CA2320544A1

CA2320544A1 - Multiphase cleaning agents with oil and/or wax

Info

Publication number: CA2320544A1
Application number: CA 2320544
Authority: CA
Inventors: Heike Wendt; Heinz-Dieter Soldanski; Jurgen Noglich
Original assignee: Henkel Kommanditgesellschaft Auf Aktien; Heike Wendt; Heinz-Dieter Soldanski; Jurgen Noglich
Current assignee: Henkel AG and Co KGaA
Priority date: 1999-09-23
Filing date: 2000-09-25
Publication date: 2001-03-23
Also published as: WO2001021754A1; AU7656300A; CO5231246A1; AR025742A1; EP1214392A1; DE19945505A1

Abstract

A liquid multiphase cleaning agent with at least two continuous phases, which contains at least one aqueous Phase I and a non-aqueous Phase II that is not miscible with this aqueous phase, and which can be temporarily converted into an emulsion by shaking, and in Phase II contains at least one oil and/or wax in a quantity of up to 50 wt.% forms, together with a spray dispenser, a product and can be used in a method for cleaning and/or care of hard surfaces, especially furniture, in which the liquid multiphase cleaning agent is temporarily converted into an emulsion by shaking, applied, preferably by spraying, to the surface to be cleaned and/or cared for, and this surface is then if necessary cleaned and/or cared for by wiping with an absorbent, soft object.

Description

MULTIPHASE CLEANING AGENTS WITH OIL AND/OR WAX
Field of the Invention The invention relates to multiphase liquid cleaning agents with an oil and/or wax, which can be temporarily emulsified by shaking, and used for cleaning and care of hard surfaces, especially furniture, a product containing the agent and a method for cleaning and/or care of hard surfaces.
1o Background of the Invention Today the usual cleaning agents for hard surfaces are as a rule aqueous preparations in the form of a stable solution or dispersion, which contain, as essential active ingredients, surfactant substances, organic solutions and, if necessary, chelating agents for the hardness constituents of the water, abrasive substances and cleansing alkalis. Cleaning agents which are especially intended for cleaning glass and ceramic surfaces are frequently formulated as solutions of the active ingredients in a mixture of water and organic solvents miscible with water, primarily low alcohols and glycol ethers. Examples of such agent are to be found in the German disclosure document 22 20 540, the US patent specifications 3 839 234 and 3 882 038 and in the European patent applications 344 847 and 393 772. Such aqueous liquid cleaners are usually available as homogenous stable solutions or dispersions.
In addition to the high primary cleansing effect of such a cleaning agent, the consumer also wants, or even expects, these to have a caring effect when treating furniture. For this purpose, caring constituents, such as oils or waxes, are incorporated into the cleaning agents.
The use of hydrophobic components of this kind in such cleaning agents to 3o improve the caring effect can however result in a reduction in cleaning efficiency and loss of the homogeneity of the agent; inhomogeneous agents are obtained whose acceptance by the consumer is to be assessed as low. In such cases there is a need for an alternative formulation of agents, which have a high cleaning efficiency and despite their inhomogeneity, a definite outer appearance and form of application that are acceptable to the consumer.

The German disclosure publication 39 10 170 describes compositions for the bacterial desorption of hard surfaces and living tissue, which are available in the form of a 2-phase preparation and when shaken form a temporary oil-in-water emulsion, the aqueous phase comprising c. 50 to 90 wt.% and the oil phase not miscible in water c. 3 to 50 wt.%, serving as mouthwash. A content of c. 0.003 wt.% of an amphiphile cationic agent, for example a cationic surfactant is essential, in a quantity enabling the formation of the oil-in-water emulsion, said emulsion breaking down and separating c. 10 seconds - 30 minutes after its formation. Anionic surfactants impair the anti-bacterial effect. Other surfactants 1o are not mentioned.
The European patent application 0 195 336 describes care products, which can be emulsified by shaking, for delicate surfaces, especially plastic surfaces or compact discs, and which, in addition to an aqueous phase, contain a further I5 organic phase, consisting of the chlorofluorocarbon (CFC) 1,1,2-trichlor-1,2,2-trifluorethane. The agents are also free from wax. Because of their environmentally harmful properties, in particular in connection with the hole in the ozone layer, the use of CFCs should however be reduced or, better still, avoided.
2o The German disclosure publications 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 for a short time by mechanical action, said oil phases containing 65 (195 01 188), 95 (195 01 187), 96.7 (195 01 187) or 98 wt.% of the cyclical decamethylpentasiloxanes (195 01 25 184), or 93.3 wt.% hexamethyldisiloxane (195 01 184). The cleansing efficiency of such agents is however inadequate.
Summary of the Invention The task of the present invention was to produce agents, stable in storage, with 3o high cleaning efficiency and caring effect for the treatment of hard surfaces in a handy form which is also acceptable to the consumer.
On object of the invention is, in a first embodiment, a liquid, multi-phase cleaning agent with at least two continuous phases, which contains at least one aqueous 35 phase I and a non-aqueous phase II that is not miscible with this aqueous phase, and which can be temporarily converted into an emulsion by shaking, and which contains in Phase II at least one oil and/or wax in a quantity of up to 50 wt.%
relative to Phase II.
s Non-miscible, non-aqueous phase means, in the context of the present invention, a phase not based on water as a solvent, whilst in the non-aqueous phase a certain quantity, relative to phase II, of water normally exceeding 20 wt.%, preferably not more than 15 wt.%, especially not more than 10 wt.% and especially preferably not more than 5 wt.% can be contained, thoroughly io dissolved.
In the simplest case an agent according to the invention consists of a continuous aqueous phase, which consists of the whole of Phase I, and a continuous non-aqueous phase, which consists of the whole of Phase II. One or more continuous 15 phases of an agent according to the invention can however also contain parts of another phase in emulsified form, so that in such an agent, for example, Phase I
exists on the one hand as continuous Phase I, which represents the continuous aqueous phase of the agent, and on the other hand, is emulsified as non-continuous Phase I in the continuous non-aqueous Phase II. The same applies to 2o Phase II and further continuous phases.
An object of the invention is, in a second embodiment, a method for cleaning and/or care of hard surfaces, especially of furniture, in which a cleaning agent according to the invention is temporarily converted into an emulsion by shaking, 25 applied to the surface to be cleaned and/or cared for, preferably by spraying, and this surface is then, if necessary, cleaned and/or cared for by wiping with an absorbent soft object.
The agents according to the invention combine a high cleaning efficiency and 3o caring effect. They have separate phases, which can be emulsified for application, remain homogenous during application, and subsequently again form separate phases. Moreover the agents according to the invention are, on the whole, highly stable in storage. Thus the individual phases in the agent are stable over a long period, without, for example, sediments forming, and the conversion into a 35 temporary emulsion remains reversible even after frequent shaking. In addition the physical form of the agents according to the invention eliminates the problem of stabilization of an agent formulated as an emulsion per se. The separation of constituents in separate phases can, in addition, increase the chemical stability of the agent.
Detailed Description of the Invention The content of at least one oil and/or wax in the agent according to the invention normally amounts to 0.01 - 30 wt.%, preferably 0.1 - 20 wt.%, especially 0.5 -wt.%, especially preferably 1 - 7.5 wt.% and ideally 2 - 5 wt.%. Relative to Phase to II, the content of at least one oil and/or wax according to the invention amounts to up to 50 wt.%, preferably 0.1 - 45 wt.%, especially 1 - 40 wt.%, especially preferably 5 - 35 wt.%, and ideally 10 - 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 oils) and waxes) the ratio by weight of oils) to Is waxes) amounts preferably to 10 : 1 - 1 : 5, especially 5 : 1 - 1 : 2, especially preferably 3 : 1 - 1 : 2, especially preferably 3 : 1 - 1 : 1, and ideally 2 :
1 to more than 1 : 1.
Suitable oils are synthetic and natural oils, especially silicones (polysiloxanes, 2o systemic name: polyorganosiloxanes) or silicone fluids. Silicones/silicone fluids are described, for example, in Rompp Lexicon Chemie [Rompp Lexicon of Chemistry]- Version 1.5, StuttgartlNew York: Georg Thieme Verlag 1998 on CD-Rom under the key word Silicones and in Ullmann's Encyclopaedia of Industrial Chemistry, Sixth Edition, 1999 Electronic Release under the key word Silicones.
25 Preferred silicones are the silicone fluids, which are either cyclical polysiloxanes, or linear polysiloxanes as described by Formula I:
~ CHs ~ - ~ CHs 30 (CHs)sSl - O - ~ - SI - O - ~ - - SI - O-~- SI(CHs)s (I) ~ CHs ~~ -~ R ~ m in which R stands for an alkyl residue, especially an alkyl residue with 2 -carbon atoms, an alkyl residue, especially a phenyl residue, or a fluorocarbon, especially -CH2 CHZCF3, n stands for a number from 0 - 4,000 and m for a number from 0 - 1,000. In the cyclic polysiloxanes, the terminal groups of Formula I
(CH3)3Si-O-and -Si(CH3)3 are missing, and are replaced by a ring closure.

5 Preferred cyclic silicone fluids are the polydimethylcyclosiloxanes [Si(CH3)30]~, for example the dimethylsiloxane tetramer (n = 4) and dimethylsiloxane pentamer (n = 5). Preferred linear silicone fluids are the poly(methylalkylsiloxanes) (Formula I:
R = C2_,4-alkyl, n = 0 - 100, m = 1 - 100), the poly(methylphenylsiloxanes) (Formula I: R = phenyl, n = 0 - 1000, m = 1 - 1,000), and the poly(fluorosiloxanes), to (Formula I: R = - CHZCH2CF3, n = 0, m = 10 - 100. Especially preferred silicone fluids are the poly(methylalkylsiloxanes) (Formula I: n = 0 - 4,000, m = 0) of Formula II, I CHs I
is (CH3)3S1- O - I - SI - O - I - SI(CH3)s (II) I cH3 h in which n stands for a number from 0 - 4,000, preferably from 1 - 1,300, especially from 10 - 1,100, especially preferably from 50 - 800 and ideally from 100 - 600.
In one preferred embodiment the agent according to the invention contains at least one oil, especially at least one silicone fluid, which has a kinematic viscosity v of preferably from 0.8 - 70,000, especially from 10 - 35,000, especially preferably from 50 - 15,000 and ideally from 200 - 6,000. The kinematic viscosity v 3o is the quotient of the dynamic viscosity rl and the density p of the fluid, i.e. v = r~/ p.
As the density of the polydimethylsiloxanes is below 1 g~cm-3 and as from a viscosity of at least 3 cSt, amounts to at least 0.9 g~cm-3, the dynamic viscosity rl in mPa~s is somewhat lower than the kinematic viscosity v in cSt. The molecular mass M of a polydimethylsiloxane can be calculated from the viscosity r125 at 25°C
according to the formula M = 464-( rlzs)°.e2s/(2 + 0.0905( 'n25)0.555}.

Linear polydimethylsiloxanes are available, for example, under the trade names Dow Corning~ 200, or Dow Corning~ 200 Fluid from the company Dow Corning and Baysilonol~ M or Baysilone~ bl M from the company Bayer, with a number indicating cinematic viscosity v in cSt (Centistokes) at 25°C being connected with each trade name, also followed in the case of the polydimethylsiloxanes of Dow Corning by the letters CS or CST, for Centistoke, e.g. Dow Corning~ 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 to CS, Dow Corning~ 200 Fluid 12500 CS, Dow Corning~ 200 Fluid 30000 CS and Dow Corning~ 200 Fluid 60000 CS; and Baysilonol~ M 3, Baysilonol~ M 20, Baysilonol~ M 100, Baysilonol~ M 300, Baysilonol~ M 30000 and Baysilonol~ M
60000. Cyclic polydimethylsiloxanes are available, for example under the trade name Dow Corning~ from the company Dow Corning, e.g. the dimethylsiloxane tetramer as Dow Corning~ 244 Fluid (v = 2.4 cSt) and Dow Corning~ 344 Fluid (v = 2.7 cSt), as well as 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.
2o Vegetable waxes include both vegetable waxes, especially candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice-germ wax, sugar cane wax, ouricury wax and montan wax, and also animal waxes, especially beeswax, shellac wax, spermaceti, lanolin (wool wax) and uropygial fat, as well as mineral waxes, especially ceresin and ozocerite, and petrochemical waxes, especially petrolatum, paraffin waxes and micro-waxes (micro-paraffins).
Examples of chemically modified waxes are the hard waxes which include montan ester waxes, sasol waxes and hydrated jojoba waxes. Suitable synthetic waxes are polyalkylene waxes (polyolefin waxes), especially polyethylene waxes, and polyalkylene glycol waxes, especially polyethylene glycol waxes. In a preferred 3o embodiment, the agent according to the invention contains at least one wax, preferably a natural wax, especially preferably beeswax, carnauba wax and/or lanolin. Waxes are described for example, in Rompp Lexicon Chemie [Rompp Lexicon of Chemistry]- Version 1.5, StuttgarflNew York: Georg Thieme Verlag 1998 on CD-Rom under the key word Waxes and in Ullmann's Encyclopaedia of Industrial Chemistry, Sixth Edition, 1999 Electronic Release under the key word Waxes.
In a special embodiment of the invention the agent is essentially CFC-free, i.e. the aqueous liquid Phase II is not based on CFCs. In this case the agents according to the invention, because of the negative environmental effects of these compounds, preferably contain no CFCs at all, whilst small quantities of up to c. 5 wt.%, relative to the whole agent, can still be tolerated. In a preferred embodiment of the invention, the continuous Phases I and II are separated from 1o each other by a clearly defined interface.
In an especially preferred embodiment of the invention, one or both of the continuous Phases I and II contain parts, preferably 0.1 - 40 vol.%, especially 0.2 -35 vol.%, especially preferably 0.5 - 30 vol.%, and ideally 1 - 20 vol.%, relative to the volume of the continuous phase in question, of the other phase as a dispersion agent. The continuous phase I or, as the case may be, II is then reduced by the volume percentage which is distributed through the other phase as a dispersion agent. Especially preferred are agents, in which Phase I is emulsified in Phase II, in quantities of 0.1 - 40 vol.%, especially 0.2 - 35 vol.%, for example c.
33 vol.%, relative to the volume of Phase II.
In a further special embodiment of the invention, in addition to the continuous phases I and II, part of both phases is present in the other phase, as an emulsion of one of the two phases in the other phase, and said emulsion is separated by two, preferably distinct, interfaces, an upper and a lower, from the parts of Phases I and II not forming part of the emulsion.
The agents according to the invention contain preferably 5 - 95 vol.% of Phase I
and 95 - 5 vol.% of Phase II.
In a further preferred embodiment of the invention, the agent contains 35 - 95 vol.% Phase I and 5 - 65 vol.% Phase II, especially 55 - 95 vol.% Phase I and 45 vol.% Phase II, and ideally 70 - 90 vol.% Phase I and 10 - 30 vol.% Phase II, for example 75, 80 or 85 vol.% Phase I and 25, 20 or 15 vol.% Phase II.

Furthermore, the continuous Phase I preferably represents the lower phase and the continuous Phase II the upper phase.
In a likewise preferred embodiment, the non-water-miscible Phase II is based on aliphatic benzine hydrocarbons and/or terpene hydrocarbons. The benzine hydrocarbons preferably have a boiling-point range of 130 - 260°C, especially 140 - 240°C, especially preferably 150 - 220°C, like for example the C9_,3-isoparaffins with a boiling-point range of 184 - 217°C, available for example as Shellsol~ T
from the company Deutsche Shell Chemie AG (Eschborn). Preferred terpene to hydrocarbons are citrus oils such as the orange oil obtained from orange peel, the orange terpenes contained in this, especially limes, or pine oil, which is extracted from roots and tree stumps, or mixtures of these. In this case Phase II
contains benzine hydrocarbons preferably in quantities of 50 - 99.99 wt.%, especially preferably 55 - 99.9 wt.%, especially 60 - 99 wt.%, and ideally 65 - 95 wt.%, for example 70 - 90 wt.%.
As surface-active substances, for the agents according to the invention, surfactants are suitable, especially those classed as anionic and non-ionic surfactants. The agents preferably contain one or more anionic and/or non-ionic 2o surfactants, with the anionic surfactants being contained in particular in Phase I.
The quantity of anionic surfactants, relative to Phase I, is not normally more than 10 wt.%, preferably between 0.01 and 5 wt.%, especially between 0.01 and 0.5 wt.%, especially preferably between 0.01 and 0.3 wt.%. To the extent that the agents contain non-ionic surfactants, their concentration, preferably in Phase I, relative to Phase I, is normally not more than 3 wt.%, preferably between 0.001 and 0.3 wt.%, and especially between 0.001 and 0.1 wt.%, and in Phase II, relative to Phase II, normally not more than 5 wt.%, preferably between 0.001 and 0.5 wt.%, especially between 0.001 and 0.2 wt.%, especially preferably between 0.005 and 0.1 wt.% and ideally between 0.01 and 0.05 wt.%.
Substances suitable as one or more anionic surfactants are preferably C$-C~8-alkylbenzene sulfonates, especially with c. 12 C atoms in the alkyl part, C$-C2o-alkane sulfonates, Cs-C,8-monoalkylsulfates, Ce-C,8-alkylpolyglycolethersulfates with 2 - 6 ethylene oxide units (EO) in the ether part and sulfosuccinic acid esters with 8 - 18 C atoms in the alcohol residues, and mixtures of these.

The anionic surfactants are preferably used as sodium salts, but can also be contained as other alkali- or alkaline-earth metallic salts, for example magnesium salts, and in the form of ammonium or amine salts.
Examples of such surfactants include sodium-coconut-alkylsulfate, sodium-sec.-alkane sulfate with c. 15 C atoms and sodium dioctylsulfosuccinate. Fat alkylsulfates with 12 - 14 C atoms such as sodium laurylethersulfate with 2 EO
have proved especially suitable. As non-ionic surfactants, the following substances should especially be mentioned: C8-C,8-alcoholpolyglycolethers, i.e.
1o ethoxylated alcohols with 8 - 18 C atoms in the alkyl part and 2 - 15 ethylene oxide units (EO), C8-C,8-carbonic acid polyglycolesters with 2 - 15 EO, ethoxylated fatty acid amides with 12 - 18 C atoms in the fatty acid part and EO, long-chained amine oxides with 14 - 20 C atoms and long-chained alkylpolyglycosides with 8 - 14 C atoms in the alkyl part and 1 - 3 glycoside units.
The agents preferably contain one or more non-ionic surfactants from the group of ethyoxylates of long-chained alcohols, alkylpolyglycosides and mixtures of these.
Examples of such surfactants are oleyl-cetyl-alcohol with 5 EO, nonylphenol with 10 EO, laurinic acid diethanolamide, coconut-alkyldimethylamine oxide and coconut-alkylpolyglucoside with, on average, 1.4 glucose units.
The following substances are preferred as non-ionic surfactants in the aqueous phase in addition to the additive products of ethylene oxide and long-chained alcohols: in particular fat alcohols, especially with 4 - 8 ethylene oxide units, which contain alkylpolyglycosides, and again the representatives of these with 8 -atoms in the alkyl part and up to 2 glucose units. In the non-aqueous Phase II, substances especially preferred as non-ionic surfactants are fat alcohol polyglycolethers, especially with 2 - 8 EO, for example oleyl-cetyl-alcohol+5-EO-ether, and/or fatty acid polyglycolester (FAE) especially with 2 - 10 EO, for example tallow fatty acid+6-EO-esters. Also for the non-ionic surfactants, in 3o particular the alcoholpolyglycolethers and carbonic acid polyglycolesters, for Phase II the degree of ethoxylation is determined on the basis of the C-chain length, so that shorter C chains with lower degrees of ethoxylation or longer C
chains with higher degrees of ethoxylation are combined.

. CA 02320544 2000-09-25 In a special embodiment of the invention, the agents contain one or more anionic and non-ionic surfactants. In this case combinations of anionic surfactant in Phase I and non-ionic surfactant in Phase II are especially advantageous, for example combinations of fat alkylsulfates and/or fat alcohol polyglycolether sulfates in s Phase I with fat alcohol polyglycolethers and/or FAE in Phase II, especially C~2_~4-fat alcohol sulfates and/or C,2_,4-fat alcohol polyglycolethersulfates with, preferably, 2 ethylene oxide units (EO) in Phase I, and non-ionic surfactant, especially C,6_,$-fat alcohol polyglycolethers with preferably 2 - 8 EO and/or C,4_,8-fatty acid polyglycolesters with preferably 2 - 10 EO, in Phase II.
In addition, the cleaning agents according to the invention can contain one or more water-soluble organic solvents. The quantity of one or more organic solvents in Phase I amounts to preferably 0.1 - 15 wt.%, especially 1 - 10 wt.%, especially preferably 2 - 8.5 wt.%, and ideally 4 - 7 wt.%, for example 5 or 6 wt.%, relative to the aqueous Phase I.
Suitable solvents are for example water-soluble hydrocarbons with one or more hydroxy groups, preferably the alcohols and glycols with 2 or 6 C atoms, especially 2 or 3 C atoms, and their ethers in the form of glycol ethers/ether 2o alcohols and mixtures of these.
As alcohols, ethanol, isopropanol and n-propanol are in particular used.
Suitable ether alcohols include sufficiently water-soluble compounds with preferably no more than 10 C atoms in the molecule. Examples of such ether alcohols are:
ethylene glycolmonobutylether, propylene glycolmonobutylether, diethyleneglycolmonobutylether, propylene glycolmono-tertiary butyl ether and propylene glycolmonoethylether, out of which ethylene glycolmonobutylether and propylene glycolmonoethylether are preferred. If alcohol and ether alcohol are used together with each other, their weight ratio should preferably lie between 1 2 and 4 :1. Ethanol is especially preferred within the framework 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 lower alcohols with 2 or atoms, of glycols with 2 or 3 C atoms, and of glycol ethers with up to 10 C
atoms and mixtures of these, especially ethanol.

The agents can preferably be converted to the temporary emulsion according to the invention by shaking up to three times, preferably up to twice, and especially preferably once, so that the temporary emulsion generated by the shaking remains stable for a period of time sufficent for comfortable application of the agent, of c. 0.5 - 10 min, preferably 1 - 5 min, and especially 1.5 - 4 min, i.e. on the one hand it does not break down directly after the shaking ceases, and on the other hand, it does not remain stable for a long period. The term stable here shall be taken to mean that after the period in question at least 90 wt.% of the agent is present as the temporary emulsion generated by shaking. Besides the selection to and dosage of basic and active components, a regulating agent is also present for adjustment of the latter properties of agents according to the invention by regulating the viscosity of the individual phases.
The aqueous Phase I preferably has a viscosity according to Brookfield (Model DV-II+, spindle 31, rotating frequency 20 min-', 20°C) of 0.1 - 200 mPa~s, especially 0.5 - 100 mPa~s, especially preferably 1 - 60 mPa~s, and ideally 5 -mPa~s. For this purpose the agent, or the contained phases, contain one or more viscosity regulators. The quantity of viscosity regulators in Phase I, relative to Phase I, normally amounts to up to 0.5 wt.%, preferably 0.001 - 0.3 wt.%, 2o especially 0.01 - 0.2 wt.%, and especially preferably 0.02 - 0.1 wt.%.
Suitable viscosity regulators include synthetic polymers such as the homo- and/or copolymers of the acrylic acid and/or their derivatives and their salts, for example the products of the company Goodrich, available under the trade name Carbopol~, especially the cross-linked acrylic acid copolymer Carbopol~ ETD
2623. In the international application WO 97138076, referred to in this connection, and whose content is hereby included in this application, a number of further polymers derived from the acrylic acid are listed, which also represent suitable viscosity regulators.
3o In addition the agents according to the invention contain volatile alkali in Phase I.
As such, ammonia and/or one or more alkanolamines which can contain up to 9 C
atoms in the molecule are preferred. As alkanolamines the ethanolamines are preferred, and of these the monoethanolamine. The content of ammonia and/or alkanolamine, relative to Phase I, amounts to preferably 0.01 - 3 wt.%, especially 0.02 - 1 wt.%, and especially preferably 0.05 - 0.5 wt.%.

Besides the volatile alkali the agents according to the invention can in addition contain carbonic acid in Phase I, with the equivalent ratio of amine and/or ammonia to carbonic acid being preferably between 1 : 0.9 and 1 : 0.1.
Carbonic acids with up to 6 C atoms are suitable, and these may be mono-, di- or polycarbonic acids. Depending on the equivalent weight of amine and carbonic acid, the content of carbonic acid, relative to Phase I is preferably between 0.01 and 2.7 wt.%, especially between 0.01 and 0.9 wt.%. Examples of suitable carbonic acid are acetic acid, glycolic acid, lactic acid, citric acid, succinic acid and adipic acid, of which acetic acid, citric acid and lactic acid are preferably used.
1o Acetic acid is especially preferably used.
Besides the aforementioned components the agent according to the invention can contain further auxiliary substances and additives, such as are usual in agents of this kind. These include in particular dyes, perfume oils, pH-regulators (e.g.
citric 1s acid, alkanomines, or NaOH), preservatives, chelating agents for alkaline-earth ions, enzymes, bleach systems and antistatic substances. The quantity of such additives does not normally exceed 2 wt.% of the cleaning agent. The lower limit for use depends on the nature of the additive and can for example amount to up to 0.001 wt.% or less in the case of dyes. The quantity of auxiliary substances is 2o preferably between 0.01 and 1 wt.%.
The pH value of the aqueous Phase I can - in adaptation to the purpose in question - be varied over a broad range from strongly acid, through neutral, to highly alkaline; however a range of 1 - 12 is preferred, especially 2 - 11.
In a neutral embodiment the pH value amounts to more than 6 - less than 8, preferably 6.5 - 7.5 and especially approx. 7.
In a preferred embodiment of the invention the agents are adjusted to be alkaline 3o with a pH value of 8 - 12, preferably 8 - 11, especially 8 - 10.5, for example between 8 and 9, for moderate alkalinity or above 9 - 10.5, 11 or even 12, e.g. 10 for stronger alkalinity.

In a likewise preferred embodiment of the invention the agents are adjusted to be acid with a pH value of 1 - 6, preferably 1.5 - 5.5, especially 2 - 5, especially preferably 2.2 - 4.5, for example 2.3, 3 or 4.
In a preferred embodiment the agents according to the invention contain 70 -vol.%, especially 70 - 90 vol.%, aqueous Phase I containing 0 - 10 wt.% anionic surfactant, 0 - 3 wt.% non-ionic surfactant, 0 - 5 wt.% water-soluble organic solvent, 0 - 0.5 wt.% viscosity regulator, 0 - 3 wt.% volatile alkali, 0 - 0.2 wt.% perfume and, ad 100 wt. water, and 5 - 30 vol.%, especially 10 - 30 vol.%, non-aqueous Phase II, containing 0 - 99.9 wt.% aliphatic benzine hydrocarbons, 0 - 99.9 wt.% non-ionic terpene hydrocarbons, 0.1 - 50 wt.% of at least one oil and/or wax, 0 - 5 wt.% non-ionic surfactant and, 0 - 1 wt.% perfume, 2o where the wt.% figures relate to the relevant phase, the total benzine and terpene hydrocarbons of Phase II are made up to (adJ 100 wt.% and the phases may additionally contain small quantities of dye. Especially preferably, the anionic surfactants are contained in quantities of 0.1 - 5 wt.%, preferably 0.01 - 0.5 wt.%, especially 0.1 - 0.3 wt.%, and/or the non-ionic surfactants in quantities of 0.001 -0.5 wt.%, preferably 0.005 - 0.1 wt.%, especially 0.01 - 0.05 wt.%.
The agent according to the invention is sprayable and can therefore be used in a spray dispenser.
3o The third object of the invention is accordingly a product containing an agent according to the invention and a spray dispenser.
The preferred spray dispenser is a manually activated spray dispenser, especially selected from the group comprising aerosol spray dispensers, self-priming spray dispensers, pump spray dispensers and trigger spray dispensers, especially pump spray dispenser and trigger spray dispensers with a container made from transparent polyethylene or polyethylene terephthalate. Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein relating to spray dispensers, to which global reference is made in this regard and whose content is hereby included in this application.
Application of the agents according to the invention occurs preferably in that the agent converted temporarily into an emulsion is applied in quantities of c.
1.5 - 10 g per m2, especially 3 - 7 g per mz, to the surface to be cleaned and/of cared for, to and these surfaces are then immediately wiped with an absorbent, soft object, so that they are cleaned and/or cared for. The application of the agents is preferably achieved by means of suitable spraying devices, especially a spray dispenser or a product according to the invention, to achieve as even a distribution as possible.
For wiping, sponges or cloths are particularly suitable; these can be rinsed out with water from time to time during treatment of larger surfaces.
The agents according to the invention are produced by separate mixing of the individual phases directly from their own particular raw materials, then putting the phases together and intermixing them, and finally leaving the mixture to stand until 2o the temporary emulsion separates. They can also be produced by directly mixing up their raw materials, then intermixing and finally leaving the mixture to stand until the temporary emulsion separates. If a component is not completely insoluble in a phase other than that to which the component in question is assigned, or with which it is introduced into the agent, this other phase may also contain corresponding constituents of the component concerned within the framework of the adjustment of solubility stability by diffusion.

Examales Table 1 shows the composition of the agent E1 according to the invention, as an example. C9_,3-isoparaffins were used as aliphatic benzine hydrocarbon. The 5 agent contained a transparent aqueous Phase I below, and a creamy emulsion of Phase I in non-aqueous Phase II above, with the volume of emulsified Phase I
making up approximately one-third of the volume of Phase II, in a volume ratio of Phase I to the emulsion of Phase I in Phase II of approximately 80 : 20, and separated by a distinct interface. The temporary emulsion generated by shaking 1o remained stable for a period of time of approximately 3 min sufficient for comfortable use of the agent, followed by renewed phase separation.
Table 1 Composition [wt.%j E1 Silicon fluid Dow Corning~ 200 Fluid 7.5 Sodium-C,2_,4-fat alkylsulfate 0.2 Ethanol 4,g Cross-linked acrylic acid copolymer<a~ 0.025 Aliphatic benzine-hydrocarbon~b~ 7.5 Aqueous ammonia solution, 25 wt.% 0.046 Perfume 0.06 Dye <0.001 Water ad 100 pH value of Phase I g a Carbopol~ ETD 2623 1 s ~b~ Shellsol'~ T

Claims

1. A liquid, multiphase cleaning agent composition having at least two continuous phases, comprising at least one aqueous phase and a non-aqueous liquid phase, not miscible with the aqueous phase, and the composition being capable of being temporarily converted into an emulsion by shaking, wherein the composition contains in the aqueous phase, at least one oil and/or wax in a quantity of up to 50 wt.%, relative to the aqueous phase.

2. A composition as claimed in claim 1, wherein there is present at least one oil and/or wax in a quantity of 0.01 - 30 wt.%.

3. A composition as claimed in claim 2, wherein the quantity is from 0.1 - 20 wt. %.

4. A composition as claimed in claim 1, wherein the quantity is from 0.5 - 15 wt. %.

5. A composition as claimed in claim 1, wherein the quantity is from 1 - 7.5 wt. %.

6. A composition as claimed in claim 1, wherein the quantity is from 2 - 5 wt.%.

7. A composition as claimed in any of claims 1 to 6, wherein there is present at least one oil.

8. A composition as claimed in any of claims 2 to 7, wherein the oil is a silicone fluid.

9. A composition as claimed in any of claims 1 to 8, wherein there is present at least one wax.

10. A composition as claimed in claim 9, wherein the wax is a natural wax.

11. A composition as claimed in claim 10, wherein the natural wax is beeswax, carnauba wax and/or lanolin.

12. A composition as claimed in any of claims 1 to 11, wherein the continuous phases are separated from each other by a distinct boundary layer.

13. A composition as claimed in any of claims 1 to 12, wherein one or both of the continuous phases contain parts relative to the volume of the continuous phase in question, of the other phase as a dispersion agent.

14. A composition as claimed in claim 13, wherein the parts comprise 0.1 - 40 vol.%.

15. A composition as claimed in claim 13, wherein the parts comprise 0.2 - 35 vol.%.

16. A composition as claimed in claim 13, wherein the parts comprise 0.5 - 30 vol.%.

17. A composition as claimed in claim 13, wherein the parts comprise 1 - 20 vol.%.

18. A composition as claimed in any of claims 1 to 17, wherein the aqueous phase is emulsified in quantities of 0.1 - 40 vol.%, relative to the volume of the non-aqueous phase, in the non-aqueous phase.

19. A composition as claimed in claim 18, wherein the quantities are 0.2 - 35 vol.%.

20. A composition as claimed in any of claims 1 to 19, wherein a part of both phases is present in the other phase as an emulsion of one of the two phases, said emulsion being separated from the parts of the phases not forming part of the emulsion, by two, preferably distinct interfaces, an upper and a lower.

21. A composition as claimed in any of claims 1 to 20, comprising 35 - 95 vol.%
of aqueous phase and 5 - 65 vol.% of non-aqueous phase.

22. A composition as claimed in claim 21, wherein there is present 55 - 95 vol.%
of aqueous phase and 5 - 45 vol.% of non-aqueous phase.

23. A composition as claimed in claim 21, wherein there is present 70 - 90 vol.%
of aqueous phase and 10 - 30 vol.% of non-aqueous phase.

24. A composition as claimed in any of claims 1 to 23, wherein the non-aqueous phase is based on aliphatic benzine hydrocarbons, and/or terpene hydrocarbons.

25. A composition as claimed in claim 24, wherein the hydrocarbons have a boiling range of 130 - 260°C.

26. A composition as claimed in claim 24, wherein the hydrocarbons have a boiling range of 140 - 240°C.

27. A composition as claimed in claim 24, wherein the hydrocarbons have a boiling range of 150 - 220°C.

28. A composition as claimed in any of claims 24 to 27, wherein the terpene hydrocarbons are orange oil and/or pine oil.

29. A composition as claimed in any of claims 1 to 28, wherein the non-aqueous phase contains aliphatic benzine hydrocarbons in quantities, relative to the non-aqueous phase, of 50 - 99.99 wt.%.

30. A composition as claimed in claim 29, wherein the quantities are 55 - 99.9 wt. %.

31. A composition as claimed in claim 29, wherein the quantities are 60 - 99 wt. %.

32. A composition as claimed in claim 29, wherein the quantities are 65 - 95 wt. %.

33. A composition as claimed in any of claims 1 to 32, wherein one or more anionic and/or non-ionic surfactants are present.

34. A composition as claimed in any of claims 1 to 33, wherein one or more anionic surfactants from the group of C8-C16-alkylbenzene sulfonates, C8-C20-alkane sulfonates, C8-C18-monoalkylsulfates, C8-C18-alkylpolyglykolether sulfates with 2 - 6 ethylene oxide units and C8-C18-alkylalcohol-sulfosuccinic acid esters and mixtures of these are present.

35. A composition as claimed in any of claims 1 to 34, wherein there is present non-ionic surfactant from the ethoxylate group of long-chained alcohols, alkylpolyglycosides and mixtures of these in either or both phases.

36. A composition as claimed in any of claims 1 to 35, wherein one or more anionic and non-ionic surfactants are present.

37. A composition as claimed in any of claims 1 to 36, wherein there is present C12-14-fat alcohol sulfates and/or C12-14-fat alcohol polyglycolethersulfates in the aqueous phase, and non-ionic surfactant in the non-aqueous phase.

38. A composition as claimed in claim 37, wherein the sulfates in the aqueous phase contain 2 ethylene oxide units (EO) and the ethers contain 2 - 8 EO
and the esters contain 2 - 10 EO in the non-aqueous phase.

39. A composition as claimed in any of claims 1 to 38, wherein one or more water-soluble organic solvents are present.

40. A composition as claimed in claim 39, wherein the solvents are selected from the group of lower alcohols with 2 or 3 C atoms, of the glycols with 2 or 3 C atoms and of the glycol ethers with up to 10 C atoms and mixtures of these solvents.

41. A composition as claimed in claim 40, wherein the solvent is ethanol.

42. A composition as claimed in any of claims 1 to 41, wherein the aqueous phase, relative to 0.1 - 15 wt.% solvent is present.

43. A composition as claimed in claim 42, wherein 1-10 wt.% solvent is present.

44. A composition as claimed in any of claims 1 to 42, wherein one or more viscosity regulators in quantities relative to the aqueous phase of up to 0.5 wt.% are present.

45. A composition as claimed in claim 44, wherein the regulators are selected from homo- and/or copolymers of acrylic acid or their derivatives and their salts.

46. A composition as claimed in claim 44 or 45, wherein the quantities are 0.001 - 0.3 wt.%.

47. A composition as claimed in claim 44 or 45, wherein the quantities are 0.01-0.2 wt.%.

48. A composition as claimed in claim 44 or 45, wherein the quantities are 0.02-0.1 wt.%.

49. A composition as claimed in any of claims 1 to 48, wherein the aqueous phase has a viscosity of 0.1 - 200 mPa~s.

50. A composition as claimed in claim 49, wherein the viscosity is 0.5-100 mPa~s.

51. A composition as claimed in claim 49, wherein the viscosity is 1 - 60 mPa~s.

52. A composition as claimed in any of claims 1 to 52, wherein the aqueous phase contains volatile alkali.

53. A composition as claimed in claim 52, wherein the volatile alkali is ammonia and/or one or more alkanolamines with up to 9 C atoms.

54. A composition as claimed in claim 52 or 53, wherein the quantities relative to the aqueous phase comprise 0.01 - 3 wt.%.

55. A composition as claimed in claim 52 or 53, wherein the quantities relative to the aqueous phase comprise 0.02 - 1 wt.%.

56. A composition as claimed in claim 52 or 53, wherein the quantities relative to the aqueous phase comprise 0.05 - 0.5 wt.%.

57. A composition as claimed in any of claims 1 to 56, comprising 70 - 95 vol.% of aqueous phase comprising 10 wt.% anionic surfactant, 0 - 3 wt.% non-ionic surfactant, 0 - 5 wt.% water-soluble organic solvent, 0 - 0.5 wt.% viscosity regulator, 0 - 3 wt.% volatile alkali, 0 - 0.2 wt.% perfume and, ad 100 wt. water, and 5 - 30 vol.% a non-aqueous phase comprising 0 - 99.9 wt.% aliphatic benzine hydrocarbons, 0 - 99.9 wt.% non-ionic terpene hydrocarbons, 0.1 - 50 wt.% of at least one oil and/or wax, 0 - 5 wt.% non-ionic surfactant and, 0 - 1 wt.% perfume, where the wt.% figures relate to the relevant phase, and the total aliphatic benzine and terpene hydrocarbons of the non-aqueous phase are made up to [ad] 100 wt.%.

58. A composition as claimed in any of claims 1 to 57, comprising the anionic surfactants in quantities of 0.1 - 5 wt.%, and/or the non-ionic surfactants in quantities of 0.001 - 0.5 wt.%.

59. A composition as claimed in claim 58, wherein the anionic surfactants comprise 0.1 - 0.5 wt.%.

60. A composition as claimed in claim 58, wherein the anionic surfactants comprise 0.01 - 0.3 wt.%.

61. A composition as claimed in claims 58 to 60, wherein the non-ionic surfactants are in quantities of 0.005 - 0.1 wt.%.

62. A composition as claimed in claims 58 to 60, wherein the non-ionic surfactants are in quantities of 0.01 - 0.05 wt.%.

63. A cleaning product comprising a cleaning agent composition as claimed in any of claims 1 to 62 in a spray dispenser.

64. A method for cleaning and caring for hard surfaces in which a cleaning agent composition as claimed in any of claims 1 to 62, wherein the composition is temporarily converted into an emulsion by shaking, the composition is applied to the surface to be cleaned and/or cared for, and this surface is then if necessary cleaned/and or cared for by wiping with an absorbent, soft object.

65. A method as claimed in claim 64, wherein the composition is applied to the hard surface by spraying.