EP1214392A1

EP1214392A1 - Multi-phase cleaning agent containing oil and/or wax

Info

Publication number: EP1214392A1
Application number: EP00966018A
Authority: EP
Inventors: Heike Wendt; Heinz-Dieter Soldanski; Jürgen Noglich
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1999-09-23
Filing date: 2000-09-15
Publication date: 2002-06-19
Also published as: AU7656300A; AR025742A1; DE19945505A1; CA2320544A1; WO2001021754A1; CO5231246A1

Abstract

The invention relates to a liquid, multi-phase cleaning agent with at least two continuous phases. Said cleaning agent has at least one aqueous phase I and one non-aqueous, liquid phase II, which is immiscible with said aqueous phase I, can be temporarily converted to an emulsion by agitation and contains in phase II a quantity of at least one oil and/or wax of up to 50 wt.- %, in relation to phase II. The cleaning agent, together with a spray dispenser form a product which can be used in a method for cleaning and/or protecting hard surfaces, in particular, of furniture. According to said method, the liquid, multi-phase cleaning agent is temporarily converted to an emulsion by agitation, is applied to the surface to be cleaned and/or protected, preferably by spraying and said surface is subsequently cleaned and/or protected using an absorbent, soft object, optionally by wiping.

Description

'Multi-phase cleaning agent with oil and / or wax'

The invention relates to multi-phase liquid cleaning agents with an oil and / or wax, which can be temporarily emulsified by shaking and can be used for cleaning and / or maintaining hard surfaces, in particular furniture, a product containing the agent and a method for cleaning and / or maintenance of hard surfaces.

The cleaning agents for hard surfaces that are common today are usually aqueous preparations in the form of a stable solution or dispersion which contain, as essential active ingredients, surface-active substances, organic solvents and, if appropriate, complexing agents for the hardness constituents of water, abrasives and cleaning alkalis. Detergents, which are primarily intended for cleaning glass and ceramic surfaces, are often formulated as solutions of the active substances in a mixture of water and water-miscible organic solvents, primarily lower alcohols and glycol ethers. Examples of such agents can be found in German Offenlegungsschrift 22 20 540, US Pat. Nos. 3,839,234 and 3,882,038 and in European Patent Applications 344 847 and 393 772. Such aqueous liquid cleaners are usually present as homogeneous, stable solutions or dispersions.

In addition to the high primary cleaning effect of such a cleaning agent, a care effect is also desired or even expected by the consumer, particularly when treating furniture. For this purpose, care ingredients, such as oils or waxes, are incorporated into the cleaning agents.

However, the use of such hydrophobic components in such cleaning agents to improve the care effect can lead to a reduction in the cleaning performance, the homogeneity of the agent being lost and inhomogeneous agents being obtained, the acceptance of which can be regarded as low by the consumer. In such cases, the alternative formulation of agents that require high cleaning stung and despite their inhomogeneity have a defined and acceptable form of appearance and application for the consumer.

German Offenlegungsschrift 39 10 170 describes compositions serving as mouthwash for the desorption of bacteria from solid surfaces and living tissues, which are in the form of a 2-phase preparation and form a temporary oil-in-water emulsion of limited life when shaken, where the aqueous phase comprises approximately 50 to 97% by weight and the water-immiscible oil phase comprises approximately 3 to 50% by weight. What is essential is a content of about 0.003 to 2% by weight of an amphiphilic cationic agent, for example a cationic surfactant, in an amount which enables the formation of the oil-in-water emulsion, this emulsion being about 10 seconds to 30 minutes collapses after their formation and separates. Anionic surfactants impair the antibacterial effect. No other surfactants are mentioned.

European patent application 0 195 336 describes shaking emulsifiable care products for sensitive surfaces, in particular plastic surfaces or compact disc disks, which in addition to an aqueous phase also contain an organic phase which consists of chlorofluorocarbon (CFRP) 1, 1, 2-trichloro- 1,2,2-trifluoroethane. The agents are also free of wax. Due to their environmentally harmful properties, especially in connection with the ozone hole, the use of CFRP should be reduced or better avoided.

The German laid-open documents 195 01 184, 195 01 187 and 195 01 188 (Henkel KGaA) disclose hair treatment agents in the form of 2-phase systems which have an oil phase and a water phase and can be mixed briefly by mechanical action, the oil phases 65 (195 01 188), 95 (195 01 187), 96.7 (195 01 187) or 98% by weight of the cyclic decamethylpentasiloxane (195 01 184) or 93.3% by weight hexamethyldisiloxane (195 01 184). However, the cleaning performance of such agents is inadequate.

The object of the present invention was to provide storage-stable agents with a high cleaning performance and a caring effect for the treatment of hard surfaces in an easily manageable and acceptable form for the consumer. In a first embodiment, the invention relates to a liquid, multi-phase cleaning agent with at least two continuous phases, which has at least one aqueous phase I and a non-aqueous liquid phase II which is immiscible with this aqueous phase and which can be temporarily converted into an emulsion by shaking, and which in phase II contains at least one oil and / or wax in an amount, based on phase II, of up to 50% by weight.

In the context of the present invention, immiscible, nonaqueous phase means a phase which is not based on water as the solvent, in the nonaqueous phase II a certain amount, based on phase II, of water of usually not more than 20% by weight, preferably not more than 15% by weight, in particular not more than 10% by weight, particularly preferably not more than 5% by weight, can be present in dissolved form.

In the simplest case, an agent according to the invention consists of a continuous aqueous phase which consists of the entire phase I and a continuous non-aqueous liquid 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 continuous aqueous phase of the agent, and one other part than discontinuous phase I is emulsified in the continuous non-aqueous phase II. The same applies to phase II and other continuous phases.

In a second embodiment, the invention relates to a method for cleaning and / or maintaining hard surfaces, in particular furniture, in which a cleaning agent according to the invention is temporarily converted into an emulsion by shaking onto the surface to be cleaned and / or cared for, preferably by spraying, applied and this surface is then cleaned and / or maintained if necessary by wiping with an absorbent soft object.

The agents according to the invention combine a high cleaning performance and a caring effect. They show separate phases which can be emulsified for use, remain homogeneous during use and then form separate phases again. Furthermore, the agents according to the invention are distinguished by an overall high storage stability. The individual phases are stable on average over a long period of time that, for example, deposits were formed and the transfer to a temporary emulsion remains reversible even after frequent shaking. In addition, the physical form of the agents according to the invention does not address the problem of stabilizing an agent formulated as an emulsion per se. The separation of ingredients into separate phases can also promote the chemical stability of the agent.

The content of at least one oil and / or wax in the agent according to the invention is usually 0.01 to 30% by weight, preferably 0.1 to 20% by weight, in particular 0.5 to 15% by weight, particularly preferably 1 to 7.5% by weight and most preferably 2 to 5% by weight. Based on phase II, the content of at least one oil and / or wax according to the invention is up to 50% by weight, preferably 0.1 to 45% by weight, in particular 1 to 40% by weight, particularly preferably 5 to 35% by weight .-% and most preferably 10 to 30 wt .-%. The agent can also contain mixtures of two or more oils or of two or more waxes or of at least one oil and at least one wax. In mixtures of oil (s) and wax (s), the weight ratio of oil (s) to wax (s) is preferably 10 to 1 to 1 to 5, in particular 5 to 1 to 1 to 2, particularly preferably 3 to 1 up to 1 to 1, most preferably 2 to 1 to more than 1 to 1.

Suitable oils are synthetic and natural oils, in particular silicones (polysiloxanes, systematic designation polyorganosiloxanes) or silicone oils. Silicones or silicone fluids are described, for example, in Römpp Lexikon Chemie - Version 1.5, Stuttgart / New York: GeorgThieme Verlag 1998 on CD-ROM under the keyword Silicone and in Ullmann's Enzyclopedia of lndustrial Chemistιγ, Sixth Edition, 1999 Electronic Release described under the keyword Silicones. Preferred silicones are the silicone oils, which are either cyclic polysiloxanes or linear polysiloxanes of the formula I,

(I)

in which R represents an alkyl radical, in particular an alkyl radical having 2 to 14 carbon atoms, an aryl radical, in particular a phenyl radical, or a fluorocarbon, in particular -CH ₂ CH ₂ CF ₃ , n for a number from 0 to 4,000 and m for a number of 0 to 1,000 stand. The terminal groups (CH ₃ ) ₃ Si-O- and -Si (CH ₃ ) _{3 of} the formula I are missing in the cyclic polysiloxanes and instead there is a ring closure.

Preferred cyclic silicone oils are the polydimethylcyclsiloxanes [Si (CH ₃ ) ₃ O] ", for example the dimethylsiloxane tetramer (t? = 4) and dimethylsiloxane pentamer (n = 5). Preferred linear silicone oils are the poly (methylalkylsiloxanes) (formula I: R = C _2-14 -alkyl, n = 0 to 100, m = 1 to 100), the poly (methylphenylsiloxanes) (formula I: R = phenyl. N = 0 to 1,000, m = 1 to 1,000) and the poly (fluorosiloxanes) (formula I: R = -CH ₂ CH ₂ CF ₃ , n = 0, m = 10 to 100). Particularly preferred silicone oils are the poly (methylalkylsiloxanes) (formula I: n = 0 to 4,000, m = 0) of the formula II,

(N)

in which n stands for a number from 0 to 4,000, preferably from 1 to 1,300, in particular from 10 to 1,100, particularly preferably from 50 to 800 and extremely preferably from 100 to 600.

In a preferred embodiment, the agent according to the invention contains at least one oil, in particular at least one silicone oil, which preferably has a kinematic viscosity v of 0.8 to 70,000, in particular 10 to 35,000, particularly preferably 50 to 15,000 and extremely preferably 200 to 6,000, having. The kinematic viscosity v is the quotient of the dynamic viscosity η and the density p of the liquid, ie v = η / p. Since the density of the polydimethylsiloxanes is less than 1 g ^"3 and from a viscosity of at least 3 cSt at least 0.9 g ^{" 3} , the dynamic viscosity η in mPa-s is somewhat lower than the kinematic viscosity v in cSt. The molar mass M of a polydimethylsiloxane can be calculated on the basis of the viscosity η ₂₅ at 25 ° C. using the formula M = 464- (η ₂₅ ) ⁸²⁵ / {2 + 0.0905- (η ₂₅ ) ⁰ ' ⁵⁵⁵ }.

Linear polydimethylsiloxanes are available, for example, under the trade names Dow Coring ^® 200 or Dow Corning ⁹ 200 Fluid from Dow Corning and BaysilonöP M or Baysilone ^® Oil M from Bayer, the kinematic viscosity being associated with the respective trade name v in cSt (Centistoke) at 25 ° C followed by the number in the case of Dow Corning's polydimethylsiloxanes Letters CS or CST for Centistoke follow, e.g. Dow Coming ^® 200 Fluid 0.65 CS, Dow Corning ^® 200 Fluid 1 CS, Dow Corning ^® 200 Fluid 5 CS, Dow Corning ^® 200 Fluid 100 CS, Dow Corning ^® 200 Fluid 350 CS, Dow Corning ^® 200 Fluid 500 CS, Dow Corning ^® 200 Fluid 1000 CS, Dow Corning ^® 200 Fluid 5000 CS, Dow Corning ^® 200 Fluid 12500 CS, Dow Corning ^® 200 Fluid 30000 CS and Dow Corning ^® 200 Fluid 60000 CS as well as Baysilonöt ^® M 3, Baysilonö M 20, Baysilonöf ^® M 100, BaysilonόT M 300, Baysilonö ^® M 30000 and Baysilonöf * M 60000. Cyclic polydimethylsiloxanes are available, for example, under the trade name Dow Cornind ^® from Dow Corning, for example the dimethylsiloxane tetramer as Dow Corning ^® 244 Fluid (v = 2.4 cSt) and Dow Corning ^® 344 Fluid (v = 2.7 cSt) as well as the dimethylsiloxane pentamer as Dow Corning ^® 245 Fluid (v = 4 cSt) and Dow Corning ^® 345 Fluid (v = 6 cSt).

Suitable waxes are natural, chemically modified (natural) and synthetic waxes. Vegetable waxes include both vegetable waxes, in particular candellila wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax and montan wax, as well as animal waxes, in particular beeswax, shellac wax, walnut, lanolin (wool wax) and mineral wax , in particular ceresin and ozokerite, and petrochemical waxes, in particular petrolatum, paraffin waxes and micro waxes (microparaffins). Exemplary chemically modified waxes are the montan ester waxes, sasol waxes and hydrogenated jojoba waxes belonging to the hard waxes. Suitable synthetic waxes are polyalkylene waxes (polyolefin waxes), in particular polyethylene waxes, and polyalkylene glycol waxes, in particular polyethylene glycol waxes. In a preferred embodiment, the agent according to the invention contains at least one wax, in particular a natural wax, particularly preferably beeswax, carnauba wax and / or lanolin. Waxes are described, for example, in the Römpp Lexikon Chemie - Version 1.5, Stuttgart / New York: Georg Thieme Verlag 1998 on CD-ROM under the keyword waxes and in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 1999 Electronic Release under the keyword waxes.

In a special embodiment of the invention, the agent is essentially CFRP-free, ie the non-aqueous liquid phase II is not based on CFRP. Because of the negative environmental influences of these compounds, the agents according to the invention preferably contain no CFRP at all, although small amounts, based on the total agent, of up to about 5% by weight are still tolerable. 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 40% by volume, in particular 0.2 to 35% by volume, particularly preferably 0.5 to 30% by volume. %, most preferably 1 to 20 vol .-%, 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 in amounts of 0.1 to 40% by volume, in particular 0.2 to 35% by volume, for example approximately 33% by volume, based on the volume of phase II, are particularly preferred. is emulsified in phase II.

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 being opposed by two, preferably sharp, interfaces, an upper and a lower one the parts of phases I and II not involved in the emulsion are delimited.

The agents according to the invention preferably contain 5 to 95% by volume of phase I and 95 to 5% by volume of phase II.

In a further preferred embodiment of the invention, the composition contains 35 to 95% by volume of phase I and 5 to 65% by volume of phase II, in particular 55 to 95% by volume of phase I and 5 to 45% by volume of phase II , extremely preferably 70 to 90% by volume of Phase I and 10 to 30% by volume of Phase II, for example 75, 80 or 85% by volume of Phase I and 25, 20 or 15% by volume of Phase II the continuous phase I preferably represents the lower phase and the continuous phase II the upper phase.

In a likewise preferred embodiment, the water-immiscible phase II is based on aliphatic gasoline hydrocarbons and / or terpene hydrocarbons. The petrol hydrocarbons preferably have a boiling point range from 130 to 260 ° C., in particular from 140 to 240 ° C., particularly preferably from 150 to 220 ° C., such as the C ₉ . ₁₃ isoparaffins with a boiling point range from 184 to 217 ° C, available for example as ShellsoP T from Deutsche Shell Chemie AG (Eschborn). Preferred terpene hydrocarbons are citrus oils like that Orange oil obtained from the peel of oranges, the orange terpenes contained therein, in particular limonene, or pine oil, the pine oil extracted from roots and stumps, and mixtures thereof. Here phase II contains gasoline hydrocarbons preferably in amounts of 50 to 99.99% by weight, particularly preferably 55 to 99.9% by weight, in particular 60 to 99% by weight, extremely preferably 65 to 95% by weight. %, for example 70 to 90% by weight.

Suitable surfactants for the agents according to the invention are surfactants, in particular from the classes of anionic and nonionic surfactants. The agents preferably contain one or more anionic and / or nonionic surfactants, the anionic surfactants being contained in phase I in particular. The amount of anionic surfactant, based on phase I, is usually not more than 10% by weight, preferably between 0.01 and 5% by weight, in particular between 0.01 and 0.5% by weight, particularly preferably between 0.1 and 0.3% by weight. If the agents contain nonionic surfactants, their concentration in phase I, based on phase I, is usually not more than 3% by weight, preferably between 0.001 and 0.3% by weight and in particular between 0.001 and 0.1 % By weight, and in phase II, based on phase II, usually not more than 5% by weight, preferably between 0.001 and 0.5% by weight and in particular between 0.001 and 0.2% by weight, particularly preferably between 0.005 and 0.1% by weight, most preferably between 0.01 and 0.05% by weight.

Suitable one or more anionic surfactants are preferably C ₈ -C ₁₈ alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl part, C ₈ -C ₂₀ alkanesulfonates, C ₈ -C ₁₈ monoalkyl sulfates, C ₈ -C ₁₈ alkyl polyglycol ether sulfates with 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic acid esters with 8 to 18 C atoms in the alcohol residues and mixtures thereof.

The anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or amine salts.

Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkane sulfonate with about 15 carbon atoms and sodium dioctyl sulfosuccinate. Fatty alkyl sulfates with 12 to 14 carbon atoms and sodium lauryl ether sulfate with 2 EO have proven particularly suitable. As nonionic surfactants, especially C ₈ -C ₁₈ alcohol polyglycol ethers, ie ethoxylated alcohols with 8 to 18 C atoms in the alkyl part and 2 to 15 ethylene oxide units (EO), C ₈ -C ₁₈ carboxylic acid polyglycol esters with 2 to 15 EO, ethoxylated fatty acid amides with 12 to 18 carbon atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides with 14 to 20 carbon atoms and long-chain alkyl polyglycosides with 8 to 14 carbon atoms in the alkyl part and 1 to 3 glycoside units. The agents preferably contain one or more nonionic surfactants from the group of the ethoxylates of longer-chain alcohols, the alkyl polyglycosides and mixtures thereof. Examples of such surfactants are oleyl-cetyl alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, cocoalkyl dimethylamine oxide and cocoalkyl polyglucoside with an average of 1.4 giucose units.

Preferred nonionic surfactants in the aqueous phase, in addition to the addition products of ethylene oxide and longer-chain alcohols, in particular fatty alcohols, with in particular 4 to 8 ethylene oxide units, are the alkyl polyglycosides, and of these the representatives with 8 to 10 carbon atoms in the alkyl part and up to 2 glucose - units. In the non-aqueous phase II, fatty alcohol polyglycol ethers with in particular 2 to 8 EO, for example oleyl cetyl alcohol + 5-EO ether, and / or fatty acid polyglycol esters (FSE) with in particular 2 to 10 EO, for example tallow fatty acid, are used as nonionic surfactants + 6-EO ester, particularly preferred. In the case of nonionic surfactants, especially alcohol polyglycol ethers and carboxylic acid polyglycol esters, the degree of ethoxylation for phase II is matched to the length of the C chain in such a way that shorter C chains with lower degrees of ethoxylation or longer C chains with higher degrees of ethoxylation are combined.

In a particular embodiment of the invention, the agents contain one or more anionic and nonionic surfactants. Combinations of anionic surfactant in phase I and nonionic surfactant in phase II are particularly advantageous, for example combinations of fatty alkyl sulfates and / or fatty alcohol polyglycol ether sulfates in phase I with fatty alcohol polyglycol ethers and / or FSE in phase II, in particular C ₁₂ . ₁₄ - fatty alcohol sulfates and / or C _12-14 fatty alcohol polyglycol ether sulfates with preferably 2 ethylene oxide units (EO) in phase I and nonionic surfactant, in particular C _16-18 - fatty alcohol polyglycol ethers with preferably 2 to 8 EO and / or C _14-18 fatty acid polyglycol esters with preferably 2 to 10 EO, in phase II. Furthermore, the cleaning agents according to the invention can contain one or more water-soluble organic solvents. The amount of one or more organic solvents in phase I is preferably 0.1 to 15% by weight, in particular 1 to 10% by weight, particularly preferably 2 to 8.5% by weight, extremely preferably 4 to 7% by weight .-%, for example about 5 or 6 wt .-%, based on the aqueous phase I.

Suitable solvents are, for example, water-soluble hydrocarbons with one or more hydroxyl groups, preferably the alcohols and glycols with 2 to 6 C atoms, in particular 2 or 3 C atoms, and their ethers in the form of the glycol ethers or ether alcohols and mixtures thereof.

In particular, ethanol, isopropanol and n-propanol are used as alcohols. Sufficiently water-soluble compounds with preferably no more than 10 carbon atoms in the molecule are suitable as ether alcohols. Examples of such ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether, of which in turn ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred. If alcohol and ether alcohol are used side by side, the weight ratio of the two is preferably between 1: 2 and 4: 1. Ethanol is particularly preferred in the context of the invention.

In a preferred embodiment, the agent according to the invention contains one or more water-soluble organic solvents from the group of the lower alcohols with 2 or 3 C atoms, the glycols with 2 or 3 C atoms and the glycol ether with up to 10 C atoms and mixtures thereof, especially ethanol.

The agents can be converted into the temporary emulsion according to the invention by shaking preferably up to three times, in particular up to twice, particularly preferably once, the temporary emulsion generated by shaking over a period of time of about 0.5 to 10 minutes sufficient for convenient use of the agent , preferably 1 to 5 min, in particular 1, 5 to 4 min, is stable, ie on the one hand does not collapse again immediately after the end of the pouring and on the other hand does not persist in the long term. Here, constant is to be understood to mean that, after the respective time, at least 90% by volume of the agent is still present as the temporary emulsion generated by shaking. In addition to the selection and dosage of the basic and active components there is a regulation for adjusting the latter properties of the agents according to the invention in the control of the viscosity of the individual phases.

The aqueous phase I preferably has a Brookfield viscosity (model DV-II +, spindle 31, rotational frequency 20 min ^"1 , 20 ° C) of 0.1 to 200 mPa-s, in particular 0.5 to 100 mPa-s, particularly preferably 1 to 60 mPa s and extremely preferably 5 to 20 mPa s For this purpose, the agent or the phases it contains can contain one or more viscosity regulators, The amount of viscosity regulator in phase I, based on phase I, is usually up to 0.5% by weight, preferably 0.001 to 0.3% by weight, in particular 0.01 to 0.2% by weight, most preferably 0.02 to 0.1% by weight, suitable viscosity regulators include synthetic polymers such as homo- and / or copolymers of acrylic acid or its derivatives and salts thereof, for example the products available under the trade name Carbopol ^® by Goodrich, in particular the cross-linked acrylic acid copolymer Carbopol ^® ETD 2623. In the international application WO 97/38076, on which in this Regarding reference and the content of which is hereby incorporated into this application, a number of further polymers derived from acrylic acid are listed, which also represent suitable viscosity regulators.

The agents according to the invention can furthermore contain volatile alkali in phase I. As such, ammonia and / or one or more alkanolamines, which can contain up to 9 carbon atoms in the molecule, are preferred. The ethanolamines are preferred as alkanolamines, and of these in turn the monoethanolamine. The content of ammonia and / or alkanolamine, based on phase I, is preferably 0.01 to 3% by weight, in particular 0.02 to 1% by weight, particularly preferably 0.05 to 0.5% by weight ,

In addition to the volatile alkali, the agents according to the invention can additionally contain carboxylic acid in phase I, the equivalent ratio of amine and / or ammonia to carboxylic acid preferably being between 1: 0.9 and 1: 0.1. Carboxylic acids with up to 6 carbon atoms are suitable, which may be mono-, di- or polycarboxylic acids. Depending on the equivalent weight of amine and carboxylic acid, the content of carboxylic acid, based on phase I, is preferably between 0.01 and 2.7% by weight, in particular between 0.01 and 0.9% by weight. Examples of suitable carboxylic acids are acetic acid, glycolic acid, lactic acid, citric acid, succinic acid and adipic acid, of which preferably acetic acid, citric acid and lactic acid can be used. Acetic acid is particularly preferably used.

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 dyes, perfume oils, pH regulators (e.g. citric acid, alkanolamines or NaOH), preservatives, complexing agents for alkaline earth ions, enzymes, bleaching systems and antistatic substances. The amount of such additives is usually not more than 2% by weight in the cleaning agent. The lower limit of use depends on the type of additive and can be, for example, up to 0.001% by weight and below. The amount of auxiliaries is preferably between 0.01 and 1% by weight.

The pH of the aqueous phase I can - depending on the particular application - 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 ,

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, for moderate alkalinity or above 9 to 10, 5, 11 or even 12, e.g. 10, for stronger alkalinity.

In a likewise preferred embodiment of the invention, the agents are acidified with a pH of 1 to 6, preferably 1.5 to 5.5, in particular 2 to 5, particularly preferably 2.2 to 4.5, for example 2.3 , 3 or 4.

In a preferred embodiment, the agents according to the invention contain 70 to 95% by volume, in particular 70 to 90% by volume, of aqueous phase I, containing 0 to 10% by weight of anionic surfactant, 0 to 3% by weight of nonionic surfactant, 0 to 5% by weight of water-soluble organic solvent, 0 to 0.5% by weight of viscosity regulator, up to 3% by weight of volatile alkali, 0 to 0.2% by weight of perfume and ad 100% by weight of water, and 5 to 30% by volume, in particular 10 to 30% by volume, of non-aqueous phase II, containing 0 to 99.9% by weight of aliphatic gasoline hydrocarbons, 0 to 99.9% by weight of terpene hydrocarbons, 0.1 to 50% by weight of at least one oil and / or wax, 0 to 5% by weight .-% nonionic surfactant and 0 to 1 wt .-% perfume, the details in wt .-% based on the respective phase, the sum of the gasoline and terpene hydrocarbons phase II ad 100 wt .-% and the Phases can also contain, in particular, small amounts of dye. The anionic surfactants are particularly preferred in amounts of 0.01 to 5% by weight, preferably 0.01 to 0.5% by weight, in particular 0.1 to 0.3% by weight, and / or the non-ionic surfactants in amounts of 0.001 to 0.5 wt .-%, preferably 0.005 to 0.1 wt .-%, in particular 0.01 to 0.05 wt .-%, contain.

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

The third subject 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 preferably used 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 , of the agent to be cleaned and / or applies caring surface and immediately afterwards these surfaces with a wipes absorbent soft object, thereby cleaning and / or caring for it. The agents are preferably applied with the aid of suitable spray 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.

The agents according to the invention are produced by separately mixing the individual phases directly from their respective raw materials, then combining and mixing the phases and finally standing the agent to separate the temporary emulsion. They can also be prepared by mixing them directly from their raw materials, then mixing them and then standing the agent for separating the temporary emulsion. Insofar as a component is not completely insoluble in a phase other than the phase to which the respective component is attributed or with which it was introduced into the agent, this other i phase can also, in the context of the adjustment of solubility balances by diffusion, corresponding portions of the relevant component contain.

B e i s p i e le

The composition of the exemplary agent E1 according to the invention is shown in Table 1. C ₉ served as the aliphatic gasoline hydrocarbon. _13- Isoparaffins. The composition contained a transparent aqueous phase I at the bottom and a creamy phase I emulsion at the top in non-aqueous phase II, the volume of phase I emulsified making up about a third of the volume of phase II, in a volume ratio of phase I to phase emulsion I in phase II from about 80 to 20 and separated by a sharp interface. The temporary emulsion generated by shaking remained stable for a period of about 3 minutes sufficient for convenient use of the agent, whereupon the phases were separated again.

Table 1

Composition [% by weight] E1

Silicone oil Dow Cornind ^® 200 Fluid 350 CS 7.5

Sodium C ₁₂ .i ₄ fatty alkyl sulfate 0.2

Ethanol 4.8 crosslinked acrylic acid copolymer ^[al 0.025 aliphatic gasoline hydrocarbon ¹¹³¹ 7.5 aqueous ammonia solution, 25% by weight 0.046 perfume 0.06

Dye <0.001

Water ad 100

pH of phase I 9

^[al CarbopoF ETD 2623 ^Ibl Shellsot ^t> T

Claims

Patent claims

1. Liquid multi-phase cleaning agent with at least two continuous phases, which has at least one aqueous phase I and an immiscible, non-aqueous liquid phase II with this aqueous phase and can be temporarily converted into an emulsion by shaking, characterized in that it is in phase II at least one oil and / or wax in an amount based on

Phase II, contains up to 50 wt .-%.

2. Composition according to claim 1, characterized in that it contains at least one oil and / or wax in an amount of 0.01 to 30% by weight, preferably 0.1 to 20% by weight, in particular 0.5 to 15 % By weight, particularly preferably 1 to 7.5% by weight and extremely preferably 2 to 5% by weight.

3. Composition according to one of claims 1 or 2, characterized in that it contains at least one oil, in particular a silicone oil.

4. Composition according to one of claims 1 to 3, characterized in that it contains at least one wax, in particular a natural wax, particularly preferably beeswax, carnauba wax and / or lanolin.

5. Agent according to one of the preceding claims, characterized in that the continuous phases I and II are delimited from one another by a sharp interface.

6. Agent 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

40 vol .-%, in particular 0.2 to 35 vol .-%, particularly preferably 0.5 to 30 vol .-%, most preferably 1 to 20 vol .-%, based on the volume of the respective continuous phase of the respective contain other phase than dispersant.

7. Agent according to one of the preceding claims, characterized in that phase I in amounts of 0.1 to 40 vol .-%, preferably 0.2 to 35 vol .-%, based on the volume of phase II, in phase II is emulsified.

8. Agent according to one of the preceding claims, characterized in that in addition to the continuous phases I and II, part of the two phases as an emulsion one of the two phases is present in the other phase, this emulsion being delimited by two, preferably sharp, interfaces, an upper and a lower one, relative to the parts of phases I and II which are not involved in the emulsion.

9. Composition according to one of the preceding claims, characterized in that there are 35 to 95 vol .-% phase I and 5 to 65 vol .-% phase II, in particular 55 to 95 vol .-% phase I and 5 to 45 vol. % Phase II, most preferably 70 to 90% by volume of phase I and 10 to 30% by volume of phase II.

10. Agent according to one of the preceding claims, characterized in that it is an aliphatic gasoline hydrocarbons, preferably with a boiling range from 130 to 260 ° C, in particular from 140 to 240 ° C, particularly preferably from 150 to 220 ° C, and / or contains terpene hydrocarbons, preferably orange oil and / or pine oil, phase II.

11. Agent according to one of the preceding claims, characterized in that in phase II aliphatic gasoline hydrocarbons in amounts, based on phase II, of 50 to 99.99 wt .-%, particularly preferably 55 to 99.9 wt .-% %, in particular 60 to 99% by weight, very preferably 65 to 95% by weight.

12. Composition according to one of the preceding claims, characterized in that it contains one or more anionic and / or nonionic surfactants.

13. Composition according to one of the preceding claims, characterized in that it contains one or more anionic surfactants from the group C ₈ -C ₁₈ alkylbenzenesulfonates, C ₈ -C ₂₀ alkanesulfonates, C ₈ -C ₁₈ monoalkyl sulfates, C ₈ -C Contains ₁₈ alkyl polyglycol ether sulfates with 2 to 6 ethylene oxide units and C ₈ -C ₁₈ alkyl alcohol sulfosuccinic acid esters and mixtures thereof.

14. Composition according to one of the preceding claims, characterized in that it contains nonionic surfactant from the group of ethoxylates of longer-chain alcohols, the alkyl polyglycosides and mixtures thereof in phase I and / or II.

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

16. Composition according to one of the preceding claims, characterized in that it is anionic, in particular C _12-14 fatty alcohol sulfates and / or C _12-14 - fatty alcohol polyglycol ether sulfates with preferably 2 ethylene oxide units (EO), and in phase II nonionic surfactant, in phase I, in particular contains C _16-18 fatty alcohol polyglycol ethers with preferably 2 to 8 EO and / or C _14-18 fatty acid polyglycol esters with preferably 2 to 10 EO.

17. Agent according to one of the preceding claims, characterized in that it contains one or more water-soluble organic solvents, preferably from the group of the lower alcohols having 2 or 3 carbon atoms, the glycols having 2 or 0 3 carbon atoms and the glycol ether contains up to 10 carbon atoms and mixtures thereof, especially ethanol.

18. Agent according to one of the preceding claims, characterized in that it contains in phase I, based on phase I, 0.1 to 15 wt .-%, preferably 1 to 10 wt .-%, solvent.

5 19. Agent according to one of the preceding claims, characterized in that it has one or more viscosity regulators, in particular homopolymers and / or copolymers of acrylic acid or its derivatives and their salts, in amounts, based on phase I, of up to Contains 0.5% by weight, preferably 0.001 to 0.3% by weight, in particular 0.01 to 0.2% by weight, most preferably 0.02 to 0.1% by weight.

20. Agent according to one of the preceding claims, characterized in that it has a phase I with a viscosity of 0.1 to 200 mPa-s, in particular 0.5 to 100 mPa-s, extremely preferably 1 to 60 mPa-s, contains.

21. Composition according to one of the preceding claims, characterized in that it is volatile alkali, in particular ammonia and / or one or more in phase I.

25 alkanolamines with up to 9 carbon atoms, preferably in amounts, based on phase I, of 0.01 to 3% by weight, in particular 0.02 to 1% by weight, particularly preferably 0.05 to 0.5 % By weight.

22. Composition according to one of the preceding claims, characterized in that it contains 70 to 95 vol .-% aqueous phase I

30 0 to 10% by weight of anionic surfactant,

0 to 3% by weight of nonionic surfactant, 0 to 5% by weight of water-soluble organic solvent,

0 to 0.5% by weight viscosity regulator,

0 to 3% by weight of volatile alkali,

0 to 0.2% by weight of perfume and s ad 100% by weight of water, and

Containing 5 to 30% by volume of non-aqueous phase II

0 to 99.9% by weight of aliphatic gasoline hydrocarbons,

0 to 99.9% by weight of terpene hydrocarbons,

0.1 to 50 wt .-% of at least one oil and / or wax, 0 0 to 5 wt .-% nonionic surfactant and

0 to 1% by weight of perfume, the details in% by weight being based on the respective phase

Sum of aliphatic gasoline and terpene hydrocarbons phase II ad

100% by weight completed.

s

23. Composition according to the preceding claim, characterized in that it contains the anionic surfactants in amounts of 0.01 to 5% by weight, preferably 0.01 to 0.5% by weight, in particular 0.1 to 0.3 % By weight, and / or the nonionic surfactants in amounts of 0.001 to 0.5% by weight, preferably 0.005 to 0.1% by weight, in particular 0.01 to 0.05% by weight.

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

25. A method for cleaning and / or maintaining hard surfaces, in particular of furniture, in which a cleaning agent according to one of the preceding claims is temporarily converted into an emulsion by shaking, applied to the surface to be cleaned and / or cared for, preferably by spraying, and this surface is then cleaned and / or maintained if necessary by wiping with an absorbent soft object.