WO2001021753A1 - Anti-microbial, aqueous, multi-phase cleaning agent - Google Patents

Abstract

The invention relates to an aqueous, liquid, multi-phase, surface-active cleaning agent with at least two continuous phases. Said cleaning agent has at least one lower aqueous phase I and one upper aqueous phase II, which is immiscible with phase I, can be temporarily converted to an emulsion by agitation and contains at least one anti-microbial active ingredient. The cleaning agent, together with a spray dispenser form a product which can be used to clean and/or disinfect or hygienically treat hard surfaces and can be prepared directly from its raw materials by first mixing them and subsequently leaving the agent to stand, in order to separate the temporary emulsion.

Description

 "Antimicrobial aqueous multiphase detergent"

The invention relates to antimicrobial aqueous multiphase liquid cleaning agents which can be temporarily emulsified by shaking, their use for cleaning and / or disinfection or sanitation of hard surfaces, a product containing the agent and a process for their production.

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 (e.g. citrates, gluconates, soda, polycarboxylates) 0 to 10% by weight of hydrotropes (e.g. alcohols, urea), 0 to 10% by weight water-soluble solvents (e.g. alcohols, glycol ethers) and optionally u. a. Contain skin protection agents, dyes and fragrances. For use in the sanitary sector as so-called bathroom cleaners, however, such cleaning agents are often acidified by adding acids in order to be able to remove lime and water stains better. 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 in the form of homogeneous, stable solutions or dispersions. However, the use of certain, in particular hydrophobic, components in such cleaning agents to improve cleaning performance can result in this homogeneity being lost and inhomogeneous agents being obtained, the acceptance of which can be assessed as low by the consumer. In such cases, alternative formulations are required which, despite their inhomogeneity, have a defined external appearance and application form which is acceptable to the consumer. 1

In addition to the high primary cleaning effect of such a cleaning agent, an antimicrobial effect is also increasingly expected today. For this purpose, antimicrobial agents, for example surface-active quaternary compounds, are incorporated into the cleaning agents. The use of antimicrobial agents usually limits the flexibility in the formulation of a cleaning agent significantly, since, for example, the pH must be adapted to the antimicrobial agents and, depending on the antimicrobial agent, there are incompatibilities with certain other ingredients, such as the incompatibility of surface-active quaternary compounds with the highly effective anionic surfactants. Therefore, the antimicrobial effect is usually realized at the expense of the cleaning effect.

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,

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 contained as surfactants, preferably at least one anionic surfactant being contained.

From German Offenlegungsschriften 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 paraffm oil and being able to be mixed briefly by mechanical action. The object of the present invention was to provide storage-stable agents with high cleaning performance and antimicrobial activity for cleaning and / or disinfection or sanitation of hard surfaces in an easily manageable form which is acceptable to the consumer.

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 which is immiscible with this phase and can be temporarily converted into an emulsion by shaking, and the at least one contains antimicrobial agent.

The invention also relates to the use of an agent according to the invention for cleaning and / or disinfecting or sanitizing hard surfaces.

In the context of the teaching according to the invention, the terms disinfection, sanitation, antimicrobial action and antimicrobial active substance have the customary meaning as used, for example, by KH Wallhäußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th edition - Stuttgart; New York : Thieme, 1995) is reproduced. While disinfection in the narrower sense of medical practice means the killing of - theoretically - all infectious germs, sanitation means the greatest possible elimination of all - including the saprophytic - germs, which are normally harmless to humans. The extent of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial agent content or increasing dilution of the agent for use.

In the context of the present invention, temporary is understood to mean that preferably 90% of the demixing of the emulsion formed by shaking into the separated 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 segregation into the phase state before shaking is carried out within a further 15 minutes to 50 hours.

Furthermore, in the context of the present invention - unless expressly stated otherwise - the use of a salt as well as the use of the T

corresponding acid / base pair of the salt, which only gives the salt or its solution in situ with neutralization, even if the respective alternative is not always explicitly formulated in the present teaching. In this sense, sodium citrate and the combination of citric acid / sodium hydroxide are equivalent alternatives.

Finally, if a specific component can be used for various purposes within the scope of the present invention, 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.

In addition to an antimicrobial effect, the agents according to the invention are notable for high cleaning performance, in particular on greasy soiling, in the case of diluted and undiluted use. The multi-phase, in particular two-phase, enables the realization of an antimicrobial effect and at the same time high cleaning performance. A particular advantage is the low foaming power, which has a positive effect on the cleaning performance, of the agents according to the invention without the addition of foam inhibitors such as soaps. In addition, the agents show favorable residue behavior. The individual phases on average are stable for a long time without z. B. form deposits, and the transfer into a temporary emulsion remains reversible even after frequent shaking. 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 solvents, solubilizers or emulsifiers, in particular the hydrophobic components and perfume oils described below. In addition, the multi-phase, in particular two-phase, enables the chemical stability of the agent to be improved by separating ingredients into separate phases.

Antimicrobial agent

For the antimicrobial activity, the agent according to the invention contains at least one antimicrobial active ingredient, preferably selected from the groups of alcohols, Aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, surface active agents, pyridine derivatives, pyridine derivatives Compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides, in particular selected from ethanol, n-propanol, i-propanol , 1, 3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chloro-henol, 2,2'-methylene-bis- (6- bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '- (1st , 10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis- (4-chloro r-phenyl) -3, 12-diimino-2,4, 11, 13-tetraazatetrade-candiimidamide, antimicrobial quaternary surface-active compounds, guanidines, amphoterics, particularly preferably at least one antimicrobial-active surface-active quaternary compound, most preferably with an ammonium sulfonium -, phosphonium, iodonium or arsonium group, as described, for example, by KH Wallhäußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th Ed. - Stuttgart; New York: Thieme, 1995).

The agent according to the invention particularly preferably contains at least one quaternary ammonium compound (QAV) with an antimicobial action according to the general formula (R'XR ") ^") ^) ^ XT, in which R ¹ to R ^{1V are} identical or different C ¹ -C ₂₂ -alkyl radicals , C ₇ -C ₈ aralkyl radicals or heterocyclic radicals, with two or in the case of an aromatic integration as in pyridine even three radicals together with the nitrogen atom the heterocycle, for. B. a pyridinium or imidazolinium compound form, represent and X ^~ halide ions, sulfate ions, hydroxide ions or similar anions. For an optimal antimicrobial effect, at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV are by reacting tertiary amines with alkylating agents, such as. B. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with one long alkyl residue and two Methyl groups are particularly easy to achieve, and the quaternization of tertiary amines with two long residues and one methyl group can also be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkon B (m, /> - dichlorobenzyldimethyl-Ci2-alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyl-dodecyl-bis- (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57-09-0), benzetonium chloride (N, N -Dimethyl-N- [2- [2 - [^ - (l, l, 3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] - benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chlorides such as di - «- decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5 ) and thiazoline iodide (CAS No. 15764-48-1) and their mixtures. Particularly preferred QAV are the benzalkonium chlorides with C ₈ -C ₈ -alkyl radicals, in particular C ₂ -C] ₄ -alkyl-benzyl-dimethylammonium chloride.

In a further particularly preferred embodiment of the invention, the agent contains at least one antimicrobial acid, preferably organic acid, particularly preferably selected from the group comprising undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, formic acid and acetic acid, as the antimicrobial agent (s) and mixtures thereof, most preferably selected from the group comprising lactic acid, benzoic acid, salicylic acid and formic acid and mixtures thereof, in particular mixtures of salicylic acid with formic acid, lactic acid and / or benzoic acid, for example mixtures of salicylic acid with formic acid.

The content of at least one antimicrobial active ingredient, preferably at least one surface-active quaternary compound and / or an antimicrobial acid, in particular at least one surface-active quaternary ammonium compound and / or an organic acid, is usually 0.1 to 10% by weight, preferably 0.2 to 5% by weight, in particular 0.5 to 3% by weight, particularly preferably 1 to 2% by weight, for example 1.5% by weight.

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 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 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 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, particularly preferably 60: 40 to 40: 60, extremely preferably 55: 45 to 45: 55, for example 50:50.

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 0.01 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, particularly preferably 3 to 12% by weight .-%, very preferably 5 to 10 wt .-%, wherein any antimicrobial surface-active compounds contained are not considered in terms of quantity as surfactants but as antimicrobial agents.

Nonionic surfactants

Suitable nonionic surfactants, so-called nonionic surfactants, are, for example, C ₆ -C ₂₂ alkyl alcohol polyglycol ethers, alkyl polyglycosides and nitrogenous surfactants or also sulfo-succinic acid di-C] -C ₂ -alkyl esters or mixtures thereof, especially the first two. The compositions contain nonionic surfactants in amounts, based on the composition, of usually 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 14% by weight, particularly preferably 3 to 12% by weight. %, most preferably 5 to 10% by weight, for example 8.5% by weight. Presumably, non-ionic surfactants with their nonionic character advantageously contribute to the fact that the individual phases are stable on average over a long period of time without z. B. form deposits, and the transfer to a temporary emulsion remains reversible even after frequent shaking.

C ₆ -C ₂₂ alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be described by the formula II, R ^I O- (CH ₂ CH (CH ₃ ) O) _p (CH ₂ CH2θ) _e -H, 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,? stands 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, the branched-chain primary alcohols obtainable by oxosynthesis, or to fatty alcohols, in particular 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 ₄ fatty alcohol + lPO-r-6EO ether (p = 1, e = 6), -C -C ₆ - fatty alcohol + 5.5-EO (p = 0, e = 5.5) , Cι ₂ -Cι ₈ fatty alcohol + 7EO ether (p = 0, e = 7) and isodecanol + 6-EO (R ¹ = isomer mixture of Cι ₀ -oxoalcohol residues, /? = 0, e = 6) and their mixtures , In preferred mixtures, at least one representative of formula II with a linear alkyl radical R ^{1 is combined} with at least one representative of formula II with a branched alkyl radical R ¹ , for example

and isodecanol + 6-EO. It is further preferred here that the linear alkyl radical comprises more carbon atoms than the branched alkyl radical.

End-capped C ₆ -C ₂₂ 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 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 corresponding to formula II in which R ¹ is a technical fatty alcohol radical, preferably Ci _{2 /} ι ₄ -Kokosalkylrest,> 0, and e is 5 to 10 are provided, which are closed with a Butylgmppe.

Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula III, R OfG] _* , in which R 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 is 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 can assume the values x = 1 to 6, the value x for a certain alkyl glycoside is an analytically determined arithmetic 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 (formula III) can be derived from primary alcohols having 8 to 22, 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.

-y

However, the alkyl or alkenyl radical R 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 surfactants may be included as further nonionic surfactants, e.g. B. fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides which have 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 the lauric acid, myristic acid and palmitic acid monoethanolamides.

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

Suitable anionic surfactants are the preferred C ₆ -C ₂₂ alkyl sulfates, C ₆ -C ₂₂ alkyl ether sulfates, ie the sulfation products of the alcohol ethers of the formula II, and / or anionic sulfonic acids or their salts, the sulfonates, but also C ₆ - C ₂₂ -carboxylic acid amidethersulfate, sulfosuccinic acid-C ι -C 1 - alkyl, C ₆ -C ₂₂ - ether carboxylates Alkylpolyglykol-, C ₆ -C 22 N-acyl taurides, C ₆ -C ₂₂ N-sarcosinates and C ₆ -C ₂₂ alkyl isethionates or mixtures thereof.

Anionally active sulfonic acids in the sense of the teaching according to the invention are sulfonic acids of the formula R-SO ₃ H which have a partially or completely straight-chain and / or branched and / or cyclic and partially or completely saturated and / or unsaturated and / or aromatic C ₆ . ₃₂ -C hydrocarbon radical R carry, for example C _6-22 alkane sulfonic acids, C ₆ - ₂₂ α-olefin sulfonic acids, sulfonated C ₆ -C ₂₂ fatty acids and

C _6- ι ₀ -arenesulfonic acids such as Cι _-22- alkylbenzenesulfonic acids or Cι- ₂₂ -alkylnaphthalenesulfonic acids, preferably linear C _8- ι ₆ -alkylbenzenesulfonic acids, especially linear C _10- ι ₄ -alkyl, C _10- i ₃ -alkyl - And Cπ-alkylbenzenesulfonic acids.

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 anionic sulfonic acids also in the form of the acid, for. B. dodecylbenzenesulfonic acid, Cio-Cπ-alkyl-benzenesulfonic acid and / or Cιo -CC ₄ -alkylbenzenesulfonic acid used. When using sulfonic acid, this is usually done in situ with one or more corresponding bases, e.g. B. alkali metal and alkaline earth metal hydroxides, especially sodium, potassium and magnesium hydroxide, and ammonia or mono-, di-, tri- or tetraalkylamine, - depending on the pH of the agent to be adjusted partially or completely - neutralized to the aforementioned salts Agents contain one or more anionic surfactants in amounts, based on the composition, of 0 to less than 30% by weight, preferably 0.1 to 20% by weight, in particular 0.5 to 10% by weight, most preferably 0.7 to 5% by weight, for example 1 or 1.2% by weight.

When using the particularly preferred alkylbenzenesulfonic acids, especially with a high sodium chloride content and / or when adjusting the pH, it can also be used AI

Sodium hydroxide, turbidity in the area of the interface between phases I and II. The use of citric acid or citrate counteracts this problem. A further improvement occurs 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 and low or low haze of the phase boundary layer.

Because of their foam-suppressing and thickening properties, the agents according to the invention can also use soaps, i.e. Alkali or ammonium salts of saturated or unsaturated C6-C22 fatty acids. The soaps can be used in an amount of up to 5% by weight, preferably from 0.1 to 2% by weight.

When using cationic antimicrobial agents such as surface-active quaternary compounds, especially quaternary ammonium compounds, however, the agents preferably contain as little anionic surfactants as possible, including soaps, and in a particularly preferred embodiment of the invention are completely free of anionic surfactants, including soaps, since these often have more or are less compatible with the antimicrobial quaternary compounds. It is self-evident for the person skilled in the art that he must verify the compatibility of the anionic surfactants with the antimicrobial active substances with regard to the germ-reducing effect.

Amphoteric surfactants

Suitable amphoteric surfactants are, for example, betaines of the formula R) (R ⁴ ) (R) N ⁺ CH ₂ COO ^" , in which R ^{3 is} an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms and R ⁴ and R, optionally interrupted by heteroatoms or heteroatom groups ⁵ identical or different alkyl radicals with 1 to 3 carbon atoms, in particular C ₀ -C ₂₂ -alkyl-dimethylcarboxymethylbetaine and Cn-Cπ-alkyl-amidopropyl-dimethylcarboxymethylbetaine. The compositions contain one or more amphoteric surfactants in amounts, based on the composition, of 0 to 15% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight. Cationic surfactants

Suitable cationic surfactants are, for example, the surface-active quaternary compounds described above, in particular the surface-active quaternary ammonium compounds. If surface-active quaternary compounds are not already present as antimicrobial active ingredients, the compositions contain one or more 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.

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, but also have a positive effect on the phase separation and its reversibility. Here, the defined inhomogeneous form of the multiphase agents according to the invention enables stable incorporation - in particular also in larger amounts - of the hydrophobic components which are used in single-phase aqueous solutions or stable emulsions or microemulsions only through the use of solvents, solubilizers or emulsifiers in mostly very limited amounts can be incorporated stably.

Suitable hydrophobic components are, for example, dialkyl ethers with the same or different C ₄ -C ₄ -alkyl radicals, in particular linear dioctyl ether; with aliphatic or aromatic alcohols, e.g. As methanol, ethanol, propanol, n-butanol, tert-butanol or phenol, or carboxylic acids, e.g. B. acetic or carbonic acid, etherified-esterified and / or etherified monomeric or homo- or heteropolymeric, especially monomeric and homodi- and trimeric, C ₂ - - alkylene glycols, for example those under the trade name Dowanor from Dow Chemical and the under the trade names Arcosolv and Arconate from Arco Chemical and hereinafter referred to with their / NCT name in accordance with the International Dictionary of Cosmetic Ingredients by The Cosmetic, Toiletry, and Fragrance Association (CTFA), e.g. B. Butoxydiglycol (Dowanol ^® DB), Methoxydiglycol (Dowanof DM), PPG-2 Methyl Ether (Dowanof DPM), PPG-2 Methyl Ether Acetate (Dowanof DPMÄ), PPG-2 Butyl Ether (Dowanof DPnB), PPG-2 Propyl Ether (Dowanof DPnP), Butoxyethanol (Dowanof EB), Phenoxyethanol (Dowanof EPh), Methoxyisopropanol (Dowanof PM), PPG-1 Methyl Ether Acetate (Dowanof PMA), Butoxyisopropanol (Dowanof PnB), Propylene Glycol Propyl Ether (Dowanof PnP), Phenoxyisopropanol (Dowanof PPh), PPG-3 Methyl ether (Dowanof TPM) and PPG-3 butyl ether (Dowanof TPnB) as well as ethoxyisopropanol (Arcosolv ^® PE), tert-butoxyisopropanol (Arcosolv ^® PTB), PPG-2 tert-butyl ether (Arcosolv ^® DPTB) and propylene carbonate (Arconate ^® PC), in particular PPG-2 propyl ether (dipropylene glycol n-butyl ether, Dowanof DPnP); Hydrocarbons with a boiling range of 100 to 300 ° C, especially 140 to 280 ° C, for. B. 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 etherified or esterified mono- or polymeric C ₂ -C ₄ -alkylene glycols, of dialkyl ethers and hydrocarbons, of dialkyl ethers and ethereal oils, of hydrocarbons and ethereal oils, of dialkyl ethers and hydrocarbons and essential oils and of these mixtures. Particularly preferred mixtures of hydrophobic components are mixtures of dialkyl ethers and etherified or esterified mono- or polymeric C ₂ -C ₄ -alkylene glycols, for example di-π-octyl ether and dipropylene glycol - «- butyl ether (PPG-2 propyl 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 , most preferably 3 to 8% by weight, e.g. B. 5% by weight. λ≤

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, as strong electrolytes which increase the ionic strength, support the phase separation through the salt effect. Sodium chloride has proven to be particularly effective here. 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.

Surprisingly, it was found that the use of acids, preferably organic acids such as carboxylic acids and / or inorganic acids, particularly preferably at least one acid selected from the group consisting of salicylic acid, lactic acid, benzene acid and boric acid, also stabilizes the phase separation of the agents.

If additional acids are added, the proportion of citric acid can be reduced, for example, while maintaining a stable phase separation of the cleaning agent.

When using 13% by weight of citric acid, 9% by weight of monoethanolamine, based on the detergent composition, and the presence of Na benzoate, a phase separation of the detergent composition from about 1/3 lower to about 2/3 upper phase can be obtained. When using lactic acid, the phase ratio of the cleaning agent can be adjusted to about 40 parts lower and 60 parts upper phase with the same citric acid contents.

By reducing the water content of the detergent composition, the phase ratio can be shifted to 30 parts of the upper and 70 parts of the lower phase with a proportion of 12% by weight of citric acid and a suitable amount of monoethanolamine.

When using 3% by weight Na benzoate, 14% by weight citric acid and 10% by weight monoethanolamine, a phase ratio of

Prepare detergent composition of 1: 1. When using 3% by weight of lactic acid, 13% by weight of citric acid and 12% by weight of monoethanolamine, the proportion of the lower phases can be increased.

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, and sodium and potassium carbonate and bicarbonate, and also alkali metal and alkaline earth metal hydroxides, in particular sodium and potassium Ammonia and amines, especially mono- and triethanolamine, or their mixtures. 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-l, 2,4-tricarboxylic acid, phosphonates and phosphates, for example the sodium salts of methane diphosphonic acid, the pentasodium triphosphate known as sodium tripolyphosphate or Sodium hexametaphosphate such as a mixture of condensed orthophosphates of the formula I, in which n stands for an average of about 12.

Particularly preferred builders are citric acid or citrates, in particular sodium citrate, and aminotrimethylenephosphonic acid and mixtures thereof, in which the weight ratio of citric acid or citrate, based on citric acid, to aminotrimethylenephosphonic acid is preferably 1 to 10 to 100 to 1, in particular 1 to 1 up to 40 to 1, particularly preferably 2 to 1 to 20 to 1, most preferably 5 to 1 to 10 to 1, for example 8 to 1.

If the builder is also intended to act as a pH-stabilizing buffer, alkali metal and alkaline earth metal carbonates and bicarbonates, preferably sodium carbonate (soda), are preferred, in particular together with citric acid or - optionally generated in situ from citric acid and hydroxide - citrate, e.g. As sodium or potassium citrate, particularly preferably together with the mixture of citric acid or citrate and aminotrimethylenephosphonic acid 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 compositions contain builders in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, particularly preferably 3 to 12% by weight , most preferably 5 to 10% by weight, for example 7.3% by weight. The 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 trialkanolarnmonium 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 IH ₂ O instead of citrate. The builder salts also act as phase separation aids. The complexing builders also serve in particular for ensure a clear application solution when using the agents with hard water.

A preferred builder is - optionally generated in situ from citric acid and hydroxide - citrate from the group of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium citrates, preferably mono-, di- or triethanolammonium citrates, or their Mixtures, especially sodium citrate and / or potassium citrate, since citrates combine builder and phase separation aid properties in a particularly advantageous manner.

An advantageous alkaline 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 non-opacity of the phase boundary layer.

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 significantly improve the cleaning performance - in particular in amounts above 0.9% by weight. Perfume oils in particular regularly cause problems when they are incorporated, especially in larger quantities, into single-phase aqueous solutions or stable emulsions or microemulsions and make it necessary to use solvents, solubilizers or emulsifiers, but without being able to stabilize larger perfume oil contents. This is where the great advantage of the defined inhomogeneous form of the multi-phase agents according to the invention comes into play, which enables the perfume oils to be incorporated in a stable manner, especially in larger quantities.

Accordingly, the invention furthermore relates to the use of perfume oils in a liquid multiphase cleaning agent with at least two continuous phases, which has at least one lower aqueous phase I and one upper aqueous or non-aqueous phase II which is immiscible with this phase and temporarily shakes into one by shaking Emulsion can be transferred to improve cleaning performance. The agent according to the use is preferably an aqueous liquid multiphase surfactant-containing cleaning agent with at least two continuous phases, the at least one lower aqueous phase I and one with this phase has immiscible upper aqueous phase II, in particular an agent according to the invention.

The components of the suitable perfume oils described in the following are placed in parentheses, e.g. B. "(5.0)", which is exemplary information on the composition of the respective perfume oil in wt .-% o, based on the perfume oil. "Geraniol (105.0)" means that the perfume oil geraniol z. B. in an amount of 105.0 wt .-% o can contain.

A suitable perfume oil with a fresh fruity fragrance contains, for example, Dynascone 10 (5.0), Cyclovertal (7.5), Hexylacetat (35.0), Allylheptanoat (200.0), Amylbutyrat (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), isobomylacetate (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), β-pinene (20.0), γ-terpinene (95.0) and Litsea Cubeba oil (55.0) ,

The content of one or more perfume oils is usually 0.1 to 15% by weight, preferably 0.5 to 10% by weight, in particular 1 to 5% by weight, particularly preferably 1.5 to 4% by weight , most preferably 2 to 3% by weight, e.g. B. 2.5% by weight.

enzymes

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

Customary in detergents and cleaning agents enzymes, for example proteases (z are suitable. B. BLAP ^® L 260, S 260 BLAP ^® SLD, BLAP S 260 ^® ALD, BLAP S 260 ^® LD and BLAP S 260 from Biozym or Dura∑ym, Savinase ^® and Alcalase ^® from Novo Nordisk), amylases (e.g. Termamyf from Novo Nordisk), cellulases (e.g. KAC 500 ^® from Fa Kao, Celluzyme ^® from Novo Nordisk), lipases (e.g. Lipolase 100 L ^® and Lipolase 100 T ^® from Novo Nordisk) and peroxidases and reductases.

The nonionic surfactants in general, and the alkyl polyglycosides improve in particular the storage stability of the enzyme-containing embodiment as well as the citric acid or its salts and the hydrophobic components, in particular the - optionally etherified or esterified - mono- or polymeric _C2-C4 alkylene glycols, e.g. , B. the products sold under the trade names Dowanof, Arcosolv ^® and Arconate ^® 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 terms of ionic strength - less ionic upper phase II.

PH value

The pH of the agents according to the invention can be varied over a wide range, from strongly acidic to neutral to highly alkaline, but a range from 1 to 12, in particular 2 to 11, is preferred accessible through routine tests - pH dependence of the antimicrobial effect of the antimicrobial agent (s) used must be taken into account. Thus, the pH should be as optimal as possible for the antimicrobial effect of the respective antimicrobial active ingredient (s) and / or if a specific pH value is specified for a specific cleaning purpose, the antimicrobial active ingredient (s) should be selected accordingly. In the context of the present invention, the pH of the agents according to the invention is to be understood as the pH of the agent in the form of the temporary emulsion.

In a neutral embodiment, the pH is above 6 to below 8, preferably 6.5 to 7.5 and in particular about 7.

In a preferred embodiment of the invention, the agents are alkaline with a pH of 8 to 12, preferably 8 to 11, in particular 8 to 10.5, for example between 8 and 9, e.g. B. 8.3, for moderate alkalinity or over 9 to 10.5, 11 or even 12, e.g. B. 10, for greater alkalinity. This is particularly preferred when using antimicrobial quaternary compounds, since their antimicrobial activity generally increases with increasing pH, while occasionally they are completely absent in the acidic range below pH 3.

Suitable pH regulators are, on the one hand, acids such as the mineral acids, e.g. B. hydrochloric acid, but especially citric acid, and on the other hand the aforementioned 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 special embodiment, small amounts of corresponding buffer substances, in the alkaline embodiment described, for example, soda or sodium bicarbonate.

In a likewise preferred embodiment of the invention, the agents are acidified with a pH of 1 to 6, preferably 2 to 6, in particular 3 to 5.5, particularly preferably 3.5 to 5, for example 4, 4.4 or 4 ; 5. In order to set such a pH, the agents contain at least one acid. Inorganic acids, for example the mineral acids, for. Hydrochloric acid, and organic acids, for example saturated or unsaturated Cι _-6 mono-, di- and tricarboxylic acids and hydroxycarboxylic acids with one or more Hydroxygrappen, z. B. citric acid, maleic acid, formic acid and acetic acid, amidosulfuric acid, C _6-22 fatty acids and anionic sulfonic acids, and mixtures thereof, e.g. As that available under the trade name Sokalan ^® DCS from the Fa. BASF succinic glutaric acid-adipic acid mixture. Particularly preferred acids are citric acid, preferably used in the form of its monohydrate citric acid-IH ₂ O, and the anionic sulfonic acids and combinations of citric acid with one or more anionic sulfonic acids, in particular with alkylarene sulfonic acids. Citric acid advantageously combines acid, builder and phase separation aid properties, while the anionic sulfonic acids act simultaneously as an acid and an anionic surfactant. Optionally, one or more alkalis can also be used, for example the alkali metal, alkaline earth metal and Ammonium hydroxides and carbonates and ammonia, preferably sodium and potassium hydroxide, with potassium hydroxide being particularly preferred.

viscosity

The viscosity of the agent according to the invention at 20 ° C. is preferably 5 to 1,000 mPa-s, in particular 10 to 500 mPa-s, particularly preferably 10 to 200 mPa-s, measured using a Brookfield rotary viscometer of the LVT or LVDV-II + type with small sample adapter at a speed of 30 min ^"1 , whereby the Brookfield spindle used as the measuring body should be selected so that the torque is in a favorable range and the measuring range is not exceeded. In this context spindle 31 is preferred and - if required for viscosities above about 240 mPa-s - preferably use spindle 25.

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 (/ NC7 name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association ( CTFA): Carbomer), also called Carboxyvinylpolymers are called. Such polyacrylic acids are available, inter alia, from BFGoodrich under the trade name Carbopof, e.g. B. Carbopof 940 (molecular weight approx.4,000,000), Carbopof 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 of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C _{4 -4} -alkanols, to which, for example, the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (G4S 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 Acusof are available, e.g. B. the anionic non-associative polymers Aculyn ^® 33 (crosslinked), Acusof 810 and Acusof 830 (CAS 25852-37-3); (ii) Crosslinked high molecular acrylic copolymers, for example the copolymers of C ₁₀ crosslinked with an allyl ether of sucrose or pentaerythritol. ₃₀ -alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple esters (/ NC / acrylates / C 10-30 alkyl acrylate crosspolymer), preferably formed with C -alkanols, and which belong, for example, from BFGoodrich are available under the trade name Carbopof, e.g. B. the hydrophobized Carbopof ETD 2623 and Carbopof 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, carrageenan and their salts, guar, guaran, tragacant, gellan, ramsan, dextran or xanthan and their derivatives, e.g. B. propoxylated guar, and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide rubber, for example starches of various origins and starch derivatives, e.g. B. hydroxyethyl starch, starch phosphate ester or starch acetate, or carboxymethyl cellulose or their sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate. A particularly preferred polymer is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 to 15 x 10 ⁶ and is available, for example, from Kelco under the trade name Keltrof, e.g. , B. as cream-colored powder Keltrof T (transparent) or as white granulate Keltrof RD (Λeadily E> ispersable).

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, solvents (e.g. ethanol, isopropanol, glycol ether), solubilizers, hydrotropes (e.g. sodium cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), cleaning enhancers, disinfectants, antistatic agents, preservatives (e.g. B. glutaraldehyde), bleaching systems and dyes as well as opacifiers or skin protection agents, as described in ΕP-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 auxiliary and additive and can be, for example, up to 0.001% by weight and less for dyes. 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.

The agents according to the invention can be prepared by mixing them directly from their raw materials, then mixing them and then standing the agent to separate the temporary emulsion. The invention accordingly furthermore 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. The reversible phase separation is caused by the complex interplay of a number of components and their characteristics are determined. The surfactant present can already lead to phase separation according to the invention. If necessary, only the additional use of hydrophobic component, builder and / or perfume causes the phase separation. Otherwise the use of phase separation aids is required.

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 referenced in this regard and the contents of which are hereby incorporated into this application.

Particularly suitable detergent compositions as shown in Tables 2-9 can be used as C ₂ -Ci ₄ fatty alcohol-1, 3 EO ether sulfate sodium salt Texapon SPN 70, as alkane sulfonate sodium salt Hostapur SAS 60, as alkyl polyglycoside APG 600 UP-W, as betaine derivative Dehyton PK 45 OKA and as fatty alcohol ethoxylate dehydol PO 5.

B e i s p i el e

The agents E1 to E51 according to the invention were produced as described above. Tables 1-9 show the composition in% by weight, pH value and the quantified volume ratio of the upper phase II to the lower phase I. Unless stated otherwise, the compositions contain E1 to E51 ad 100. The pH adjustment in E1 to E51 can be carried out, for example, if necessary by adding hydroxides such as NaOH and / or KOH.

The agents E1, E2 and E3 contained a perfume oil with an aromatic fragrance, consisting of 700.0% by weight of orange oil, 130.0% by weight of o-pinene, 20.0% by weight of o-pinene , 95.0% by weight of γ-terpinene and 55.0% by weight of o Litsea Cubeba oil.

Analogous to the means El ', E2' and E3 ', in contrast to the means El, E2 and E3, contain a perfume oil with a fresh, fruity note, consisting of 5.0% by weight of Dynascone 10, 7.5% by weight Cyclovertal, 35.0% by weight of hexyl acetate, 200.0% by weight of ₀ allyl heptanoate, 5.0% by weight of amyl butyrate, 10.0% by weight of prenylacetate, 70.0% by weight of o Aldehyde C 14 SOG, 15.0% by weight of manzanate, 30.0% by weight of melusate, 200.0% by weight of ortho butylcyclohexyl acetate, 5.0% by weight of cinnamaldehyde, 10.0 % By weight o isobomylacetate, 2.5% by weight o dihydrofloriffone TD, 100.0% by weight o floramate, 30.0% by weight o phenylethyl alcohol, 105.0% by weight o geraniol, 150, 0% by weight of cyclohexyl salicylate and 20.0% by weight of citronellol.

In contrast to the agents El, E2 and E3, other similar agents El ', E2' and E3 'contain a perfume oil with a fresh, floral fragrance, consisting of 250.0% by weight of bergamot oil, 50.0% by weight o Messina lemon oil, 2.0% by weight o Citronellal, 50.0% by weight o Sweet orange oil, 50.0% by weight o Lavender oil, 50.0% by weight o Terpineol, 100.0% by weight -% o Lilial, 80.0% by weight o Phenylethyl alcohol, 100.0% by weight o Citronellol, 20.0% by weight o Geraniol, 60.0% by weight o Benzyl acetate, 50.0%. -% o Isoraldein 70, 30.0% by weight o Ylang, 1.0% by weight o Ambroxan 10% o in IPM, 47.0% by weight o Heliotropin and 60.0% by weight o Habanolide , f

Table 1

Composition El E2 E3

Ci ₂ -C ₁₆ fatty alcohol + 5.5EO 2 - -

Ci ₂ -Cι ₈ fatty alcohol + 7EO - 1 1

Dodecylbenzenesulfonic acid - 3 3

Isodecanol + 6EO 6.5 - -

PPG-2 butyl ether 5.0 - -

C _n -Ci ₃ isoparaffins (/ NC / C9-13 - 2 2 isoparaffin) ^[a]

C ₁₂ -C ₁₄ - alkyl-benzyl-dimethyl-1,5 - - ammonium chloride

Salicylic acid - 0.6 0.6

Formic acid - 1.6 -

Aminotrimethylene phosphonic acid 0.5 - -

Citric acid H ₂ θ 4.0 3.4 8

ΝaOH 2.6 - -

KOH - 1.1 2.5

Sodium carbonate 0.2 - -

Isopropanol - 2 2

Perfume oil (see below) 2.5 1 1

Dye <0.001 ^{| bl} <0.001 ^{| c |} <0.001 ^{| cl}

Water, fully desalinated ad \ 00 ad 100 ad 100 pH 9.9 3.6 3.8

Appearance Phase II / Phase I clear / clear clear / clear clear / clear Volume ratio II: I 50:50 50:50 50:50 Color Phase II / Phase I green / colorless blue / colorless blue / colorless

^[a] Shellsof T (Shell Chemicals in Europe, DE) with a boiling range from 200 to 260 ° C

^[b] Color index name: Cl 42080 or Acid Blue 7

^[b] Color index name: Cl 61568 or Solvent Blue 104

All agents showed two continuous phases, which temporarily formed a creamy-looking emulsion when shaken. Even after repeated shaking, separate phases formed again when left standing. The storage stability was checked by assessing the medium after four weeks of storage at room temperature of 20 ° C, at elevated temperature of 40 ° C or in the cold at a temperature of 5 ° C. The agent showed - regardless of the storage temperature - no visually perceptible change, in particular the agent could still be reversibly transferred into the temporary emulsion by shaking.

The agents were assessed by the test subjects as visually appealing and easy to use and achieved good cleaning results - in undiluted as well as in diluted form - especially when removing greasy dirt in the form of the dirt caused in the kitchen by the preparation of greasy or oily dishes. ,

Table 2: 2-phase antibacterial detergent compositions

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

color = colorless u = lower phase o = upper phase

Investigation of the antimicrobial effectiveness

The antimicrobial effectiveness of the agents El to E51 was examined with a view to the reduction in the number of live germs in the quantitative suspension test based on the test method DIN EN 1276.

The test standard DIN EN 1276 describes a test method for and the

Minimum requirements for the bactericidal effects of chemical disinfectants and antiseptic products for the food sector, industry, household and public institutions. According to this, products under simulated load and under the required test conditions (test concentration 5%; exposure time 5 minutes at 20 ° C) must contain the live germ count of the four reference strains Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 10536), Pseudomonas aeruginosa (ATCC 15442 ) and Enterococcus hirae (ATCC 10541) by at least 5 orders of magnitude. As proof of an antimicrobial effect, reduction factors of the live germ count of at least 10 ^{5 are not} required in every case and for the entire spectrum of test germs. For an antimicrobial effect based on the killing of test organisms, the significance level for reduction factors of at least 10 ^{2 must} be set, whereby no gaps in effectiveness against individual relevant test germs should be discernible.

The formulation tested in each case was examined under the load simulated for clean conditions (0.03% bovine albumin). Deviating from the requirements of DIN EN 1276, a higher bacterial count of the test microbial suspension was chosen to ensure that even when using a larger dilution step in the neutralization medium (1: 100 instead of 1:10) a bacterial count reduction of at least 5 powers of ten could be reliably determined. In addition to the stipulations of the test specification DIN EN 1276, the test batches - where relevant - were evaluated using dilution series in order to be able to numerically record reduction factors for the live germ count of <10.

For example, under the selected test conditions, Mittel El was able to reduce the number of live organisms in the test organisms Staphylococcus aureus, Escherichia coli and Enterococcus hirae to below the limit of quantification provided by the test method reduce, which corresponds to reduction factors of> 10 ⁵ . Against the Gram-negative test germ Pseudomonas aeruginosa, the agent achieved a reduction factor of the live germ count of 4.6-10 ³ .

The means E2 and E3 were able to reduce the live germ counts of all four test organisms to below the limit of quantification provided by the test method under the selected test conditions, which corresponds to reduction factors of> 10 ⁵ .

The agents E4 to E51 correspond essentially to agents E2 and E3 in their antimicrobial action.

All three agents showed a clear antimicrobial effect against all test germs.

Claims

P ate n tan voices

1. Aqueous liquid multiphase 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, characterized in that it contains at least one contains antimicrobial agent.

2. Composition according to claim 1, characterized in that it contains at least one antimicrobial acid, preferably organic acid, particularly preferably selected from the group comprising undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, formic acid and acetic acid and mixtures thereof.

3. Composition according to one of claims 1 or 2, characterized in that it contains a surface-active quaternary compound, preferably with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, in particular a quaternary ammonium compound.

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

6. Composition 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. 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 being two sharp interfaces, an upper and a lower one, are delimited from 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. Composition according to one of the preceding claims, characterized in that it contains one or more nonionic surfactants, preferably C ₆ -C ₂₂ alkyl alcohol polyglycol ethers and / or alkyl polyglycosides, in particular -C22 alkyl alcohol polyglycol ethers.

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

11. Agent according to one of claims 1 to 8, characterized in that it is free of anionic surfactants.

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

13. Agent according to one of the preceding claims, characterized in that it additionally contains hydrophobic components from the Grappe dialkyl ethers with identical or different C ₄ - to C] ₄ -alkyl radicals, in particular dioctyl ether, the etherified or esterified mono- or polymeric C ₂ - C ₄ -alkylene glycols, the hydrocarbons with a boiling range of 100 to 300 ° C, especially 140 to 280 ° C, the essential oils, especially 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, preferably from the Grappe

Contains alkali metal and alkaline earth metal chlorides and sulfates, in particular sodium and potassium chloride and sulfate, as well as ammonium chloride and sulfate or their mixtures and / or acids.

15. Composition according to one of the preceding claims, characterized in that it additionally has one or more builders, preferably from the group of alkali metal citrates, gluconates, nitrilotriacetates, carbonates and bicarbonates, and alkali metal and alkaline earth metal hydroxides, ammonia and amines, in particular mono - And triethanolamine, or mixtures thereof, in particular from the grappa of citric acid or citrates and aminotrimethylenephosphonic acid and mixtures thereof.

16. Composition according to the preceding speech, characterized in that it contains citrate from the grapple of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium citrates, preferably mono-, di- or

Triethanolammonium citrates, or mixtures thereof, in particular sodium citrate and / or potassium citrate, contains.

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

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

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.

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

21. Use of an agent according to one of the preceding agent claims for cleaning and / or disinfection or sanitation of hard surfaces.