WO2002044314A1

WO2002044314A1 - Multi-phase detergent with bleach

Info

Publication number: WO2002044314A1
Application number: PCT/EP2001/013656
Authority: WO
Inventors: Georg Meine; Ryszard Katowicz; Alexander Ditze
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2000-12-02
Filing date: 2001-11-23
Publication date: 2002-06-06
Also published as: AU2002219139A1; DE10060096A1

Abstract

The invention relates to an aqueous, liquid, multi-phase detergent containing a tenside and comprising at least two phases, which has at least a phase I and a phase II, which can be shaken to form a temporary emulsion, suspension and/or dispersion and/or aerosol and which contains at least one bleaching agent. The inventive detergent can be used to clean textiles and hard surfaces and can be produced by direct mixture of the raw materials, subsequent thorough mixing of these and finally, allowing the detergent to stand in order to separate the temporary emulsion, suspension and/or dispersion and/or aerosol.

Description

_« Multi-phase detergent with bleach"

The invention relates to aqueous, multi-phase, liquid detergent and cleaning agent containing bleach, which can be temporarily emulsified by shaking and can be used for cleaning all types of surfaces, a process for their preparation and their use for cleaning surfaces.

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

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 can result in this homogeneity being lost and inhomogeneous agents being obtained, the acceptance of which can be estimated as low by the consumer. In such cases, alternative formulations are required which, despite their inhomogeneity, have a defined external appearance and application form which is acceptable to the consumer.

European patent application 116 422 describes a liquid hair or body shampoo with two aqueous phases which can be temporarily dispersed into one another by shaking are and both phases are 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. Additional builder salts can optionally be contained in the lower phase. Anionic, cationic, amphoteric and / or nonionic surfactants can be present as surfactants, preferably at least one anionic surfactant being contained.

Hair treatment agents in the form of a 2-phase system are known from German Offenlegungsschriften 19501 184, '187 and' 188 (Henkel KGaÄ), which have an oil phase and a water phase, the oil phase being based on silicone oil or paraffin oil, and briefly due to mechanical action are miscible.

For particularly stubborn soiling, bleaches are used in cleaning agents, the task of which is to contribute to the dissolution of this soiling by means of oxidation processes. Corresponding bleaches have long been known, particularly in the case of solid matter cleaners. The integration of bleaching systems in liquid products has so far failed due to the low storage stability of these compositions.

In water-free recipes, the viscosity setting proves to be particularly problematic. In addition, opened bottles with anhydrous compositions remove atmospheric moisture, with the result that the bleaching component reacts. Activators which are introduced homogeneously into aqueous systems and which are necessary in the case of less reactive bleaching agents in order to achieve a minimum activity and which are intended to improve the bleaching performance, in particular in the low temperature range, are destroyed. In addition, perfume oils, enzymes and dyes used are affected by the reactive bleach.

The object of the present invention was to provide high-performance and storage-stable agents for cleaning all types of surfaces, such as textiles, carpets, and in particular hard surfaces in a defined inhomogeneous, easy-to-handle and acceptable form for the consumer. The object of the present invention was, in particular, to provide washing and cleaning agents containing multiphase bleach, which can be used universally for cleaning all types of surfaces.

The invention relates to an aqueous liquid multi-phase surfactant-containing washing and cleaning agent with at least two phases, which has at least one phase I and one phase II and can be temporarily converted into an emulsion, suspension and / or dispersion and / or aerosol by shaking, and that contains at least one bleach.

The invention also relates to the use of an agent according to the invention for cleaning textile and hard surfaces, and to a method for producing detergents and cleaning agents according to the invention.

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

In the context of the present invention, the term “phase” is understood to mean both gaseous, liquid and solid phases. Multi-phase detergents and cleaning agents in the sense of the invention are both liquid / liquid and liquid / solid mixtures and liquid / gaseous mixtures. Furthermore, the washing and cleaning agents according to the invention can also be produced in the form of solid / liquid, solid / gaseous, solid / solid, gaseous / solid, gaseous / liquid and gaseous / gaseous mixtures.

Furthermore, within the scope of the present invention - unless expressly stated otherwise - the use of a salt is just as possible as the use of the corresponding acid / base pair of the salt which only gives the salt or its solution in situ with neutralization, even if the the respective alternative is not always explicitly formulated in the present teaching. In this sense, potassium citrate and the combination of citric acid / potassium hydroxide or potassium alkylbenzenesulfonate and the combination of AU - ylbenzenesulfonic acid / potassium hydroxide represent equivalent alternatives. If, within the scope of the present invention, a certain component can finally be used for different purposes, its use is deliberately repeated below, if necessary. This applies, for example, to citric acid, which is used both as an acid for pH adjustment, as a phase separation aid and builder, and to the anionic sulfonic acids, which also act as acids and also as anionic surfactants.

The agents according to the invention are distinguished by a high cleaning ability with diluted and undiluted use - both on hard surfaces in the bathroom or kitchen area, and also on textiles and carpets and the like. In addition, the agents show favorable residue behavior. The individual phases on average are stable over a long period of time, the bleaching effect remaining essentially constant without, for example, Form deposits, and the transfer into a temporary emulsion, suspension or dispersion and / or aerosol remains reversible even after frequent shaking. Furthermore, the agents enable the stable incorporation of components which can only be incorporated stably in single-phase aqueous solutions or stable emulsions or microemulsions by using solvents, solubilizers or emulsifiers. In addition, the separation of ingredients in separate phases can promote the chemical stability of the agent.

Surprisingly, it has been shown that the spatial separation of activators, catalysts, enzymes, perfume oils, surfactants, additives of a sensitive type (for example vitamins, antioxidants, antibacterial active ingredients, care components, lipids, odor adsorbers, cyclodextrins, quaternary surfactant components) and the bleaching component, and also the separation of positively and negatively charged particles / components, as is possible in a simple manner in multi-phase washing and cleaning agents according to the invention, the storage stability and bleaching activity can be maintained over long periods of time.

PH value

The pH of the agents according to the invention is usually 1 to 10, preferably 2 to 8, particularly preferably 3 to 6, most preferably 5 to 6. To adjust the pH value according to the invention, the agents contain at least one acid. Inorganic acids, for example the mineral acids, for example hydrochloric acid, and organic acids, for example saturated or unsaturated Cj, are suitable. ₆ mono-, di- and tricarboxylic acids and hydroxycarboxylic acids with one or more hydroxyl groups, for example citric acid, maleic acid, formic acid and acetic acid, amidosulfuric acid, C ₆ . ₂₂ fatty acids and anionic sulfonic acids, and mixtures thereof, for example that available under the trade name Sokalan ^® DCS from the Fa. BASF succinic glutaric acid-adipic acid mixture.

If appropriate, one or more alkalis can additionally be used, for example the alkali metal, alkaline earth metal and ammonium hydroxides and carbonates and ammonia, preferably sodium and potassium hydroxide, K-dium hydroxide being particularly preferred.

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 . ₃ -hydrocarbon radical R wear, for example, C ₆ - sulfonic acids ₂₂ alkane, in particular secondary alkane sulfonate (SAS), such as Hostapur ^® SAS 60, C ₆ (from Clariant.). ₂ -α-olefin sulfonic acids and - ^ - alkyl-Co-io-arenesulfonic acids such as Ci- _22- alkylbenzenesulfonic acids or d- _22- alkylnaphthalenesulfonic acids, preferably linear C ₈ . ₁₆ alkylbenzenesulfonic acids, in particular linear C ₁₀ -alkyl, C ₁₀ . ₁₃ alkyl and C ₁₂ alkylbenzenesulfonic acids. In addition, fatty alkyl sulfates or branched alkyl sulfates such as Neodol ^® 45 sulfate are suitable.

Particularly preferred acids are citric acid, preferably used in the form of its monohydrate citric acid-1H ₂ 0, and the anionic sulfonic acids and combinations of citric acid with one or more anionic sulfonic acids, especially with alkylarene sulfonic acids. Citric acid advantageously combines acid, builder and phase releasing agent properties, while the anionic sulfonic acids act simultaneously as an acid and an anionic surfactant.

The agent according to the invention contains one or more acids in a strength and molar mass which are sufficient to adjust the desired acidic pH Acids to be selected according to the amount by weight which is usually between 0.1 and 30% by weight, in particular between 1 and 20% by weight. If necessary, in particular if the acid also fulfills other functions, as described above and also below, it may be advantageous to use more acid than is necessary for pH adjustment. In this case, the agent according to the invention additionally contains one or more alkalis.

phases

When the washing and cleaning agents according to the invention are formulated as liquid / liquid mixtures, there are preferably two continuous liquid aqueous phases which are not miscible with one another and can be temporarily converted into an emulsion by shaking.

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

In a preferred embodiment of the invention, the continuous phases I and II are delimited from one another by a sharp interface.

In a further preferred embodiment of the invention, one or both of the continuous phases I and II contain parts, preferably 0.1 to 25% by volume, in particular 0.2 to 15% by volume, based on the volume of the respective continuous phase, the other phase as a dispersant. The continuous phase I or II is then reduced by the volume that is distributed as a dispersant in the other phase. Agents in which phase I is emulsified in phase II in amounts of 0.1 to 25% by volume, preferably 0.2 to 15% by volume, based on the volume of phase II, are particularly preferred. In a further preferred embodiment of the invention, in addition to the continuous phases I and II, part of the two phases is present as an emulsion of one of the two phases in the other phase, this emulsion not being present due to two sharp interfaces, an upper and a lower one parts of phases I and II involved in the emulsion are delimited.

The agents according to the invention contain phase I and phase II in a volume ratio of 90:10 to 10:90, preferably 75:25 to 25:75, in particular 65:35 to 35:65.

Washing and cleaning agents according to the invention in the form of liquid / solid mixtures preferably have an upper aqueous phase I and a lower solid phase II, both phases being able to be temporarily converted into a dispersion by shaking. It is particularly preferred if the lower, solid phase is essentially formed by the bleaching agent or bleaching system. In particularly preferred embodiments, the bleaching agent is therefore present as a sediment in the liquid phase I.

However, the bleaching agent can also be present as a separate, solid phase in multi-phase compositions with two or more liquid phases. When such agents according to the invention are shaken, an emulsion of the liquid phases is temporarily formed, which disperses the solid phase.

In a further embodiment of the invention, the washing and cleaning agent is in a combination of a liquid and a gaseous phase. In addition to air, the gas phase preferably contains other gaseous constituents, such as, for example, Pf-f oils, protective gas (N ₂ , argon, helium and the like), oxygen and / or ozone (preferably as oxidizing agent / disinfectant additives). Carbon dioxide (CO ₂ ) is also suitable, in particular in equilibrium with water (H ₂ O + CO ₂ = H ₂ CO ₃ ).

In addition to an improved release of paraffin oils, the advantages of the agents according to the invention are the stabilization of the sensitive additives with regard to storage stability and an improved visual appearance. bleach

In bleaching agents according to the invention, preference is given to compounds which split off H ₂ O ₂ in water, particularly preferably also H ₂ O itself.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as persulfates or persulfuric acid. The urea oxohydrate percarbonide, which can be described by the formula H2N-CO-NH ₂ Η ₂ O2, can also be used. In particular, when using the agents for cleaning hard surfaces, for example in automatic dishwashing, they can, if desired, also contain bleaching agents from the group of organic bleaching agents, although their use is in principle also possible for agents for textile washing. Typical organic bleaching agents are the dacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and Magnesii-m-monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalidonic acid (ε-phthalidoxy phthalimidoxy phthalimidoxy acid) , PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-disperoxyazelaic acid, diperoxysebacassoxy acid, diperoxy acid, diperoxy acid, diperoxy acid, diperoxy acid Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

Bleach activators

Preferred embodiments of the present invention additionally contain one or more bleach activators which increase the bleaching performance, in particular at low temperatures. The bleach activators will be selected by the person skilled in the art with regard to their dissolution behavior so that the bleach activators are essentially in the phase, which contains the bleaching agent in a lower concentration, in order to avoid unnecessary contact between the two groups of substances.

Depending on the bleaching agent used, the bleach activators are selected from compounds such as, for example, tetraacetylethylene diamine (TAED), pentaacetyl glucose (PAG), Na-p-isononanoyl-benzene-sulfonate (z ^' -NOBS), N-methyl-diacetamide (from Montefluos), Iso - propenyl acetate, isatoic anhydride, N-acetyl-caprolactam, N-benzoylcaprolactam, 1-benzoyl-3-amino- (l, 2,4) triazole, l-acetyl-3 (N-acetyl-N-benzoyl) - ( 1,2,4) triazole, MMA (BASF), nitrile quats, triethyl citrate, mixed anhydrides of citric acid and acetic acid, in particular triple acetic anhydrides of citric acid, Mn salts and the like.

hydrophobic components

In a particularly advantageous embodiment of the invention, the agents contain one or more hydrophobic components. The hydrophobic components not only improve the cleaning effect against hydrophobic contaminants such as greasy dirt, but also have a positive effect on the phase separation and its reversibility. Suitable hydrophobic components are, for example, dialkyl ethers with identical or different C ₄ to C ₁₄ alkyl radicals, in particular linear dioctyl ether; Hydrocarbons with a boiling range from 100 to 300 ° C, in particular 140 to 280 ° C, for example aliphatic hydrocarbons with a boiling range from 145 to 200 ° C, isoparafins with a boiling range from 200 to 260 ° C; essential oils, in particular limonene and pine oil extracted from pine roots and stumps; and also mixtures of these hydrophobic components, in particular mixtures of two or three of the hydrophobic components mentioned. Preferred mixtures of hydrophobic components are mixtures of various dialkyl ethers, of dialkyl ethers and hydrocarbons, of dialkyl ethers and essential oils, of hydrocarbons and essential oils, of dialkyl ethers and hydrocarbons and essential oils and of these mixtures. The agents contain hydrophobic components in amounts, based on the composition, of 0 to 20% by weight, preferably 0.1 to 14% by weight, in particular 0.5 to 10% by weight, most preferably 0.8 to 7 wt .-%. Phase separation auxiliaries

The agents according to the invention can contain one or more phase separation aids. In addition to citric acid or citrates, 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, while sodium sulfate and in particular magnesium sulfate have a less phase-separating effect. The compositions contain phase separation aids in amounts, based on the composition, of 0 to 30% by weight, preferably 1 to 20% by weight, in particular 3 to 15% by weight, extremely preferably 5 to 12% by weight.

surfactants

The agents according to the invention can contain anionic, nonionic, 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 0.01 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 14% by weight, extremely preferably 3 to 10% by weight. -%.

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 C ₆ -C ₂₂ alkyl benzene sulfonates, in particular dodecylbenzenesulfonate, but also C ₆ -C ₂₂ alkane sulfonates, C ₆ -C ₂₂ c olefin sulfonates, sulfonated C ₆ -C ₂₂ fatty acids, C ₆ -C ₂ 2 carboxamide ether sulfates, sulfosuccinic acid mono -CC ₁₂ alkyl esters, C6-C ₂₂ -Alkylpolyglykolethercar- boxylate, C ₆ -C ₂₂ -N-acyl taurides, C ₆ -C ₂ -N-sarcosinates and C ₆ -C ₂₂ alkyl isethionates or mixtures thereof. They are in the form of their alkali metal and alkaline earth metal salts, in particular sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetrlykyl monium salts and, in the case of sulfonates, also in the form of their corresponding acid, for example, dodecylbenzenesulfonic acid. When sulfonic acid is used, it is usually mixed in situ with one or more corresponding bases, for example alkali metal and alkaline earth metal hydroxides, in particular sodium, potassium and magnesium hydroxide, as well as ammonia or mono-, di-, tri- or tetraalkylamine, neutralized to the aforementioned salts. The compositions contain anionic surfactants in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 14% by weight, extremely preferably 2 to 10% by weight. %.

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

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

Nonionic surfactants

Suitable nonionic surfactants are, for example, C ₆ -C ₂₂ alkyl alcohol polyglycol ethers, alkyl polyglycosides and nitrogenous surfactants or else sulfosuccinic acid di-CrCπ alkyl esters or mixtures thereof, in particular the first two. The compositions contain nonionic surfactants in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 0.5 to 14% by weight, extremely preferably 1 to 10% by weight.

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

The C ₆ -C ₂ 2 -alkyl alcohol polyglycol ethers of the formula I can be obtained by adding propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to fatty alcohols. hold. Typical examples are polyglycol ethers of the formula I in which R 'represents an alkyl radical having 8 to 22 carbon atoms, p represents 0 to 2 and e represents numbers from 2 to 7. Preferred representatives are, for example, CoC ₁₄ -FettalkohoHTPO + 6EO ether (p = 1, e = 6 •), and C ₁ 2-C ₁₈ fatty alcohol + 7EO ether (p = 0, e = 7) and mixtures thereof.

End-capped C ₆ -C ₂₂ alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group is etherified in the form-II II. The end-capped C ₆ -C _{2 2} -alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry. C6-C22 alkyl alcohol polyglycol ethers are preferably reacted with alkyl halides, especially butyl or benzyl chloride, in the presence of bases. Typical examples are mixed ethers of the formula I in which R! stand for a technical fatty alcohol residue, preferably C _{12 14} -K0- kosalkyl residue, p for 0 and e for 5 to 10, which are closed with a butyl group.

Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula II, R "O [G] χ, in which R" for a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] for a glycosidically linked sugar radical and x stands for a number from 1 to 10. APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry. The index number x in the general formula II indicates the degree of oligomerization (DP degree), i.e. 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 can above all assume the values x = 1 to 6, the value x is for a specific alkyl glycoside an analytically calculated quantity, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.7 and 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 II) 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, as described, for example, in Course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from RoELEN's oxo synthesis.

However, the alkyl or alkenyl radical R "is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Furthermore, elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol and their eruc To call mixtures.

Nitrogen-containing surfactants may be included as further nonionic surfactants, e.g. Fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides which have alkyl groups with 10 to 22 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.

Amphoteric surfactants

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^" , in which R ^iü an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms, which may be interrupted by heteroatoms or heteroatom groups and R ^1V and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₂₂ -alkyl-dimethylcarboxymethylbetaine and Cπ-C ₁₇ -alkylamidopropyl-dimethylcarboxymethylbetaine. The compositions contain amphoteric surfactants in amounts, based on the composition, from 0 to 15% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight.

Cationic surfactants

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^ XR ^ XR ^ 'XR ^ N ⁺ X ^' , in which R ^vi to R ^{ix represent} four identical or different types, in particular two long-chain and two short-chain, alkyl radicals and X ^" stand for an anion, in particular a halide ion, for example didecyl-dimemyl ---- mmonium chloride, alkyl-benzyl-didecyl ---- mmonium chloride, Al- ^ l-dimemyl-hydroxyethyl --- mmonium chloride, bromide or methyl sulfate, especially with C ₂ alkyl, and mixtures thereof. hold cationic surfactants in amounts, based on the composition, of 0 to 10% by weight, preferably 0.01 to 5% by weight, in particular 0.1 to 3% by weight.

In a preferred embodiment, the compositions of the invention comprise anionic and nonionic surfactants together, preferably C ₆ -C ₂₂ alkylbenzene sulfonates, C ₆ -C ₂₂ alkyl sulfates and / or C ₆ -C 22 alkyl ether sulfates alongside C ₆ -C ₂₂ glycol ethers and -Alkylalkoholpoly- / or alkyl polyglycosides, in particular C ₆ -C ₂₂ alkylbenzenesulfonates in addition to C ₆ -C ₂₂ alkyl alcohol polyglycol ethers.

Builder

Furthermore, the agents according to the invention can contain one or more builders. 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 phosphonates and phosphates, for example sodium hexametaphosphate. 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, extremely preferably 2 to 10% by weight , The builder salts also act as phase separation aids.

A preferred builder is citrate from the group 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, extremely preferably potassium citrate.

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

If the builder is also to act as a pH-stabilizing buffer, alkali metal and alkaline earth metal carbonates and bicarbonates, for example soda, are preferred. viscosity

The viscosity of the liquid phase (s) at 20 ° C. is preferably 5 to 100,000 mPa-s, in particular 10 to 5000 mPa-s, particularly preferably 10 to 200 mPa-s, measured using a Brookfield rotary viscometer of the LVT type or LVDV-II + with small sample adapter at a speed of 30 min ^"1 , the Brookfield spindle being used as the measuring body being selected so that the torque is in a favorable range and the measuring range is not exceeded. In this context, spindle 31 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 (/ NC / name according to the International Dictionary of Cosmetic Ingredients from 77ze Cosmetic, Toiletry, and Fragrance Association (CTFÄ): Carbomer), also known as carboxyvinyl polymers. Such polyacrylic acids are available, inter alia, from BFGoodrich under the trade name Carbopof, for example 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 consisting of acrylic acid, meth- acrylic acid and its simple, preferably formed with C _M alkanols, esters (INCI acrylates copolymer), for example the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (C4S name according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and Methyl methacrylate (CAS 25852-37-3) belong and which are available, for example, from Rohm & Haas under the trade names Aculyn ^® and Acusof, for example 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. ₃ o-alkyl acrylates with one or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters (INCI acrylates / C 10-30 alkyl acrylate crosspolymer), which are preferably formed with d- ₄ -alkanols, and which are, for example, from BFGoodrich are available under the trade name Carbopof, e.g. the hydrophobized Carbopof ETD 2623 and Carbopof 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) as well as Carbopof AQUA 30 (formerly Carbopof EX 473). In addition to the thickening effect, these agents can have other effects in laundry detergents, such as protection against graying.

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. 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. Hydroxyethyl starch, starch phosphate ester or starch acetate, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxy ethyl 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 ^χ 10 ⁶ and is available, for example, from Kelco under the trade name Keltrof, for example as cream-colored powder Keltrof T (Transparent) or as white granulate Keltrof RD (Readily Dispersable).

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 perfume and fragrances, polymers, soil release agents, solvents (e.g. ethanol, isopropanol, glycol ether), solubilizers, hydrotropes (e.g. cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), cleaning enhancers, disinfectants, antistatic agents, preservatives, bleaching systems , Enzymes and dyes as well as opacifiers or skin protection agents, as described in EP-A-522 506. In addition, the agents can also contain insecticides and insect repellents, as well as pH indicators and / or so-called anti-fouling agents. Preferred anti-fouling agents are strong oxidizing agents such as bromine in combination with alcohol or ether components or hydrophobic components. Bromine is particularly preferred in combination with glutaraldehyde and decanol. However, any other prior art anti-fouling agents can also be used in the context of the present invention, for example the anti-fouling emulsions disclosed in WO 00/15562.

The amount of such auxiliaries and additives is usually not more than 12% by weight in the cleaning agent. The lower limit of use depends on the type of additive and can be up to 0.001% by weight and below, for example in the case of dyes. The amount of auxiliaries is preferably between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.

Preferred auxiliaries and additives are perfume and fragrances and dyes, since the perfume and fragrances generally also support the phase separation in addition to the fragrance effect, while the phases can be colored differently by adding dyes, which improves the visual perception of the separated phases as well as tracking the emulsion formation or separation, and so the handling of the agent is made 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 reversible phase separation is caused by the complex interplay of a number of components and their characteristics are determined. The surfactant present, together with the acid, can already lead to the 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.

example

The agents E1 (liquid / liquid) and E2 (liquid / solid) according to the invention were produced as described above. Table 1 shows their composition in% by weight, the pH values and also the quantified volume ratios of the lower phase I to the upper phase II.

Table 1

Composition [% by weight] El E2

C ₁₀ . _13- alkylbenzenesulfonic acid 4 20

C ₁₂ - ₂₂ fatty alcohol + 7EO ether 2 5

Citric acid - 1 H ₂ O 6.5 5

Potassium hydroxide 5.9 -

Dioctyl ether 4.5 -

H ₂ O ₂ 0.45

Perborate monohydrate - 15

TAED - 5th

Perfume 1.5 1.2

Dyes <0.01 <0.01

Glutaraldehyde 0.05 0.05

Water ad 100 ad 100 pH 5.8 6.2

Volume ratio phase I: phase II 60:40 75:25

The agent El showed two continuous, transparent phases which temporarily formed a creamy-looking emulsion when shaken. Even after repeated shaking, separate phases formed again when left standing.

Storage stability was checked by storing the agent at an elevated temperature of 40 ° C, after which the H ₂ θ ₂ content was determined. The agent showed no visually perceptible change, in particular the agent could still be reversibly transferred into the temporary emulsion by shaking. The H ₂ θ ₂ content after 10 months was 0.2%. The agent was assessed by the test subjects as visually appealing and easy to use and achieved good cleaning results in both the bathroom and kitchen areas - in undiluted and diluted form - especially when removing limescale and water stains as well as strongly adhering greasy dirt in the form of Connection to a full bath in the bathtub after the bath water has been drained off and the dirt left in the kitchen by the preparation of greasy or oily dishes.

The agent E2 had a transparent liquid phase I and a solid phase II, which could be temporarily converted into a slightly cloudy dispersion by shaking. Even after repeated shaking, the sediment again formed under the clear liquid phase after standing.

Furthermore, two-phase detergents E3-E22 according to the invention, each with a liquid phase and a solid phase, were produced by the process according to the invention, which contain different bleach activators and, as bleaching agents, each contain perborate monohydrate. The compositions are shown in Table 2, the associated bleach activators used in Table 3.

Table 2

Composition [wt% ^1] E3-12 E13-E22

Alkyl polyglycoside 5 5

Ci ₂ - ₂₂ fatty alcohol + 7 EO ether 15 15

LAS-Na 5 5

Edenor K12-18 3 1

Citric Acid x 1 H ₂ O 5 5

KOH / NaOH / MEA to pH 8.5 to pH 7

Perborate monohydrate 20 20

Bleach activator 5 5

Perfume, dyes, water ad 100% ad 100%

Volume ratio phase I: phase II approx. 75:25 approx. 75:25 Table 3

Example bleach activator

E3 E13 tetraacetylethylenediamine

E4 E14 pentaacetyl glucose

E5 E15 Na-p-isononanylbenzenesulfonate

E6 E16 N-methyldiacetamide (Montefluos ^® )

E7 E17 isopropenyl acetate

E8 E18 isatoic anhydride

E9 E19 N-acetylcaprolactam

E10 E20 N-benzoylcaprolactam

Eil E21 1 -Benzoyl-3-amino-1, 2,4-triazole

E12 E22 1 -acetyl-3 (N-acetyl-N-benzoyl) -l, 2,4-triazole

Agents E3-E22 had excellent storage stability and showed no visible changes. By shaking, they could be reversibly converted into temporarily stable dispersions.

Claims

claims

1. Aqueous, liquid, multi-phase surfactant-containing washing and cleaning agent with at least two phases, which has at least one phase I and one phase II and can be temporarily converted into an emulsion, suspension and / or dispersion and / or aerosol by shaking, characterized in that it contains at least one bleach.

2. Composition according to claim 1, characterized in that it has a pH of 9 to 4 in the form of the temporary emulsion, suspension and / or dispersion and / or aerosol.

3. Composition according to one of the preceding claims, characterized in that it contains H ₂ O ₂ and or H ₂ O ₂ forming substances in water as bleaching agents.

4. Composition according to one of the preceding claims, characterized in that it contains percarbonates, perborates, peroxopyrophosphates, perhydrates, peroxydehydrates and / or inorganic and / or organic peracids as bleaching agents.

5. Agent according to one of the preceding claims, characterized in that it additionally contains at least one bleach activator.

6. Composition according to claim 6, characterized in that the bleach activators are essentially contained in the phase which contains the bleaching agent in a lower concentration.

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

8. Agent according to one of the preceding claims, characterized in that one or both of phases I and II parts, preferably 0.1 to 25 vol .-%, in particular 0.2 to 15 vol .-%, based on the volume of the respective continuous phase, each containing the other phase as a dispersant.

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

10. Agent according to one of the preceding claims, characterized in that in addition to phases I and II, part of the two phases is present as an emulsion, suspension and / or dispersion and / or aerosol of one of the two phases in the other phase, this emulsion, Suspension and / or dispersion and / or aerosol is delimited by two sharp interfaces, an upper and a lower, compared to the parts of phases I and II not involved in the emulsion, suspension and / or dispersion and / or aerosol.

11. Agent 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.

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

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

14. Composition according to one of the preceding claims, characterized in that it is anionic and nonionic surfactant, preferably C ₆ -C ₂₂ alkyl benzene sulfonates, C ₆ -C ₂₂ alkyl sulfates and / or C ₆ -C ₂₂ alkyl ether sulfates in addition to C ₆ -C ₂₂ alkyl alcohol polyglycol ethers and / or alkyl polyglycosides, in particular C ₆ -C ₂₂ alkyl benzene sulfonates in addition to C ₆ -C ₂₂ alkyl alcohol polyglycol ethers.

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

16. Composition according to one of the two preceding claims, characterized in that it contains potassium hydride as a builder.

17. 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, suspension and or dispersion and / or aerosol.

18. Use of an agent according to one of claims 1 to 16 for cleaning surfaces of all kinds.