ^" , in which R ⁶ to R ^{9 represent} four identical or different types, in particular two long and two short-chain, alkyl radicals and X ^" for an anion, in particular a Ha- logenidion, are, for example, didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof. The compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10% by weight, preferably 0.01 to 5% by weight, in particular 0.1 to 3% by weight.

In a preferred embodiment, the agents according to the invention contain anionic and nonionic surfactants next to one another, preferably C ₈ -C ₁₈ alkylbenzene sulfonates, C ₈ -C ₁₈ alkyl sulfates and / or C ₈ -C ₁₈ alkyl ether sulfates in addition to C ₈ -C ₁₈ alkyl - Alcohol polyglycol ethers and / or alkyl polyglycosides, in particular C ₈ -C ₁₈ alkylbenzene sulfonates in addition to C ₈ -C ₁₈ alkyl alcohol polyglycol ethers.

In addition to the citric acid and / or citrate, the agents according to the invention can also contain one or more other builders. Suitable builders are, for example, alkali metal gluconates, nitrilotriacetates, carbonates and bicarbonates, in particular sodium gluconate and nitrilotriacetate, and sodium and potassium carbonate and bicarbonate, and also alkali metal and alkaline earth metal hydroxides, in particular sodium and potassium hydroxide, ammonia and amines. in particular mono- 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 phosphonates and phosphates, for example the pentasodium triphosphate known as sodium tripolyphosphate or sodium hexamethaphosphate such as a mixture of condensed orthophosphates of the formula I, in which n stands for an average of about 12 . The compositions contain builders in amounts, based on the composition, of 0 to 20% by weight, preferably 0.01 to 12% by weight, in particular 0.1 to 8% by weight, extremely preferably 0.3 to 5 % By weight. The builders also act as phase separation aids.

A particularly preferred builder is potassium hydroxide, since it has a particularly positive effect on the phase separation, the clarity and color brilliance of the phases as well as the sharpness and low or low haze of the phase boundary layer.

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, solvents (e.g. ethanol, isopropanol, glycol ether), solubilizers, hydrotropes (e.g. cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), cleaning enhancers, viscosity regulators (e.g. synthetic polymers such as polysaccharides, polyacrylates, in naturally occurring polymers and their derivatives such as xanthan gum, other polysaccharides and / or gelatin), disinfectants, antistatic agents, preservatives, bleaching systems, enzymes, perfume, colorants and fragrances as well as opacifiers or skin protection agents, as described in EP-A-522 556. The amount of such additives is usually not more than 12% by weight in the cleaning agent. The lower limit of use depends on the type of additive and can be up to 0.001% by weight and below, for example in the case of dyes. The amount of auxiliaries is preferably between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.

In a preferred embodiment of the invention, the compositions contain one or more perfumes in an amount of 0.1 to 5, preferably 0.2 to 3, in particular 0.5 to 2, particularly preferably 1 to 1.5% by weight . When a hydrophobic component is used at the same time, the perfume and the hydrophobic component are predominantly in the same phase, which is generally the upper phase II. This has the advantageous effect of an intensified fragrance experience when smelling on a container which is open or open at the top and contains such an agent according to the invention. Perfumes also influence the phase separation properties of the agents according to the invention with their essential oils, the ratio of phase I to phase II generally shifting in favor of phase I with increasing perfume content.

The pH of the agents according to the invention can be varied over a wide range, but a range from 2.5 to 12, in particular 5 to 10.5, is preferred. In the context of the present invention, the pH of the agents according to the invention means the pH of the medium in the form of the temporary emulsion.

In a preferred embodiment of the invention, the agents are alkaline with a pH of 8 to 12, preferably 8.5 to 11.5, in particular 9 to 11, most preferably 9.3 to 10.5.

Suitable pH regulators are, on the one hand, mineral acids, for example hydrochloric acid, but especially citric acid, and, on the other hand, the above-mentioned alkaline builders, preferably sodium hydroxide, but especially because of the advantages already mentioned, potassium hydroxide. To stabilize or buffer the pH, the agent according to the invention contains, in a particular embodiment, small amounts of corresponding buffer substances, for example soda in the alkaline embodiment described.

The agents according to the invention can be mixed directly from their raw materials. subsequent mixing and final standing of the agent for separating the temporary emulsion.

The agent according to the invention is sprayable and can therefore be used in a spray dispenser.

Another object of the invention is accordingly a product containing an agent according to the invention and a spray dispenser.

The spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group comprising aerosol spray dispensers, self-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a container made of transparent polyethylene or polyethylene terephthalate. Spray dispensers are described in greater detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein for spray dispensers, all of which are referred to in this regard and the contents of which are hereby incorporated into this application.

The agents according to the invention are used, for example, in such a way that the agent temporarily converted into an emulsion by shaking in amounts of about 1.5 to 10 g per m ² , in particular 3 to 7 g per m ² , onto the surface to be cleaned applies and immediately wipes this surface with an absorbent soft object and thereby cleans it. The agents are applied, for example, with the aid of suitable spraying devices, in particular a spray dispenser or a product according to the invention, in order to achieve a distribution which is as uniform as possible. Sponges or cloths, which can be rinsed out with water from time to time when treating larger areas, are particularly suitable for wiping. Example

example 1

Agents E1 to E6 according to the invention and comparative agent V1 were prepared as described above. Table 1 shows their compositions in% by weight, their pH and, for E1 to E6, the quantified volume ratio of lower phase I to upper phase II. The lower phase I also accounted for slightly more than half of the total volume in V1. In addition, agents E1 to E6 and V1 contained 0.05% by weight of glutaraldehyde as a preservative and, with the exception of E5, also small amounts of dye, which colored the lower phase turquoise and the upper phase blue.

Table 1

Composition [% by weight] E1 E2 E3 E4 E5 E6 V1

Dodecylbenzenesulfonic acid 3

C ₁₀ -C ₁₄ fatty alcohol + 1 PO + 1 EO ether 2

C ₁₂ -C ₁₈ fatty alcohol + 7EO ether

C ₁₂ . ₁₄ -fatty alcohol + 9EO-butyl ether 2

C ₈ . _10- alkyl-1,5-glucoside 4

Citric acid - 1 H ₂ O 6.2 6.5 8 6.2

Sodium chloride 6.9

Potassium hydroxide 5.5 5.6 5.5 5.78

Sodium hydroxide - - - - 4.7 5.6 0.5

Dioctyl ether 5 5 5 5 5 5 5

Perfume 0.9 0.9 0.9 0.9 0.9 0.9 0.5

Water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 pH 9.5 9.5 9.5 9.5 9 9.5 10.15

Volume ratio phase I: phase II 60:40 60:40 70:30 60:40 70:30 60:40

All means showed two continuous phases, which temporarily formed a creamy-looking emulsion when shaken. However, while the upper phase II in V1 was slightly milky and turbidity occurred in the area of the phase boundary, in particular after repeated shaking, the agents according to the invention also demonstrated multiple shakes - transparent phases with a haze-free sharp phase boundary and more brilliant colors.

Example 2

The cleaning ability of agents E7 and V2 to V6, which were prepared in accordance with the compositions given in Table 2 as described above, was tested in diluted and undiluted form.

Unless otherwise stated below, the cleaning effect was tested in accordance with the quality standards for floor care and cleaning agents of the Industrial Association for Cleaning and Care Products. V. (IPP), Frankfurt / M. (Soaps - oils - fats - waxes 1986, 112, 371-372). The test was carried out with 10 ml diluted test substance with a concentration of 1, 5 or 6 ml / l and soiling 2 as well as with 6 ml undiluted test substance and a soiling from oil, fat, white spirit and a carbon black / pigment mixture.

The method is based on wiping a white dirt carrier treated with test dirt under defined conditions with a sponge soaked in the test material and measuring the cleaning effect photoelectrically against the untreated white dirt carrier.

A device similar to the washability and abrasion tester 494 from Erichsen GmbH, D-58675 Hemer-Sundwig, was used as the wiping device with a brass guide rail and an 820 g weight attachment.

The whiteness measurement was carried out using a Micro-Color color difference measuring device from Dr. Lange, D-40549 Düsseldorf, performed with averaging over 21 measured values per test strip.

The cleaning power was determined in each case in a triple determination and is given in Table 2 as the relative cleaning power RV _re , in% for the two dilutions and the undiluted form. Table 2

Composition [% by weight] E7 V2 V3 V4 V5 V6

Dodecylbenzenesulfonic acid 6 6 6 6 6 6

C ₁₂ -ι ₈ fatty alcohol + 7EO ether 4 4 4 4 4 4

Sodium hydroxide 0.78 0.78 0.78 0.78 0.78 0.78

C ₁₂ . ₁₄ -Fatty alcohol + 2EO- 3 3 3 3 3 3 ether sulfate sodium salt

C ₁₂ . ₁₈ coconut oil fatty acid 1 1 1 1 1 1

Trisodium citrate 3 - - - - -

Sodium gluconate - - 3 - - -

Sodium tripolyphosphate - - - 3 - 3

Urea - - - - 5 5

Water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100

Cleaning ability

RV _re diluted (1, 5 ml / l) [%] 90 74 86 88 76 90

RV _rel diluted (6 ml / l) [%] 102 100 98 102 98 102

RV _rel undiluted [%] 172 100 131 147 103 138

The agent E7 according to the invention not only showed a consistently better cleaning ability than the builder-free comparison agent V1, but was also at least as good in its cleaning ability as other builder-containing comparison agents V2 to V6 and in most cases even superior, this superiority being particularly clear when used undiluted on stubborn stains becomes.

Claims

P ate n ta claims

1. 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 immiscible with this phase, upper aqueous phase II and can be temporarily converted into an emulsion by shaking, characterized in that it contains citric acid and / or contains at least one citrate.

2. Composition according to claim 1, characterized in that it is citric acid and / or at least one citrate in an amount of 0.1 to 30 wt .-%, preferably 1 to 20 wt .-%, in particular 2 to 15 wt .-% , most preferably 4 to 12 wt .-%, contains.

3. Composition according to claim 1 or 2, characterized in that it is citrate from the group of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanol ammonium citrates, preferably mono-, di- or triethanolammonium citrates, or their mixtures, especially sodium citrate, most preferably contains potassium citrate.

4. Agent 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 vol .-%, in particular 0.2 to 15 vol .-%, based on the volume the respective continuous phase, the other phase as dispersant.

6. Agent according to one of the preceding claims, characterized in that

Phase I in amounts of 0.1 to 25% by volume, preferably 0.2 to 15% by volume, based on the volume of phase II, is emulsified in phase II.

7. Composition 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 , compared to the parts of phases I and II not involved in the emulsion.

8. Composition according to one of the preceding claims, characterized in that it contains phase I and phase II in a volume ratio of 90:10 to 10:90, preferably 75:25 to 25:75, in particular 65:35 to 35:65.

9. Agent according to one of the preceding claims, characterized in that it s additionally hydrophobic components from the group of dialkyl ethers with identical or different C ₄ - to C ₁₄ -alkyl radicals, in particular dioctyl ether, hydrocarbons with a boiling range from 100 to 300 ° C, in particular 140 to 280 ° C, essential oils, in particular limonene and pine oil, and their mixtures, in particular mixtures of two or three of the hydrophobic components mentioned, 0 contains.

10. Agent according to one of the preceding claims, characterized in that it contains additional phase separation aid, preferably from the group of alkali metal and alkaline earth metal chlorides and sulfates, in particular sodium and potassium chloride and sulfate, and ammonium chloride and sulfate or mixtures thereof .

5 11. Agent according to one of the preceding claims, characterized in that it is anionic surfactant, preferably from the group of C ₈ -C ₁₈ alkyl sulfates, C ₈ -C ₁₈ alkyl ether sulfates and C ₈ -C ₁₈ alkyl benzene sulfonates and mixtures thereof , contains.

12. Composition according to the preceding claim, characterized in that it contains at least one anionic surfactant in the form of its potassium salt.

13. Agent according to one of the preceding claims, characterized in that it contains nonionic surfactant, preferably from the group of the C ₈ -C ₁₈ alkyl alcohol polyglycol ethers, the alkyl polyglycosides and mixtures thereof.

14. Composition according to one of the preceding claims, characterized in that it is anionic and nonionic surfactant, preferably C ₈ -C ₁₈ alkylbenzenesulfonates, 5 C ₈ -C ₁₈ alkyl sulfates and / or C ₈ -C ₁₈ alkyl ether sulfates in addition to C ₈ - C ₁₈ alkyl alcohol polyglycol ethers and / or alkyl polyglycosides, in particular C ₈ -C ₁₈ alkyl benzene sulfonates in addition to C ₈ -C ₁₈ alkyl alcohol polyglycol ethers.

15. Agent according to one of the preceding claims, characterized in that it contains one or more cationic surfactants.

16. Composition according to one of the preceding claims, characterized in that there are additional builders, preferably from the group of alkali metal gluconates, nitrilotriacetates, carbonates and bicarbonates, and alkali metal and alkaline earth metal hydroxides, ammonia and amines, in particular mono- and triethanolamine, or s their mixtures.

17. Composition according to the preceding claim, characterized in that it contains potassium hydroxide as an additional builder.

18. Agent according to one of the preceding claims, characterized in that it contains one or more perfumes in an amount of 0.1 to 5, preferably 0.2 to 3, 0 in particular 0.5 to 2, particularly preferably 1 to 1.5 % By weight.

19. A method for producing an agent according to any one of the preceding claims by mixing directly from its raw materials, then mixing and finally standing the agent to separate the temporary emulsion.

5 20. Use of 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 an upper aqueous phase II which is immiscible with this phase and which can be temporarily converted into an emulsion by shaking, as well as citric acid and / or contains at least one citrate for cleaning hard surfaces.

21. Use of citric acid and / or at least one citrate in 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 which is immiscible with this phase and which temporarily shakes into 5 shakes an emulsion can be transferred as a phase separation aid and / or to reduce turbidity in the area of the boundary layer between phases I and II.

22. Use according to the preceding claim, characterized in that

Potassium citrate and / or citric acid in combination with potassium hydroxide 30 is used.

23. A process for the preparation of 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 which is immiscible with this phase and which can be temporarily converted into an emulsion by shaking. characterized in that citric acid and / or at least one

Citrate is used as an aid for separating the phases and / or for reducing turbidity in the area of the boundary layer between phases I and II.

24. The method according to the preceding claim, characterized in that potassium citrate and / or citric acid is used in combination with potassium hydroxide.

25. Product containing an agent according to one of the preceding agent claims and a spray dispenser.