Storage-stable microemulsion

Abstract

1. A multiphase system, comprising (A) water; (B) one or more liquid compounds having a solubility of less than 2 g in 1,000 g of water at 25 °C; (C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 ° C; (D) one or more liquid amphiphilic compounds; (E) one or more tensides selected from an anionic tenside (E1), a cationic tenside (E2), a non-ionic tenside (E3) and an amphoteric tenside (E4); and (F) optionally one or more additives.

Description

intelligent fluids GmbH December 19, 2025 120901P1328PCSTORAGE-STABLE MICROEMULSIONFIELD OF THE DISCLOSURE

[0001] The present disclosure is generally related to solutions for cleaning of surfaces, and more specifically related to efficaciously forming microemulsions for removing contaminants from surfaces and devices in industrial and commercial applications.BACKGROUND

[0002] Efficient and thorough cleaning of surfaces or devices, especially in an industrial setting, is a necessary step in the manufacture of goods, especially those dealing with food products or multi-step manufacturing. Clean-in-place (CIP) cleaning techniques are a specific cleaning regimen adapted for removing contaminants from the internal components of equipment such as tanks, lines, pumps and other equipment used for processing typically liquid product streams such as beverages, milk, juices, corn stillage, ethanol, beer, wine, etc. These product streams leave soil deposits on the inside of the equipment that need to be removed. The soil deposits can include protein, fat, carbohydrate, and mineral deposits from the products themselves. These soils can provide an environment for microbial growth and those microorganisms can form an additional soil that needs to be removed, including vegetative bacteria, spores, and biofilms. CIP cleaning involves passing cleaning compositions or solutions through the system without dismantling any system components. The minimum CIP technique involves passing the cleaning solution through the equipment and then resuming normal processing.

[0003] In addition, in other settings, such as a workshop or household, deposits on surfaces or devices may occur, including grease, dirt, cooking oils, and microbial growth and othermicroorganisms. These surfaces or devices must also be cleaned by applying a cleaning solution and then scrubbing or wiping the surface or device.

[0004] Although conventional techniques are effective to remove most soils or bulk particles, they are not always sufficient at removing all types of contaminants. In particular, microorganisms and biofilms derived therefrom can be difficult to remove completely from the equipment surface by the conventional cleaning processes. These unremoved contaminants can cause serious quality, health, and / or safety issues.

[0005] In addition, the cleaning agents that may be used can themselves cause serious quality, health, and / or safety issues.

[0006] In addition, some cleaning agents may cause environmental or health damage if used in sufficient quantity.

[0007] In addition, most of the presently used cleaning agents are not storage stable.

[0008] EP 3151971 B1 discloses a system and method for spraying a dispensable mixture.

[0009] For the cleaning processes, there is therefore a great need for more effective cleaning agents which are more protective of the environment, health, and the substrate, and which can be stored without degradation.

[0010] The object of the present invention, therefore, is to provide such agents and to use such agents for removing contaminants, for example photoresist coatings, from surfaces.

[0011] These agents are intended to be used as a replacement for currently-used cleaning agents. Efficient application of these agents is particularly beneficial in industrial cleaning applications where precise and controlled application is required. Therefore, a method of creating microemulsion at the point of application (so called spray-in-air technique) is desirable, since microemulsions tend to decompose over time. This method diverges from traditional water- and oil-based microemulsion methods by forming emulsions directly during use.DESCRIPTION OF THE FIGURES

[0012] Figure 1: Figure 1 shows the beginning of gas formation (time point t = 2 h after mixing) for mixture 1 comprising water components (marked as “Fluid Part A”), mixture 2 comprising oil / oil-like components (marked as “Fluid Part B”), a 1 : 1 combination of mixtures 1 and 2 (marked as “Mix A + B”) and the multiphase system 1 (marked as “Gasing Fluid”). As can be seen, the liquids of the bottles “Mix A + B” and “Gasing Fluid” immediately formed gas, while no gas formation was observed for “Fluid Part A” and “Fluid Part B”.

[0013] Figure 2: Figure 2 shows the gas formation test of Figure 1 after 1 month. As can be seen, the liquids of the bottles “Mix A + B” and “Gasing Fluid” formed a significant amount of gas, leading to overflowing and crystallization of the overflowed liquids.

[0014] Figure 3: Figure 3 shows the commercially available dispensing apparatus “Arvox Twin Sprayer” from Arva Greentech Deutschland GmbH.

[0015] Figure 4: Figure 4 shows a swapping of the chambers of the Arvox Twin sprayer apparatus.DETAILED DESCRIPTION

[0016] The present invention describes a novel method for use of cleaning agents based on a multiphase system by forming emulsions directly during use. The process leverages eco- friendly, biodegradable, and non-toxic formulations that align with sustainable industrial practices.

[0017] The object is achieved according to the invention by a multiphase system comprising two immiscible liquids, one of the liquids being water or a substance similar to water, and the other of the two liquids being a water-insoluble substance having a solubility of less than 4 g / L in water, additionally containing at least one surfactant, amphiphiles, and optionally additivesand / or auxiliary materials, the multiphase system being characterized in that it has a turbidity characteristic greater than 0 to 200 NTU.

[0018] The Nephelometric Turbidity Unit (NTU) is a unit used in water treatment for turbidity measurements of liquids. It is the unit of the turbidity of a liquid which is measured with a calibrated nephelometer.

[0019] The term “liquid” as used herein denotes a compound which is liquid at 25 °C. Such compound may be regarded as e.g. “oil”.

[0020] Water solubilities as defined herein may be taken from respective textbooks or may be determined according to methods known in the art.

[0021] The surfactant used may be a nonionic, cationic, anionic, or amphoteric surfactant.

[0022] Surfactants within the meaning of the present invention are substances which lower the surface tension of a liquid or the interfacial tension between two phases, and allow or facilitate the formation of dispersions / emulsions or act as solubilizers. Under the action of surfactants, two liquids which in fact are immiscible with one another, such as oil and water, may be finely blended (dispersed). Surfactants form a typical micelle structure, i.e., above a certain concentration they form fairly large, loose structures, which in the present context is referred to as “structure-forming”. Surfactants within the meaning of the invention have an oriented molecular structure, wherein one part of the molecule generally is composed of a hydrophobic, water-repellent carbon moiety and the other part is composed of a hydrophilic, water-tolerant moiety.

[0023] Examples of surfactants within the meaning of the invention include but are not limited to higher alcohols, in particular those with hydrophilic and lipophilic molecular parts, such as n- and iso-isomers of butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, and dodecanol, or modified derivatives thereof in the hydrophobic and / or hydrophilic part of the molecule.

[0024] As anionic surfactants, for example, alkali or ammonium salts of long-chain fatty acids, alkyl(benzene) sulfonates, paraffin sulfonates, bis(2-ethylhexyl) sulfosuccinate, and alkyl sulfates, preferably sodium dodecyl sulfate, may be used. For special applications, for example involving corrosion protection, alkyl phosphates (for example, Phospholan® PE 65, Akzo Nobel) may sometimes be used.

[0025] As nonionic surfactants, polyalkylene oxide-modified fatty alcohols, for example Berol® types (Akzo-Nobel) and Hoesch® T types (Julius Hoesch), alkyl ethoxylates, in particular selected from C9-C13 n-alkyl-ethoxylates or C9-C19 iso-alkyl-ethoxylates, as well as corresponding octyl phenols (triton types) or nonyl phenols (provided that the latter are not released to the environment in large quantities) may be used. In one special field of application, heptamethyltrisiloxanes (for example, Silwet® types, GE Silicones) may be used as agents for greatly increasing the spreading properties of the liquids or for greatly reducing the interfacial tension.

[0026] As cationic surfactants, coco bis(2-hydroxyethyl)methylammonium chloride or polyoxyethylene-modified talc methylammonium chloride, for example, may be used. The use of various amphoteric surfactants is also possible. If a broader pH range is to be covered, coco dimethyl amine oxide (Aormox® MCD, Akzo-Nobel) has proven to be suitable.

[0027] The surfactants are preferably contained in the multiphase system according to the invention in quantities of 2 to 20% by weight, based on the total weight of the multiphase system.

[0028] According to the invention, the water-insoluble substances are those having a solubility in water of less than 4 g / L, preferably less than 2 g / L. These substances should preferably have swelling and / or dissolving properties. Examples include alkanes (gasolines) and cycloalkanes (preferably cyclohexane). Aromatics such as toluene, xylenes, or other alkylbenzenes as well as naphthalenes may also be suitable. Long-chain alkanoic acid esters such as fatty oils andfatty acid methyl esters (biodiesel) are preferred. Further preferred are oils, for example esters, succinic acid esters, adipic acid esters, glutaric acid esters as well as di-n-octylether, petroleum ether and p-menthan. According to the invention, benzyl acetate is also included in the waterinsoluble substances used. Terpenes, for example monocyclic monoterpenes with a cyclohexane backbone, may also be used, wherein terpenes from citrus fruits, such as citrus terpenes and / or orange terpenes, or the limonene contained therein are particularly preferred here. The water-insoluble substances are preferably contained in the multiphase system in quantities of 1.5-30% by weight.

[0029] In a preferred embodiment, the multiphase system comprises no carbon dioxide, in particular in the form of supercritical CO2.

[0030] According to one embodiment, the at least one amphiphile is selected from: a) diols of formula I:R1R2COH— (CH2)n— COHR1R2[formula I] where n is 0, 1, 2, 3, or 4,R1and R2are independently hydrogen or an unbranched or branched C1-C3 alkyl, with the condition that when n=0, R1cannot be hydrogen, and the diol is not 2-methyl-2,4-pentanediol; or is selected from 1,3-propanediol, 1,3 -butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 2,3 -butanediol, 2,4-pentanediol, or 2,5-dimethyl-2,5-hexanediol; b) acetoacetates of formula II:(R3)3C— CO— CH2— CO— O— R4[formula II] whereR3is independently hydrogen or a Ci to C2alkyl, and R4is a branched or unbranched Ci to C4 alkyl; or is selected from ethyl acetoacetate, isopropyl acetoacetate, methyl acetoacetate, n-butyl acetoacetate, n-propyl acetoacetate, or tert-butyl acetoacetate; c) diones of formula III:CH3— (CH2)P— CO— (CH2)q— CO— (CH2)r— CH3[formula III] where p, q, r are independently 0, 1, or 2, with the condition that when the sum of p, q and r equals=2, the compound according to formula III may also be cyclic (cyclohexanedione); or is selected from 2,3-butanedione (diacetyl), 2,4-pentanedione (acetyl acetone), 3,4- hexanedione, 2,5-hexanedione, 2,3-pentanedione, 2,3-hexanedione, 1,4-cyclohexanedione, or 1,3 -cyclohexanedi one; d) esters of formula IVR6— CO— O— R7[formula IV] whereR6is a ring bond to R7, CH3, or COCH3andR7is a (CH2)2— O— ring bond to R6or a (CH2)2— O— (CH2)3— CH3, CH2— CH3, or CH2— CH(CH3) — O — ring bond to R6; or is selected from (1-m ethoxy -2-propyl) acetate, (2 -butoxyethyl) acetate, ethylene carbonate, ethyl pyruvate (2-oxopropionic acid ethyl ester), or propylene carbonate; e) maleic or fumaric acid amides of formula V:R8— HN— CO— C=C— CO— O— R9[formula V]whereR8is hydrogen, a branched or unbranched C1-C4 alkyl, or a branched or unbranched, linear or cyclic Ci-Ce alkyl, wherein the Ci-Ce alkyl is substituted with one or more groups selected from OH, NH2, COOH, CO, SO3H, OP(OH)2, and R9is hydrogen or a branched or unbranched Ci- C4 alkyl; or is selected from the following maleic acid amides and the methyl, ethyl, propyl, and butyl esters thereof: N-m ethyl maleamide; N-ethyl maleamide; N-(n-propyl) maleamide; N- (isopropyl) maleamide; N-(n-butyl) maleamide; N-(isobutyl maleamide); N-(tert-butyl maleamide), and the corresponding fumaric acid amides and the methyl, ethyl, propyl, and butyl esters thereof; f) 2,2-dimethoxypropane, pyruvic acid aldehyde- 1,1 -dimethylacetal, diacetone alcohol (2- methyl-2-pentanol-4-one), 2-butanol, 2-acetyl-gamma-butyrolactone, 3-amino-lH-l,2,4- triazole, gamma-butyrolactone, nicotinamide, ascorbic acid, N-acetylamino acids, in particular N-acetylglycine, -alanine, -cysteine, -valine, or -arginine, triethyl phosphate, n-butyl acetate, dimethylsulfoxide, or 2,2,2-trifluoroethanol.The amphiphile is particularly preferably selected from acetoacetates of formula II:(R3)3C— CO— CH2— CO— O— R4[Formula II] whereR3is H and R4is a Ci to C4 alkyl.

[0031] In a first aspect, the invention relates to a multiphase system, comprising:(A) water;(B) one or more liquid compounds having a water solubility of less than 2 g in 1,000 g of water at 25 °C;(C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 °C;(D) one or more liquid amphiphilic compounds;(E) one or more tensides selected from an anionic (El), a cationic (E2), a non-ionic tenside(E3) and an amphoteric tenside (E4); and(F) optionally one or more additives.

[0032] The present invention may in other embodiments refer to a multiphase system comprising two immiscible liquids, wherein one of the two immiscible liquids comprises(A) water; and the other of the two immiscible liquids comprises(B) one or more liquid compounds having a solubility of less than 2 g in 1,000 g of water at 25 °C;(C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 ° C;(D) one or more liquid amphiphilic compounds;(E) one or more tensides selected from an anionic tenside (El), a cationic tenside (E2), a non-ionic tenside (E3) and an amphoteric tenside (E4); and(F) optionally one or more additives.

[0033] Preferably, the multiphase system may be a composition, comprising:(A) water;(B) one or more liquid compounds having a water solubility of less than 2 g in 1,000 g of water at 25 °C;(C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 °C;(D) one or more liquid amphiphilic compounds;(E) one or more tensides selected from an anionic (El), a cationic (E2), a non-ionic tenside (E3) and an amphoteric tenside (E4); and(F) one or more additives.

[0034] The term “composition” as used herein encompasses a single-phase composition as well as an emulsion.

[0035] In one embodiment, in particular for very low contents of water, preferably less than 2 % by weight based on the total amount the composition, the composition according to the invention may exist in the form of a single-phase composition.

[0036] A composition according to the invention with very low amounts of water contained therein may, in the meaning of the invention, also be termed as a “concentrate”. This concentrate may be diluted with water according to desired properties and application requirements.

[0037] In another embodiment, preferably for water contents above 2 % by weight based on the total amount of the composition, the composition according to the invention exists in the form of an emulsion.

[0038] The emulsion may be a water-in-oil emulsion or an oil-in water-emulsion.

[0039] In a preferred embodiment, the composition according to the invention is a microemulsion.

[0040] The term “microemulsion” as used in the art and used herein encompasses a dispersion made of water, oil, and surfactant(s) that is an isotropic and thermodynamically stable system with dispersed domain diameter varying approximately from 1 to 100 nm, usually 10 to 50 nm. Thus, a “microemulsion” represents a fluid nanophase system. Herein, the term “oil” refers to any water-insoluble liquid.

[0041] Thus, the term “microemulsion” encompasses a dispersion wherein the dispersed phase is stabilized by a surfactant and / or surfactant-cosurfactant systems. According to the invention, the composition comprises water (A). The term “water” as used herein may encompass tap water, or partly or fully demineralized water.

[0042] According to the invention, the composition further comprises one or more liquid compounds (B) having a water solubility of less than 2 g in 1,000 g of water at 25 °C. Further preferably, the solubility in water of the one or more liquid compounds (B) is less than 1 g in 1,000 g of water at 25 °C.

[0043] Preferably, the liquid compounds (B) have at least 8 carbon atoms in the backbone and further preferred at least 10 carbon atoms in the backbone.

[0044] In one embodiment, the liquid compounds (B) may consist of carbon and hydrogen only, i.e., the compounds may be alkanes or alkenes such as open-chain alkanes or alkenes or cyclic alkanes or alkenes optionally substituted with one or more alkyl residues. Suitable alkenes are preferably selected from hexenes, octenes, nonenes, decenes, dodecenes, tetradecenes, and cyclic isomers thereof. Further suitable alkenes are selected from terpenes such as limonene.

[0045] In a preferred embodiment, the one or more liquid compounds (B) are selected from alkanes, alkenes, cyclic alkanes, cyclic alkenes, or mixtures thereof.

[0046] In another embodiment, the one or more liquid compounds (B) may be substituted with functional groups. All conceivable functional groups are possible such as hydroxy groups and ester groups, provided the solubility of (B) in water is less than 2 g at 25 °C, preferably less than 1 g per 1,000 g of water at 25 °C.

[0047] In a preferred embodiment, (B) is or comprises N,N-dimethyl 9-decenamide (CAS no. 1356964-77-6). The compound is commercially available.

[0048] In another preferred embodiment, (B) is or comprises methyl 9-dodecenoate (CAS no.39202-17-0). The compound is commercially available.

[0049] Due to their manufacturing process based on natural oils, both N,N-dimethyl 9- decenamide and methyl 9-dodecenoate are regarded as “green” compounds.

[0050] In another preferred embodiment, (B) is or comprises limonene. Limonene is commercially available, e.g. in form of orange oil.

[0051] In a preferred embodiment, (B) comprises N,N-dimethyl 9-decenamide or methyl 9- dodecenoate.

[0052] In another preferred embodiment, (B) comprises N,N-dimethyl 9-decenamide and methyl 9-dodecenoate.

[0053] In another preferred embodiment, (B) comprises N,N-dimethyl 9-decenamide, methyl 9-dodecenoate, and limonene.

[0054] In other preferred embodiment, (B) comprises N,N-dimethyl 9-decenamide and limonene, or methyl 9-dodecenoate and limonene.

[0055] According to the invention, the composition optionally further comprises (C) one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 °C. The liquid esters according to (C) are different from the compounds according to (B). The liquid esters according to (C) may also be regarded as “oil”.

[0056] Basically, all liquid esters may be used provided they have a water solubility of less than 2 g in 1,000 g of water at 25 °C.

[0057] The esters may be based on aliphatic carboxylic acids such as Ci-6 carboxylic acids, e.g., acetic acid, C7-20 fatty acids, aromatic acids such as benzoic acid, or mixtures thereof.

[0058] As alcohol component, preferably short chain alcohols such as methanol, ethanol or propanol are used. The use of benzyl alcohol is likewise possible.

[0059] Representative esters which are suitable in the composition according to the invention may be selected from benzyl acetate, isopropyl myristate, methyl salicylate, or mixtures thereof.

[0060] In a preferred embodiment, (C) comprises a mixture of benzyl acetate, isopropyl myristate, and methyl salicylate.

[0061] The composition according to the invention further comprises one or more liquid amphiphilic compounds (D), i.e., compounds which contain both hydrophilic and lipophilic functional groups. This means nothing else than that the compound is at least partly soluble both in polar solvents such as water (A) and in non-polar solvents such as (B) and (C).

[0062] The term “amphiphilic” as used herein means that the compound is not a tenside, i.e., the amphiphilic compound is not a compound which forms micelles at the interface between water (A) and the water-insoluble organic compounds (B) and (C).

[0063] Preferably, the liquid amphiphilic compounds (D) have a water solubility of from 2 to 120 g in 1,000g of water at 25 °C.

[0064] In one embodiment, (D) comprises one or more of (DI), (D2), (D3), (D4) and (D5):(DI) one or more ketones;(D2) one or more esters;(D3) one or more acetoacetates;(D4) one or more di-alcohols; and(D5) one or more ethers.

[0065] Basically, all liquid ketones, liquid esters, liquid acetoacetates, liquid di-alcohols and liquid ethers may be used, provided they have a water solubility of at least 2 g in 1,000 g of water at 25 °C.

[0066] In a preferred embodiment, (DI) to (D5) have a solubility from 5 to 50 g in 1,000 g of water at 25 °C, and further preferred from 5 to 30 g, or further preferred from 5 to 20 g in 1,000 g of water at 25 °C, respectively.

[0067] Compound (DI) may be a cyclic ketone such as cyclopentanone or cyclohexanone.

[0068] Compound (DI) may be selected from aliphatic ketones such as butanones, pentanones and hexanones. (DI) may be selected from 2-pentanone, 3 -pentanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 2-methyl-3 -pentanone, 2-hexanone, 3 -hexanone, 3 -methyl butanone, 3,3- dimethyl-2-butanone. Preferably, (DI) may be cyclopentanone.

[0069] (D2) may be selected from 3 -methoxy-3 -methyl- 1 -butanol esterified with Ci-4 carboxylic acids of formula (CH3O)(CH3)2C-(CH2)2-OC(O)R (R = H, Ci-4 alkyl). 3 -Methoxy - 3 -methyl- 1 -butanol is commercially available (CAS no. 56539-66-3).

[0070] In one embodiment, (D2) is 3 -methoxy-3 -methylbutylacetate. The compound is commercially available (CAS no. 103429-90-9).

[0071] In a preferred embodiment, (D2) is propylene carbonate.

[0072] In one embodiment, (D3) is selected from one or more acetoacetates of formula (CR3)3C-CO-CH2-C(O)OR4, wherein R3is independently of each other hydrogen or a Ci to C2 alkyl and R4is a branched or unbranched Ci to C4 alkyl, or ethyl acetoacetate, isopropyl acetoacetate, methyl acetoacetate, n-butyl acetoacetate, n-propyl acetoacetate, or t-butyl acetoacetate.

[0073] In one embodiment, (D4) is selected from one or more of 2-ethyl-l,4- hexanediol, 2- methyl-2,4-pentanediol, or 2-(n-butyl)-2-ethyl-l,3-pentandiol.

[0074] In one embodiment, (D5) is selected from glycol ethers of 1 -methoxy -2 -propanol, 1- methoxy-2-butanol and 3-methoxy-3-methyl-l-butanol; propylene glycol butyl ether; propylene glycol phenyl ether; diethylene glycol butyl ether; dipropylene glycol methyl ether and dipropylene glycol butyl ether; or mixtures thereof.

[0075] In a preferred embodiment, the composition according to the invention contains as amphiphilic compound at least (DI) or (D2) or (DI) and (D2).

[0076] In one embodiment, the composition according to the invention may contain besides amphiphilic compounds (DI) or (D2) or (DI) and (D2) additionally one or more of (D3) and / or (D4).

[0077] In another preferred embodiment, the composition according to the invention contains as amphiphilic compound at least (D5).

[0078] In another embodiment, the composition according to the invention may contain besides amphiphilic compounds (D5) additionally one or more of (D2).

[0079] In one embodiment, if desired, the composition according to the invention may also contain, besides amphiphilic compounds (DI), (D2), (D3), (D4) and / or (D5), further amphiphilic compounds. It is possible to subsume amphiphilic compounds as e.g. defined above again under e.g. (DI) to (D5). It has to be understood in this context, that if one component is used as one of components (DI) to (D5) in the inventive composition, then this component cannot be present “again” as “further amphiphilic compound”.

[0080] In one embodiment, the composition of the present invention does not comprise an amphiphilic compound (D3) of formula (CR3)3C-CO-CH2-C(O)OR4, wherein R3is independently of each other hydrogen or a Ci to C2 alkyl and R4is a branched or unbranched Ci to C4 alkyl, or ethyl acetoacetate, isopropyl acetoacetate, methyl acetoacetate, n-butyl acetoacetate, n-propyl acetoacetate, or t-butyl acetoacetate.

[0081] In another embodiment, the composition of the present invention does not comprise an amphiphilic compound (D4), i.e., an amphiphilic compound selected from the group consisting of 2-ethyl-l,4-hexanediol, 2-methyl-2,4-pentanediol, 2-(n- butyl)-2-ethyl-l,3-pentandiol.

[0082] According to the invention, the composition comprises (E) one or more of an anionic tenside (El), a cationic tenside (E2), a non-ionic tenside (E3) and an amphoteric tenside (E4).

[0083] As used herein, the term “tenside” is synonymously used with the term “surfactant”. A tenside encompasses any compound which forms micelles at the interface between water (A) and a water-insoluble organic solvent such as (B).

[0084] Thus, the one or more tensides (E) are chosen so that micelles are formed at the interface between water (A) and the one or more liquid compounds (B).

[0085] Suitable anionic, cationic, non-ionic, and amphoteric tensides are widely known in the art. Such tensides typically are commercially available products.

[0086] Suitable anionic tensides (El) may be selected from: soaps R-CEECOONa, wherein R = C11-17; alkyl benzenesulfonates R-CeEU-SCENa, wherein R = C10-13; alkane sulfonates R1R2CH-SO3Na, wherein R1+ R2= C12-16; a-olefin sulfonates R-CH2-CH=CH-(CH2)n-SO3Na, wherein R = C10-14; sodium salts of sulfated fatty acids derived from vegetable oils and a-sulfo fatty acid methyl esters R-CH(SO3Na)-COOCH3, wherein R = C14-16; alkyl sulfates R-CH2-O- SO3Na, wherein R = Cn-17; alkyl ether sulfates R1R2CH-O-(C2H4O)2-SO3Na, wherein R1+ R2= C 10-14; alkyl ether carboxylic acids RO-(CH2-CH2-O)n-CH2-COOH and RO-(CH(CH3)-CH2- O)n-CH2-COOH, wherein R=C4-20 and n=2-10, and two or more thereof.

[0087] Suitable cationic tensides (E2) may be selected from: quaternary ammonium chlorides such as RJR2R3R4N+CT, wherein R1, R2= Ci6-is; R3, R4= Ci, and ethoxylated C12-14 alkyl(hydroxyethyl)dimethyl ammonium chloride (CAS no.1554325-20-0), and two or more thereof.

[0088] Suitable non-ionic tensides (E3) may be selected from: primary and secondary alcohol ethoxylates RRiCH-O-(CH2-CH2-O)nH, wherein R = Cs-is and Ri = H, n=3-15 for primary alcohol ethoxylates, or R+Ri=Cio-i4 and n=3-12 for secondary alcohol ethoxylates; R-CeEU-O- (CH2-CH2-O)nH, wherein R=C8-12 and n— 5-10, such as C9-11 alcohol ethoxylate (CAS no. 68439-46-3); fatty acid ethanol amides RC(O)-N(CH2-CH2-O)nH(CH2-CH2-O)mH, whereinR=Cn-i7, n=l; 2; m =1; amine oxides Ci2H25-N(CH3)2O; hexyl-D-glucoside (CAS no. 54549- 24-5), and two or more thereof.

[0089] Suitable amphoteric tensides (E4) may be selected from: sulfobetaines RJR2R3N+- (CEh^-SCh’ and betaines R1R2R3N+-CH2-COO', wherein R1=Ci2-i8, R2, R3= Ci, respectively, and two or more thereof.

[0090] The tensides as defined above may contain water as is known in the art.

[0091] Particularly preferred anionic tensides are selected from alkyl ether carboxylic acids, sodium salts of sulfated fatty acids derived from vegetable oils, and a-sulfo fatty acid methyl esters or two or more thereof.

[0092] Particularly preferred cationic tensides are selected from ethoxylated C12-14 alkyl(hydroxyethyl)dimethyl ammonium chloride.

[0093] Particularly preferred non-ionic tensides are selected from C9-11 alcohol ethoxylates and hexyl-D-glucoside or two or more thereof.

[0094] In a preferred embodiment, the composition according to the invention comprises a mixture of tensides (El), (E2), (E3) and optionally (E4).

[0095] The composition according to the invention may contain (F) one or more additives.

[0096] In one embodiment, the additive (F) may comprise a corrosion inhibitor. A suitable corrosion inhibitor is preferably benzotri azole.

[0097] The additive (F) may comprise a fragrance, if desired.

[0098] In a preferred embodiment, the composition comprises 0.1 to 70 wt.-% of component (A), based on the total weight of the composition.

[0099] In a further preferred embodiment, the composition comprises 2 to 30 wt.-% of component (D), based on the total weight of the composition.

[0100] The amount of (A) in the composition can be at least 0.1 wt%, or at least 0.6 wt.%, or at least 1.1 wt.%, or at least 6.1 wt.%, or at least 11.1 wt%, or at least 16.1 wt%, or at least 21.1wt%, or at least 26.1 wt%, or at least 31.1 wt%, or at least 36.1 wt%, or at least 41.1 wt.-%, or at least 46.1 wt.%, or at least 51.1 wt.%, or at least 56.1 wt.%, or at least 61.1 wt.%, or at least 66.1 wt.%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). The amount of (A) in the composition can be at most 70 wt.%, or at most 65 wt.%, or at most 60 wt.%, or at most 55 wt.%, or at most 50 wt.%, or at most 45 wt.%, or at most 40 wt%, or at most 35 wt%, or at most 30 wt%, or at most 25 wt%, or at most 20 wt%, or at most 15 wt%, or at most 10 wt%, or at most 5 wt.%, or at most 1 wt%, or at most 0.5 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). In particular, (A) is present in an amount of 0.1 to 70 wt%, or 1 to 60 wt%, or 2 to 60 wt%, or 10 to 50 wt%, or 20 to 40 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F).

[0101] The amount of (B) in the composition can be at least 4 wt%, or at least 9 wt%, or at least 14 wt%, or at least 19 wt%, or at least 24 wt%, or at least 29 wt%, or at least 34 wt%, or at least 39 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). The amount of (B) in the composition can be at most 40 wt%, or at most 35 wt%, or at most 30 wt%, or at most 25 wt%, or at most 20 wt%, or at most 15 wt%, or at most 10 wt%, or at most 5 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). In particular, (B) is present in an amount of 4 to 40 wt%, or 5 to 30 wt%, or 5 to 25 wt%, or 10 to 20 wt% wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F).

[0102] The amount of (C) in the composition can be at least 0 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 35 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). The amount of (C) in the composition can be at most 40 wt%, or at most 35 wt%, or at most 30 wt%, or at most 25 wt%, or at most 20 wt%, or at most 15 wt%, or at most10 wt%, or at most 5 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). In particular, (C) is present in an amount of 0 to 40 wt%, or 5 to 30 wt%, or 5 to 25 wt%, or 10 to 30 wt%, or 20 to 20 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F).

[0103] The amount of (D) in the composition can be at least 2 wt%, or at least 7 wt%, or at least 12 wt%, or at least 17 wt%, or at least 22 wt%, or at least 27 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). The amount of (D) in the composition can be at most 30 wt%, or at most 25 wt%, or at most 20 wt%, or at most 15 wt%, or at most 10 wt%, or at most 5 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). In particular, (D) is present in an amount of 2 to 30 wt%, or 2 to 25 wt%, or 5 to 25 wt%, or 10 to 20 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F).

[0104] The amount of (E) in the composition can be at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 35 wt%, or at least 40 wt%, or at least 45 wt%, or at least 50 wt%, or at least 55 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). The amount of (E) in the composition can be at most 60 wt.%, or at most 55 wt.%, or at most 50 wt.%, or at most 45 wt.%, or at most 40 wt%, or at most 35 wt%, or at most 30 wt%, or at most 25 wt%, or at most 20 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). In particular, (E) is present in an amount of 15 to 60 wt%, or 20 to 55 wt%, or 25 to 40 wt%, or 30 to 40 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F).

[0105] The amount of (F) in the composition can be at least 0 wt%, or at least 5 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). The amount of (F) in the composition can be at most 10 wt%, or at most 5 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F). In particular, (F) is presentin an amount of 0 to 10 wt%, wherein the wt% are based on the total weight of components(A), (B), (C), (D), (E) and (F).

[0106] In a preferred embodiment, the composition according to the invention comprises:(A) water in an amount of from 0.1 to 70 wt.-%;(B) one or more liquid compounds having a water solubility of less than 2 g in 1,000 g of water at 25 °C, in an amount of from 4 to 40 wt.-%;(C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 °C, in an amount of from 0 to 40 wt.-%;(D) one or more amphiphilic liquid compounds in an amount of from 2 to 30 wt.-%;(E) one or more tensides selected from an anionic tenside (El), a cationic tenside (E2), a nonionic tenside (E3) and optionally an amphoteric tenside (E4) in an amount of from 15 to 60 wt.-%;(F) optionally one or more additives in an amount of from 0 to 10 wt.-%; based on the total amount of the composition (= 100 wt.-%).

[0107] In another embodiment, the composition comprises:(A) water in an amount of from 2 to 60 wt.-%;(B) one or more liquid compounds having a water solubility of less than 2 g in 1,000 g of water at 25 °C, in an amount of from 5 to 30 wt.-%;(C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 °C, in an amount of from 5 to 40 wt.-%, or preferably 5 to 30 wt%(D) one or more amphiphilic liquid compounds having a water solubility of from 2 to 120 g in 1,000 g of water at 25 °C, in an amount of from 2 to 25 wt.-%;(E) one or more of a tensides selected from an anionic tenside (El), a cationic tenside (E2), a non-ionic tenside (E3) and optionally an amphoteric tenside (E4) in an amount of from 20 to55 wt.-%;(F) one or more additives in an amount of from 0 to 10 wt.-%; based on the total amount of the composition (= 100 wt.-%).

[0108] In still another embodiment, the composition comprises:(A) water in an amount of from 10 to 50 wt.-%;(B) one or more liquid compounds having a water solubility of less than 2 g in 1,000 g of water at 25 °C in an amount of from 5 to 25 wt.-%;(C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 °C, in an amount of from 5 to 25 wt.-%;(D) one or more amphiphilic liquid compounds having a water solubility of from 2 to 120 g in 1,000 g of water at 25 °C, in an amount of from 5 to 25 wt.-%;(E) one or more of a tenside selected from an anionic tenside (El), a cationic tenside (E2), a non-ionic tenside (E3) and optionally an amphoteric tenside (E4) in an amount of from 25 to 40 wt.-%;(F) one or more additives in an amount of from 0 to 10 wt.-%; based on the total amount of the composition (= 100 wt.-%).

[0109] Preferably, the composition additionally contains a base such as sodium hydroxide in order to provide a pH of from 7 to 8.0, preferably 7 to 7.5.

[0110] However, the pH of the composition may also be set to an acidic range.[oni] In one embodiment the invention relates to a composition, comprising:(A) water;(B) one or more liquid compounds having a water solubility of less than 2 g in 1,000 g of water at 25 °C;(C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 °C;(D) one or more amphiphilic liquid compounds; wherein (D) comprises (DI) and (D2) or (DI) and (D2) and optionally (D3) and / or (D4);(E) one or more tensides selected from an anionic tenside (El), a cationic tenside (E2), a nonionic tenside (E3) and an amphoteric tenside (E4);(F) one or more additives.In this embodiment, (B) may be selected from alkanes, cycloalkanes, and aromatic compounds, optionally substituted. Preferred alkanes and cycloalkanes may be based on Ce to C15 alkanes and cycloalkanes. Preferred alkanes and cycloalkanes may be based on Ce to C15 alkanes and cycloalkanes. Preferred aromatic compounds may be based on benzenes, e.g. benzene, toluene, or xylene. More preferably, (B) may be selected from Ce to C15 alkenes and cycloalkenes. The alkenes or cycloalkenes may not comprise N,N-dimethyl 9-decenamide nor methyl 9- dodecenoate. Compounds (C), (D), (E) and (F) may be the same compounds as defined above. Thus, (DI) may be selected from 2-pentanone, 3 -pentanone, 3 -methyl pentanone, 4-methyl-2- pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-hexanone, 3 -hexanone, 2- methyl-3 -pentanone, cyclopentanone and cyclohexanone, preferably cyclopentanone. (D2) may be selected from 3 -methoxy-3 -methyl- 1 -butanol esterified with C 1-4 carboxylic acids of formula (CH3O)(CH3)2C-(CH2)2-OC(O)R, wherein R = H, C1-4 alkyl, preferably 3 -methoxy-3 - methylbutylacetate. (E) may comprise a mixture of (El), (E2), (E3) and optionally (E4). Accordingly, in one embodiment of this embodiment, the invention relates to a composition, comprising:(A) water;(B) one or more liquid compounds having a water solubility of less than 2 g in 1,000 g of water at 25 °C, respectively; wherein the one or more liquid compounds are selected from alkanes, cycloalkanes, alkenes, cycloalkenes and aromatic compounds, optionally substituted; whereinthe alkenes do not comprise N,N-dimethyl 9-decenamide or methyl 9-dodecenoate or a mixture thereof;(C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 °C;(D) one or more amphiphilic liquid compounds; wherein (D) comprises (DI) or (D2) or (DI) and (D2), wherein:(DI) is selected from 2-pentanone, 3-pentanone, 3-methyl pentanone, 4- methyl-2- pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2- hexanone, 3-hexanone, 2-methyl-3 -pentanone, cyclopentanone and cyclohexanone, preferably cyclopentanone;(D2) is selected from esterified 3 -methoxy-3 -methyl- 1 -butanol of formula (CH3O)(CH3)2C-(CH2)2-OC(O)R, wherein R = H, Ci-4 alkyl, preferably 3-methoxy-3- methylbutylacetate;(E) one or more tensides selected from an anionic tenside (El), a cationic tenside (E2), a nonionic tenside (E3) and an amphoteric tenside (E4);(F) one or more additives.

[0112] A further aspect of the present invention relates to the use of a multiphase system, as described above, for removing contaminants from surfaces. The surface may be a metal surface or a nonmetallic surface, preferably a silicon or glass wafer and / or a metal surface thereon, preferably copper or aluminum.

[0113] By use of the multiphase system according to the invention, where the contaminant is different than the surface or device, for example a nonmetallic contaminant on a metallic surface, it is easily stripped.

[0114] Multiple contaminants may be stripped at the same time.

[0115] One such contaminant may comprise a photoresist coating. Photoresists are used in microelectronics and microsystem technology for producing structures in the micron and submicron range, and in printed circuit board manufacture. In chemical terms, these are mixtures of prepolymers or polymers based on methyl methacrylate, novolaks, polymethyl glutarimide, or epoxy resins, together with solvents and a photosensitive component.

[0116] There are two basic types of photoresists. The so-called negative resist polymerizes by illumination, and optionally by subsequent thermal stabilization, so that after developing, the illuminated areas remain. The unilluminated areas, which are protected via a mask, remain soluble, and are removed with solvents or with alkaline solutions. The negative photoresists are used primarily in microsystem technology for producing extremely small structures in the micron and submicron range.

[0117] For the positive resists, due to the illumination the already polymerized coating once again becomes partially soluble (depolymerizes) for appropriate developer solutions. The remaining portions of the photoresist protect the portions of the silicon or silicon dioxide surface which are not to be changed, while chemical modification is possible at the exposed locations. In this way, the silicon dioxide may be removed via an etching step, using hydrofluoric acid or CF4, or the free silicon may be doped by ion bombardment.

[0118] The described operations of coating, illumination, stripping, and etching are often repeated multiple times, using different masks.

[0119] One of the most important, constantly recurring cleaning operations is removal of the photoresist. The photoresist must be removed after it has been used as a masking layer.

[0120] A further aspect of the present invention relates to a microemulsion comprising the above-described multiphase system.

[0121] A further aspect of the present invention relates to a method for creating a microemulsion using the multiphase system.

[0122] In one embodiment, the present invention relates to a process for a preparation of an oil in water (O / W) microemulsion or sub-micron emulsion composition, the method including the steps of a) admixing a first part including at least one selected from the group consisting of animal, mineral or vegetable oils, silanes, siloxanes, esters, fatty acids, fats, halogen compounds and alkoxylated alcohols; and one or more lipophilic surfactants, and a second part including water and at least one hydrophilic surfactant to achieve homogeneity, b) heating the mix of step a) to a phase assembly temperature in the range of 40-99° C, preferably 45-95° C, more preferably 65-85° C under continuous mixing to obtain an oil in water microemulsion or sub-micron emulsion, c) allowing said microemulsion or sub-micron emulsion to cool; and d) adding a third part to said microemulsion or sub-micron emulsion at a temperature between 2° C and said phase assembly temperature, said third part if necessary being premixed and heated until the components are dissolved and including at least one component selected from the group consisting of a non-surfactant amphiphilic type compound, a surfactant and water. The liquid amphiphilic compound may not be a surfactant.

[0123] In one preferred embodiment of the present invention, the method can be achieved in such a way that the first and the second part are respectively preheated to a temperature of 40- 99° C, preferably 45-95° C, and more preferably 65-85° C and then admixed to homogeneity; and subsequently the second part is added to the first part at a temperature of 40-99° C, preferably 45-95° C, and more preferably 65-85° C with continuous mixing whereby a microemulsion or sub-micron emulsion is formed at a phase assembly temperature.

[0124] The phase assembly temperature can be determined visually by the achievement of translucence in the composition or by measures such as conductivity which peaks and then is maintained at a plateau whilst phase assembly occurs.

[0125] It has been found that where a non-surfactant amphiphilic type compound such as the polyol is added, if such a compound may be added together with the second part as would conventionally be the case, a microemulsion or sub-micron emulsion is not formed. However, by adding the so called third part, phase assembly occurs at a lower temperature than would be expected and moreover, this phase appears to assist in maintaining the microemulsion or submicron emulsion characteristics of the formulation during storage at normal temperatures

[0126] The water phase of the microemulsion or sub-micron emulsion is desirably added in two aliquots, % and %; in aliquots more preferably of about 70-80% and 20-30% by weight of the total water phase. More preferably, the second aliquot is added after the microemulsion or sub-micron emulsion has formed, at a temperature substantially below the temperature of the first aliquot, and at a rapid rate so as to reduce the overall temperature of the composition preferably to below about 60° C, whereby the microemulsion or sub-micron emulsion structure is fixed.

[0127] Preferably, the microemulsion of the present invention is essentially free of organic solvents, especially of VOCs. VOCs as used herein refer to volatile organic compounds. “Essentially free” within the scope of the present invention means that the microemulsion contains less than 10% by weight, preferably less than 5% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight, especially less than 0.5% by weight, and in particular, is completely free.

[0128] The aqueous microemulsion according to the invention may be prepared using the multiphase system described above. The microemulsion may comprise components a) to e) as essential constituents.

[0129] Component a):

[0130] The aqueous microemulsion according to the invention may comprise, as component a), one or more liquid carboxylic acid esters (hereinafter “ester oils”), which represent the oilcomponent of the microemulsion. Said ester oils are non-polar and lipophilic, and are therefore particularly suitable for oily soils, including soils comprising polymer-based organic components. Moreover, the ester oils exhibit a high boiling point and are thus substantially non-volatile. Suitable liquid carboxylic acid esters have a melting point of below 20 °C and are liquid at 20 °C.

[0131] Suitable carboxylic acid esters may have 6 to 40 carbon atoms, preferably 6 to 22 carbon atoms, especially 10 to 22 carbon atoms. Further, the ester oil may comprise saturated, unsaturated or aromatic radicals.

[0132] Particularly preferred are liquid carboxylic acid esters selected from the group consisting of esters of a monohydric alcohol and a mono- or dicarboxylic acid, and esters of a dihydric alcohol and a monocarboxylic acid. The esters of monohydric alcohols with monocarboxylic acids are more preferred.

[0133] Preferred liquid carboxylic acid esters include esters derived from a C10-C22 monocarboxylic acid and methanol, preferably dodecanoic acid methyl ester or rapeseed oil methyl ester.

[0134] Further preferred are liquid carboxylic acid esters comprising a mixture of monocarboxylic acids having 10 to 22 carbon atoms and methyl esters of dicarboxylic acids having 6 to 10 carbon atoms.

[0135] In a particularly preferred embodiment, the ester oil comprises one or more components selected from the group consisting of rapeseed oil methyl ester, octyl octanoate, oleic acid ethyl ester, methyl laurate, dimethyl succinate, dimethyl adipate, dimethyl glutarate, and isopropyl myristate.

[0136] In a preferred embodiment, the aqueous microemulsion according to the present invention comprises the liquid carboxylic acid ester in an amount of from 10 to 40% by weight,preferably from 20 to 35% by weight, in each case based on the total weight of the microemulsion.

[0137] In order to obtain a well-balanced microemulsion adjusted to the other components and showing a high performance, it may be advantageous to adjust the weight ratio of the liquid carboxylic acid ester (component a)) to the sum of components c), d) and e) to from 1.5 to 10, preferably from 2.5 to 8, especially from 3 to 8, or from 4 to 8.

[0138] Component b)

[0139] The aqueous microemulsions according to the invention may comprise, as component b), one or more water-soluble salts containing one or more cations, preferably selected from the group consisting of sodium, potassium, calcium, magnesium, and ammonium.

[0140] For the purposes of the present invention, salts are considered water-soluble if at least 1 g of salt per liter of water dissolves completely at 20 °C. Alkali, alkaline earth, or ammonium salts are particularly preferred.

[0141] It has been found that the formation of the microemulsion and its temperature stability range can be controlled by the appropriate selection of salts. In the absence of salts, either a very high proportion of surfactant may be required, or the resulting microemulsion may be stable only within a temperature range that is unsuitable for practical applications. The use of salts allows the surfactant content to be reduced, providing both economic and environmental benefits. The amount of surfactant represents a balance, as increasing the surfactant content generally broadens the temperature range in which the microemulsion remains stable. Both inorganic and organic anions may serve as suitable counterions. Preferred inorganic anions are selected from the group consisting of sulfate, chloride, hydrogen sulfate, and phosphate. Preferred organic anions are selected from the group consisting of acetate, gluconate, citrate and tartrate.

[0142] In a particularly preferred embodiment, component b) comprises a water-soluble salt selected from the group consisting of sodium sulfate, sodium chloride, sodium gluconate, sodium citrate, trisodium phosphate, di sodium hydrogen phosphate, potassium sulfate, potassium chloride, ammonium sulfate, ammonium chloride, magnesium sulfate, magnesium chloride, calcium chloride, calcium acetate, magnesium acetate, and potassium sodium tartrate. Surprisingly, particularly good results are obtained with acetate salts. In a particularly preferred embodiment, the microemulsions according to the invention comprise calcium acetate and / or magnesium acetate.

[0143] To adjust the temperature window and optimize the cleaning performance of the microemulsion according to the invention, the salt is preferably present in an amount of from 0.1 to 4% by weight, more preferably from 0.25 to 3% by weight, based on the total weight of the microemulsion.

[0144] Component c)

[0145] The aqueous microemulsions according to the invention may comprise component c), which is one or more salts of sulfosuccinate esters.

[0146] In a preferred embodiment, the sulfosuccinate ester salt is an alkali metal salt, particularly a sodium salt. The sulfosuccinate ester salt functions as an anionic surfactant. Sulfosuccinate ester salts having Ce-Cn alcohol radicals have been found to be especially suitable for the microemulsions according to the invention. These salts contribute substantially to the stability of the microemulsion. More preferably, the salts of sulfosuccinate esters are selected from the group consisting of: diesters of sulfosuccinic acid alkali salts with Ce-Cio alcohols, monoesters of sulfosuccinic acid dialkali salts with Cs-Cn alcohols, and monoesters of sulfosuccinic acid dialkali salts with ethoxylated C10-C14 alcohols.

[0147] In one embodiment, the diester of the sulfosuccinic acid alkali salt contains at least one, preferably two, ethoxylated C10-C14 alcohol radicals.

[0148] The alcohol radicals may be linear or branched. In a particularly preferred embodiment, the sulfosuccinate ester salt is the sodium salt of bis(2-ethylhexyl) sulfosuccinate.

[0149] To obtain an optimized aqueous microemulsion according to the invention, the sulfosuccinate ester salts are typically present in an amount of from 1 to 10% by weight, preferably from 1.5 to 5% by weight, and more preferably from 2.0 to 5.0% by weight, based on the total weight of the microemulsion. On basis of the total weight of components c), d) and e), the salt of the sulfosuccinate esters may be preferably present in an amount of from 30 to 75% by weight, more preferably in an amount of from 40 to 70% by weight.

[0150] Component d)

[0151] As a further essential component, the microemulsions according to the invention comprise component d), which may be one or more non-ionic surfactants selected from alkoxylated sorbitan esters and alkoxylated vegetable oils. Preferably, the non-ionic surfactant is selected from ethoxylated sorbitan esters and / or ethoxylated vegetable oils.

[0152] Preferred sorbitan esters include sorbitan monoesters, in particular sorbitan monoesters having a saturated or unsaturated, linear or branched fatty acid radical. Alkoxylated sorbitan esters, which may be propoxylated and / or ethoxylated, may be used, for example. However, ethoxylated sorbitan esters are particularly preferred, especially those having an average of 3 to 30, preferably 4 to 20, ethoxylate groups.

[0153] In a preferred embodiment, the non-ionic surfactant is an ethoxylated sorbitan monoester having a saturated or unsaturated C12-C18 fatty acid radical.

[0154] In another embodiment, the non-ionic surfactant is an alkoxylated, in particular ethoxylated, castor oil.

[0155] In a preferred embodiment of the present invention, the degree of ethoxylation of the ethoxylated sorbitan ester and / or the ethoxylated vegetable oil is adjusted such that the HLB value is from 11 to 17, more preferably from 12 to 16, or from 13 to 16.

[0156] The HLB value may be calculated according to Griffin as follows: HLB = 20 * Mh / M, where Mh is the molecular weight of the hydrophilic portion of the molecule, and M is the molecular weight of the entire molecule (Griffin, W. C. Classification of Surface Active Agents by HLB, J. Soc. Cosmet. CHEM. 1, 1949).

[0157] Preferably, the non-ionic surfactant is selected from the group consisting of polyoxyethylene(4)sorbitan monolaurate, polyoxyethylene(20)sorbitan monopalmitate, and polyoxy ethylene(20)sorbitan monooleate.

[0158] Preferably, the non-ionic surfactant is present in an amount of from 1.0 to 7.0% by weight, more preferably from 1.5 to 5.0% by weight, or from 1.0 to 5.0% by weight, based on the total weight of the microemulsion.

[0159] In a particularly preferred embodiment, the non-ionic surfactant is present in an amount of from 10 to 70% by weight or from 20 to 60% by weight, preferably from 15 to 60% by weight or from 23 to 55% by weight, respectively, based on the total weight of components c), d), and e).

[0160] Component e)

[0161] As component e), the aqueous microemulsions of the present invention may further comprise one or more booster substances.

[0162] These boosters are intended to enhance the performance of the surfactant system within the microemulsions. In addition, they contribute to broadening the temperature window over which the microemulsions remain stable. Without being bound by theory, the boosters may stabilize the microemulsion by reinforcing or rigidifying the interfacial layer.

[0163] In accordance with the invention, suitable boosters comprise at least one predominantly water-soluble segment and at least one hydrophobic segment, wherein the hydrophobic segment may be located at a chain end, as a pendant (non-terminal) substituent, and / or incorporated between water-soluble segments of the booster molecule.

[0164] The boosters are preferably polymeric in nature. Although the polymer as a whole is predominantly hydrophilic, the presence of one or more hydrophobic segments enables micelle formation in aqueous media. Exemplary boosters of this general type are described, for instance, in DE 198 39 054 and DE 10 2005 049 765.

[0165] The specific chemical structure of the water-soluble segment is not critical per se. Rather, the functional interaction between the comparatively large hydrophilic segment and the hydrophobic segment(s) is considered decisive for the performance of the booster.

[0166] The water-soluble segment may be linear, branched, star-shaped, or otherwise structured, with linear architectures being preferred. As used herein, “linear” denotes a polymer backbone in which the skeletal atoms are arranged in a single, unbranched chain.

[0167] The water-soluble segment may be non-ionic or ionic, including polyelectrolytic structures. Ionic charges may be positioned at any location along the hydrophilic segment. Hybrid structures comprising both ionic and non-ionic portions are likewise contemplated.

[0168] By way of non-limiting example, the water-soluble segments may be derived from monomers such as ethylene oxide, vinylpyrrolidone, acrylic acid, methacrylic acid, maleic anhydride, or combinations thereof.

[0169] Preferred water-soluble polymers include polyethylene oxide and polyethylene glycol. Additional suitable examples include ethylene oxide / propylene oxide copolymers, polyvinyl alcohol and its water-soluble derivatives, polyvinylpyrrolidone, polyvinylpyridine, poly(maleic anhydride), poly(maleic acid), poly(acrylic acid), poly(methacrylic acid), poly(styrenesulfonic acid), and water-soluble salts thereof.

[0170] Linear water-soluble segments are particularly preferred.

[0171] The molecular weight distribution of the water-soluble moiety, defined by the ratio of the weight average molecular weight to the number average molecular weight, may be preferably < 1.2.

[0172] The number-average molecular weight of the water-soluble segment is preferably in the range from 500 to 20,000 g / mol, more preferably from 1,000 to 7,000 g / mol, and most preferably from 1,300 to 5,000 g / mol.

[0173] A particularly preferred booster structure comprises a linear water-soluble polymer carrying at least one hydrophobic group at a chain end.

[0174] The chemical identity of the hydrophobic segment is likewise not subject to strict limitations, provided that it exhibits pronounced hydrophobic or water-insoluble characteristics.

[0175] The hydrophobic segment preferably has a molecular weight of from 80 to 1,000 g / mol, more preferably from 110 to 500 g / mol, and most preferably from 110 to 280 g / mol.

[0176] Suitable hydrophobic segments include water-insoluble radicals, preferably alkyl groups containing from 6 to 50 carbon atoms, more preferably from 8 to 20 carbon atoms. These groups may be linear or branched and may optionally contain aromatic moieties or unsaturation. Hydrophobic organic radicals containing heteroatoms such as oxygen, nitrogen, fluorine, or silicon are also suitable. In certain embodiments, the hydrophobic segment itself may be polymeric.

[0177] The hydrophobic segment may be a defined radical of known molecular weight, such as an alkyl group, or may be derived from technical mixtures. Polymeric hydrophobic segments, for example polybutylene oxide, are likewise suitable.

[0178] The water-soluble polymer may carry at least one hydrophobic segment at a chain terminus.

[0179] Alternatively, more than one hydrophobic segment may be present at a chain end, and / or one or more hydrophobic segments may be positioned at non-terminal locations along the polymer backbone.

[0180] In further embodiments, hydrophobic segments may be incorporated between water- soluble segments, such that the hydrophilic backbone is interrupted by hydrophobic units.

[0181] Any combination of the structural arrangements described above is encompassed by the invention.

[0182] The weight ratio of the water-soluble segment to the hydrophobic segment is preferably from 3 to 300, more preferably from 5 to 200, and most preferably from 5 to 50.

[0183] In a particularly preferred embodiment, the booster comprises a linear water-soluble polymer bearing a single hydrophobic segment at one chain terminus.

[0184] Representative examples of suitable polymeric boosters include alkyl ethoxylates derived from C8-C20 alcohols, alkyl ethoxylates derived from C10-C20 1,2-diols, alkyl ethoxylates derived from C8-C20 a,co-diols, polyethylene glycols bearing hydrophobic end groups obtained, for example, by reaction with C8-C20 isocyanates or acid chlorides, as well as AB diblock, ABA triblock, or BAB triblock copolymers of ethylene oxide and 1,2-butylene oxide.

[0185] Alkyl ethoxylates derived from C8-C20 alcohols are particularly advantageous due to their high effectiveness and biodegradability.

[0186] Owing to their hydrophobic segments, the boosters are capable of forming micellar structures in aqueous media.

[0187] In one embodiment, hydrophobic segments are present at both termini of the water- soluble polymer.

[0188] However, linear water-soluble polymers bearing a single hydrophobic end group are preferred. Within this class, highly ethoxylated alcohol ethoxylates are particularly favored. These compounds may be regarded either as polyethylene oxide chains end-capped with a hydrophobic alkyl group or as highly hydrophilic emulsifiers. Suitable hydrophobic groups include aliphatic alcohols or alkylphenols having from 8 to 20 carbon atoms. The alcoholethoxylates preferably contain from 25 to 500 mol, more preferably from 50 to 200 mol, of ethylene oxide per mole of alcohol. A commercially available example is Brij S 100-PA (SC) from Croda company.

[0189] Preferably, the fraction of water-soluble polymer chains lacking a hydrophobic segment is kept as low as possible, for example not exceeding about 20% by weight.

[0190] In a particularly preferred embodiment, the booster is a hydrophilic polymeric additive comprising a water-soluble polymer bearing a hydrophobic, water-insoluble group having a molecular weight of from 80 to 500 g / mol at one chain terminus, the mass ratio of the water- soluble segment to the hydrophobic group being from 5 to 200. More preferably, the booster consists of a linear water-soluble polymer carrying a hydrophobic, water-insoluble end group having a molecular weight of from 110 to 500 g / mol, most preferably from 110 to 280 g / mol, with a corresponding molecular weight ratio of from 5 to 50.

[0191] In a particularly preferred embodiment, the booster comprises an alcohol ethoxylate of a C8-C20 alcohol having 25 to 500 ethoxy groups, preferably from 50 to 200 ethoxy groups.

[0192] In another preferred embodiment, the booster is present in an amount of from 3 to 20% by weight, preferably from 5 to 15% by weight, and especially from 7 to 15% by weight, in each case based on the total weight of components c), d), and e). Preferably, the aqueous microemulsions according to the invention comprise components c), d), and e) in an amount of from 2 to 20% by weight, preferably from 3 to 15% by weight, more preferably from 3 to 10% by weight, even more preferably from 3 to 8% by weight or from 4 to 8% by weight, in each case based on the total weight of the microemulsion.

[0193] The microemulsions according to the invention are suitable for use as cleaning agents in both private and commercial applications. It is particularly advantageous that the aqueous microemulsions can be employed as neutral cleaners and may thus replace aggressive alkaline cleaners known from the prior art for the removal of oily soils, such as paint residues. In oneembodiment, the microemulsions according to the invention have a pH of from 4 to 11, preferably from 5 to 9.

[0194] In addition, biocides and / or colorants as well as antirust agents and antioxidants can be added.

[0195] The additives can be comprised in amounts of from 0.01 to 3% by weight, preferably from 0.1 to 1% by weight, based on the total weight of the microemulsion.

[0196] The microemulsions according to the invention can be in the form of oil-in-water or water-in-oil microemulsions. Preferably, the microemulsions according to the invention comprise two domains, a hydrophobic and a hydrophilic domain, wherein at the interface between the two domains surface stabilizing active agents, particularly the tensides (E), are enriched in a mononuclear layer. Microemulsions may form very readily and spontaneously because of a very low interfacial tension when the individual components water, oil and a suitable surface-active system are mixed together. Since the domains have very small sizes on the order of a few nanometers in at least one dimension, microemulsions often appear visually transparent and are thermodynamically stable, i.e., without a time limit, in a particular range of temperatures, depending on the surface-active system employed. If microemulsions have low surfactant contents, they may also be turbid, and are nevertheless thermodynamically stable.

[0197] The microemulsion may be preferably stable within a temperature range of from 10 to 40° C., especially from 5 to 60° C.

[0198] In another embodiment, the microemulsions according to the invention are stable within a temperature range of from <5° C. to >60° C.

[0199] In one embodiment, the microemulsion according to the invention may be a water-in- oil or oil-in-water droplet microemulsion, in which water droplets are surrounded by oil, or oil droplets are surrounded by water, respectively.

[0200] Microemulsions comprising two domains may be particularly preferred.

[0201] Typically, the weight proportion of ester oil (component a)) in the mixture of ester oil and water is from 12 to 45% by weight, preferably from 23 to 38% by weight, based on the total weight of ester oil and water in the microemulsion.

[0202] The microemulsions of the invention are thermodynamically and temperature stable liquid systems. “Thermodynamical stable” as used herein and as known in the art refers to a microemulsion being in its lowest free-energy state (AG < 0), so it forms spontaneously and remains stable as long as its composition and conditions are constant. However, as known in the art, thermodynamically stable does not mean “storage stable”. “Storage stability” as used herein and as known in the art, refers to whether a multiphase system preserves its properties over long periods of time (“long-term”) at e.g., room temperature. It is well-known in the art that microemulsions - the multiphase system preferably is a microemulsion - are particularly susceptible to gas formation as the fine distribution of the microemulsion components may facilitate reactions between the components. In particular, degradation reactions (e.g., hydrolysis or oxidation of components) may change the overall composition of a microemulsion. Thus, it was an object of the present invention to overcome these drawbacks of low storage stability by only forming the multiphase system upon application.

[0203] Further, the microemulsions of the invention are transparent to somewhat translucent at room temperature and are isotropic. They are formed by the gentle admixture of the ingredients and do not require shearing or other addition of energy. However, unlike other microemulsion systems, the inventive microemulsions do not require the use of salt solutions for formation. Additionally, because a nonionic surfactant is used as the oil phase, the inventive microemulsions are more versatile than microemulsions with solvent-based oil phase microemulsions, as the inventive microemulsions more readily disperse or solubilize fragrance oils, or other sparingly soluble materials, without the need of hydrotropic substances or otherdispersants. Further, since the oil phase may be a surfactant, greater cleaning efficacy is achieved with the inventive microemulsions.

[0204] A further aspect of the invention relates to a use of a dispensing apparatus to form the multiphase system, which may improve the efficacy of the multiphase system by applying it to the surface in a specific or targeted manner.

[0205] Preferably, the multiphase system is a microemulsion.

[0206] The dispensing apparatus may comprise a source of material to be sprayed and a nozzle for spraying. The source may comprise the components of the multiphase system partially mixed. The material in the source may then be pumped to one or more spray nozzles, dispensing the multiphase system.

[0207] In one embodiment, the source may comprise more than one source, which are then mixed in a mixing chamber prior to the introduction to the spray. Preferably, the source comprises a first source (1) comprising the components (A), (D) and (E), preferably (A) and (E), and a second source (2) comprising the components (B), (D), and (E), preferably (B) and (D), and optionally (C) and (F). The mixture of source (1) may be understood as the “watersource”, while the mixture of source (2) may be understood as the “oil-source”. The mixtures of the source (1) and the source (2) may be immiscible with one another. By separating the multiphase system into more than one source, no multiphase system is formed prior to spraying, thus avoiding storage stability problems.

[0208] By the described separate storage of the components of the multiphase system in different sources of the dispensing apparatus, the addition of stabilizing additives, such as buffer chemicals, may not be necessary.

[0209] In one embodiment, the first liquid, i.e., the mixture of source (1), may flow into the mixing chamber at a first flow rate and the second liquid, i.e., the mixture of source (2), may flow into the mixing chamber at a second flow rate, wherein the first and second flow ratesmay be both greater than 0 mL / min and are different (i.e. not the same flow rate), preferably wherein the second flow rate is greater than the first flow rate, more preferably wherein the second flow rate is at least 2 times, preferably at least 3 times, more preferably at least 4 times, the first flow rate. An advantage of this arrangement is more effective mixing of the first and second liquids within the nozzle configuration due to generating the desired turbulence to mix the immiscible liquids. Other mixing methods, such as are commonly known in the art, may be used.

[0210] Preferably, spraying creates a multiphase system where the droplet size varies in size approximately from 1 to 100 nm, preferably 10 to 50 nm.

[0211] In one embodiment, the method of using the nozzle comprises (1) introducing the mixed multiphase system and a compressed gas (i.e., an energizing gas) into a nozzle; and (2) causing the compressed gas to flow through the nozzle under conditions such that the multiphase system forms a spray of atomized droplets at the nozzle exit. In one embodiment, the multiphase system and compressed gas flow through separate channels of the nozzle. The compressed gas may exit the nozzle at a velocity such that the spray may be shattered into extremely small droplets at the nozzle exit.

[0212] This nozzle may be of the convergent-divergent type. It may be energized by compressed gas (conventionally a light gas such as air, He, O2, or N2). A sonic field may be created at the throat of the nozzle as the compressed gas accelerates and reaches the velocity of sound. These sound waves impinge upon the entrance of a resonator cavity. This resonator cavity serves to produce high frequency waves which produce a chopping effect that breaks up the multiphase system into extremely small droplets.

[0213] Thus, in an aspect, the invention relates to a method for the manufacture of the abovedescribed multiphase system, the method comprising the following steps: providing a first liquid;providing a second liquid; and mixing the first and the second liquid in a dispensing apparatus comprising one or more nozzles in order to form the multiphase system.

[0214] In a preferred embodiment, the first and the second liquid are storage stable and the multiphase system is not storage stable.

[0215] In one embodiment, the method further comprises introducing the mixed multiphase system and a compressed gas (i.e., an energizing gas) into one or more nozzles of the dispensing apparatus, causing the compressed gas to flow through the one or more nozzles under conditions such that the multiphase system forms a spray of atomized droplets at a nozzle exit.

[0216] In one embodiment, the multiphase system and compressed gas flow through separate channels of the nozzle. The compressed gas may exit the nozzle at a velocity such that the spray may be shattered into extremely small droplets at the nozzle exit.

[0217] Preferably, the spray obtained by the above-described method may have a droplet size from 1 to 100 nm, preferably 10 to 50 nm.

[0218] The spray may be an emulsion or a microemulsion.

[0219] In a preferred embodiment, the first and the second liquids are mixed in the mixing chamber comprised in the dispensing apparatus. Preferably, the first liquid flows at a first flow rate into the mixing chamber, and the second liquid flows at a second flow rate different to the first flow rate into the mixing chamber.

[0220] In one embodiment, the environment into which the dispensing apparatus is spraying may be at higher than ambient air pressure. Utilizing a nozzle of the described type and 20-100 pounds per square inch (psi) of back pressure of energizing gas may be used to create uniform droplets of microemulsion of the desired size. When using this nozzle, it has been found that using a chamber pressure of 1,250 psig and an energizing gas pressure of 1,850 psig providesenough energy to reduce particle size substantially. The invention may be practiced with any nozzle that provides a means for using a gaseous (or near-critical or supercritical fluid) stream as energizing medium to atomize the sprayed solution into smaller droplets and / or to create turbulence around the spray droplets which increases the mass transfer rates between the droplet and antisolvent phases. Both converging-diverging nozzles as well as converging nozzles may be employed in the present invention.

[0221] In one embodiment, the sonic field may be created by a piezoelectric element which vibrates.

[0222] In one embodiment, the dispensing apparatus creates an emulsion, which is formed by high shear methods or by high-pressure homogenizer or a microfluidizer in pressures up to 30,000 psi, resulting in low dispersity index droplets between 1 nm and 100 nm in size containing the active agent. The formed emulsion is sprayed via a nozzle as is commonly known in the art.

[0223] Other nozzle types may be used to create the emulsion, such as are presently known in the art.

[0224] The dispensing apparatus may advantageously be made to be actuated between an open and closed position. Preferably, when the dispensing apparatus is activated, it imparts a shear to the composition contained inside, so that the viscosity drops and it can be atomized and sprayed. Such dispensing apparatus are well known and include finger actuated atomizing spray valves and trigger sprayers. When in the closed position, the dispensing means may provide a barrier to escape of the contents of the reservoir. The composition may be dispensed by any convenient means including for example, by pouring, by squeezing, or by spraying from a trigger sprayer. Preferably, the composition is dispensed through a trigger sprayer, for example, from a model T85NDB trigger sprayer available from Continental Sprayers.

[0225] In one embodiment, the dispensing apparatus may be one or more manually operated spray dispensing containers of synthetic organic polymeric plastic, e.g., PVC, polyethylene or polypropylene, which may include nylon closure, valve and nozzle parts, but they can also be packaged under pressure in aerosol containers.

[0226] In one embodiment, the dispensing apparatus may comprise a pressurized vessel. Pressurization may be created by an aerosol spray, a chemical reaction, a pump, a piston, pressure from another source (e.g. a water supply or pressurized air) or other means such as are commonly known in the art.

[0227] Furthermore, the multiphase system herein may be provided as a separate product, or in conjunction with an applicator, for example, a dispensing container, a cleaning implement, and / or a wiping or scrubbing substrate. Preferred dispensing containers are known in the art and will typically comprise a hand-held bottle having an aesthetically desirable and / or ergonomic shape, and a dispensing spout, trigger sprayer, or spray nozzle.

[0228] Furthermore, the dispensing apparatus may comprise a mechanism or nozzle configuration to form particles or droplets of a set size, using such means as are commonly known in the art.

[0229] In one embodiment, the dispensing apparatus may comprise a mechanism or nozzle which allows a user to alter the set size of particles or droplets. In a further embodiment, the mechanism or nozzle may allow a user to alter the amount of water, solvent, or air introduced into the multiphase system, using such means as are commonly known in the art.

[0230] A further aspect of the present invention relates to the use of the multiphase system for cleaning surfaces.

[0231] The invention is now explained with reference to exemplary embodiments, which are not to be construed as limiting the scope of protection.Example 1: Multiphase system 1

[0232] Water (A), liquid compounds (B) comprising Cs to C15 alkenes having a water solubility of less than 2 g in 1,000 g of water at 25 °C, liquid esters (C) comprising C7 to C20 aromatic acids esterified with ethanol and having a water solubility of less than 2 g in 1,000 g of water at 25 °C, amphiphilic liquid compounds (D) including propylene carbonate, tensides (E) comprising an anionic tenside (El) and a non-ionic tenside (E3), and additives (F) comprising corrosion inhibitors, defoaming agents and a fragrance are mixed together and stirred for a suitable time (e.g., 10 minutes) in order to form the multiphase system 1.

[0233] Application test of multiphase system 1 :Freshly prepared multiphase system 1 was applied using a conventional one-chamber spray bottle. Cleaning efficiency was high.

[0234] Gas formation test of multiphase system 1 :Freshly prepared multiphase system 1 has been subjected to a gas formation test for 1 month at room temperature in order to analyze its storage stability. Shortly after the beginning of the gas formation test (time point t = 2 h after mixing), gas formation was observed. Figure 1 shows this immediate gas formation for the bottle filled with the multiphase system 1 (marked as “Gasing Fluid”). Gas formation pressed the liquid into the glass tube of the respective bottle due to the closed system used within this experiment. It is assumed that propylene carbonate in combination with the system's slightly basic resulted in propylene carbonate decomposition and CO2 gas release. Microemulsions - multiphase system 1 preferably is a microemulsion - are particularly susceptible to such storage stability problems, because the fine distribution of the microemulsion components facilitates reactions between the components. Figure 2 shows the situation after 1 month of gas formation testing, where the bottle filled with multiphase system 1 showed overflowing and crystallization of the overflowed liquid.Example 2 (Comparative): Multiphase system 2

[0235] The comparative multiphase system 2 was prepared as described above for multiphase system 1, with the only difference being that an acid was added in order to acidify the liquid.

[0236] Application test of multiphase system 2:Freshly prepared multiphase system 2 was applied using a conventional one-chamber spray bottle. Cleaning efficiency against greasy stains was lower than that of multiphase system 1 due to acidic pH of multiphase system 2. Alkaline cleaners such as multiphase system 1 are preferred for cleaning surfaces.

[0237] Gas formation test of multiphase system 2:The multiphase system 2 has been tested for 2 months. No gas formation was observed, as the assumedly unstable propylene carbonate is stable in an acidic milieu.Example 3: Separation of the multiphase system 1

[0238] The highly gas forming multiphase system 1 has been separated into two mixtures: The water-like mixture 1 comprised water (A), amphiphiles (D) and an anionic tenside (El); the oil-like mixture 2 comprised the liquid compounds (B), the liquid esters (C), amphiphiles (D) including propylene carbonate, and the additives (F). One amphiphile (D) and one non-ionic tenside (E3) have been added into both mixtures 1 and 2, thereby separating multiphase system 1 in a 1 : 1 ratio gravimetrically. As the densities of mixtures 1 and 2 are nearly identical (1016.87 kg / m □respectively 1014.94 kg / m[J, multiphase system 1 was thus separated in a ratio 1 : 1 volumetrically as well, thereby ensuring that the spray generated by the chosen dispensing apparatus (Arvox Twin Sprayer, cf. Example 4) would conform to the composition of multiphase system 1. Both mixture 1 and mixture 2 are homogenous liquids with no phase separation (not even long-term, as confirmed by Figure 2). This is a prerequisite for conforming to the composition of multiphase system 1 as well, as otherwise, the composition of the spraywould shift depending on the phase taken up by the dispensing apparatus. If one or both of the mixtures were prone to phase-separation, this could be approached by equipping the dispensing apparatus with a system premixing / emulsifying the source or sources, either permanently or on-demand before application.

[0239] Application test of the separated multiphase system 1 :Mixtures 1 and 2, each of them stored in one source respectively chamber of the dispensing apparatus, were combined into a homogeneous liquid when sprayed through the nozzle of the dispensing apparatus. The cleaning efficiency of the fluid was as high as that of freshly prepared multiphase system 1 applied using a conventional one-chamber spray bottle.

[0240] Gas formation test of the separated multiphase system 1 :The separate mixtures 1 and 2 did not result in gas formation during the testing period of one month. Figure 1 shows the beginning of a gas formation test (time point t = 2 h after mixing) for the water-like mixture 1 (marked as “Fluid Part A”), the oil-like mixture 2 (marked as “Fluid Part B”), a 1 : 1 combination of mixtures 1 and 2 (marked as “Mix A + B”) and the multiphase system 1 (marked as “Gasing Fluid”). As can be seen, the fluids of the bottles “Mix A + B” and “Gasing Fluid” immediately formed gas, while no gas formation was observed for “Fluid Part A” and “Fluid Part B”. Gas formation pressed the liquid into the glass tube of the respective bottle due to the closed system used within this experiment. Figure 2 shows the gas formation test of Figure 1 after 1 month. As can be seen, the liquids of the bottles “Mix A + B” and “Gasing Fluid” formed a significant amount of gas, resulting in overflowing and crystallization of the overflowed liquids. This confirms that the combination of mixtures 1 and 2 (“Mix A + B”) and multiphase system 1 (“Gasing Fluid”) have the same storage stability problem. Mixtures 1 and mixture 2 (“Fluid Part A” respectively “Fluid Part B”), on the other hand, showed no gas formation even after one month, confirming their storage stability.

[0241] Comparison between multiphase system 1 and the combination of mixtures 1 and 2:To confirm that the separated multiphase system 1 (i.e., mixtures 1 and 2), when combined in a 1 : 1 ratio, confirms to the composition of multiphase system 1, several measurements were performed. Table 1 shows the measurement results, confirming that multiphase system 1 and the 1 : 1 combination of mixtures 1 and 2 are, notwithstanding typical deviations, virtually identical:

[0242] Table 1: Comparison between multiphase system 1 and the combination of mixtures 1 and 2Example 4: Use of a commercially available dual-chamber dispensing apparatus and use of a swapping-proof design

[0243] The commercially available “Arvox Twin Sprayer” from Arva Greentech Deutschland GmbH was used in this experiment as a dual-chamber spray bottle. Product information about the Arvox Twin Sprayer implies that the chambers of the spray bottle are emptied at the same rate. When the bottle was held straight (i.e., in an upright position, as if standing), the chambers were indeed emptied at a ratio near 1 : 1 (see Table 2: tested with tap water in both chambers, confirming the 1 : 1 ratio both gravimetrically and volumetrically). However, when the bottle was not held straight (i.e., the spray head angled at the bottom), the chambers were emptied at a ratio of 1 :0.5. This indicates that the bottle needs to be held straight when used as the inventive dispensing apparatus.

[0244] Table 2: Spray test using the Arvox Twin Sprayer

[0245] Liquids with predominantly water or oil content (as mixtures 1 and 2: mixture 1 : predominantly water content; mixture 2: predominantly oil content) cannot be separated in such a way that an apparatus dispensing liquids in a 1 : 1 ratio could produce the original liquid (as multiphase system 1). The same applies when the modules have significantly different densities and / or viscosities. Two approaches are possible: Either the dispensing apparatus could be adjusted to dispense in a ratio of other than 1 : 1, e.g. by adjusting its flow rates, or the strict separation into a water-like liquid and an oil-like liquid could be abandoned. The first approach is preferred, as the latter approach may lead to formulations having storage stability problems (cf. Experiments 1-3). Thus, as the Arvox Twin Sprayer chambers are designed to be emptiedat the same flow rate, the formation of the inventive multiphase system over the whole inventive ranges of components (A) to (F) is not possible with the state-of-the-art dispensing apparatus.

[0246] Further, swelling of the EPDM (ethylene propylene diene rubber) material used in the tubes of the Arvox Twin Sprayer was observed, likely due to the tubes coming in contact with oil-like substances such as liquid compounds (B) and / or liquid esters (C). EPDM is not oilresistant - it swells on contact with, for example, mineral oils. This problem could be approached by replacing one or both of the tubes of the Arvox Twin Sprayer with ones made from oil-resistant material, such as NPR or PTFE. Replacing only one of the tubes in the dualchamber spray bottle of Arvox is possible, but would require a bottle design that prevents userside swapping of the chambers (see Figures 3 and 4; the chambers have been swapped there; Figure 3 shows the original assembling of the two chambers A and B, while Figure 4 shows a swapping of the chambers: one of the chambers was marked by a red stripe; this marked chamber was connected to the blue cap in Figure 3, while in Figure 4, the marked chamber was connected to the green cap). Possible solutions could include protrusions in the bottle handle whereon the chambers “snap in place” or using a left-hand thread for one side instead of a righthand thread.

[0247] A swapping-proof design may also prevent undesired effects, such as clogged tubes or even chemical reactions, when connecting a chamber containing a water-like liquid instead of a chamber containing an oil-like liquid (and vice versa).

[0248] The inventive dispensing apparatus allows for “mix & match” chamber configurations, enabling the partial or entire omission of e.g. additives, such as corrosion inhibitors, defoaming agents and fragrances, based on the cleaning scenario. For instance, a chamber comprising a water-like liquid such as mixture 1 could be paired with a chamber comprising an oil-like liquid such as mixture 2 either containing a fragrance or not containing one.

Claims

CLAIMS1. A multiphase system, comprising(A) water;(B) one or more liquid compounds having a solubility of less than 2 g in 1,000 g of water at 25 °C;(C) optionally one or more liquid esters having a water solubility of less than 2 g in 1,000 g of water at 25 ° C;(D) one or more liquid amphiphilic compounds;(E) one or more tensides selected from an anionic tenside (El), a cationic tenside (E2), a non-ionic tenside (E3) and an amphoteric tenside (E4); and(F) optionally one or more additives.

2. The multiphase system according to claim 1, wherein the one or more liquid compounds (B) are selected from alkanes, alkenes, cyclic alkanes, cyclic alkenes, or mixtures thereof.

3. The multiphase system according to any one of claims 1 to 2, wherein the one or more liquid esters (C) are selected from Ci-6-carboxylic acids, C7-20 fatty acids, aromatic acids, or mixtures thereof.

4. The multiphase system according to claim 3, wherein the one or more liquid esters (C) is selected from benzyl acetate, isopropyl myristate, methyl salicylate, or mixtures thereof.

5. The multiphase system according to any one of claims 1 to 4, wherein the one or more liquid amphiphilic compounds (D) comprise one or more of (DI), (D2), (D3), (D4) and (D5):(DI) one or more ketones;(D2) one or more esters;(D3) one or more acetoacetates;(D4) one or more di-alcohols; and(D5) one or more ethers.

6. The multiphase system according to any one of claims 1 to 5, wherein the one or more tensides (E) are chosen so that micelles are formed at the interface between water (A) and the one or more liquid compounds (B).

7. The multiphase system according to any one of claims 1 to 6, wherein the multiphase system does not comprise carbon dioxide, in particular in the form of supercritical CO2.

8. The multiphase system according to any one of claims 1 to 7, wherein the multiphase system is a microemulsion.

9. Use of the multiphase system according to any one of claims 1 to 8 for cleaning surfaces.

10. Method for the manufacture of the multiphase system according to any one of claims 1 to 8, the method comprising the following steps: providing a first liquid; providing a second liquid; and mixing the first and the second liquid in a dispensing apparatus comprising one or more nozzles in order to form the multiphase system.

11. Method according to claim 10, wherein the first and the second liquid are storage stable and the multiphase system is not storage stable.

12. Method according to any one of claims 10 to 11, wherein the first and the second liquid are mixed in a mixing chamber comprised in the dispensing apparatus.

13. Method according to any one of claims 10 to 12, wherein the first liquid flows at a first flow rate, and the second liquid flows at a second flow rate different to the first flow rate.

14. Method according to any one of claims 10 to 13, wherein the multiphase system according to any one of claims 1 to 8 and a compressed gas are introduced into the one50or more nozzles of the dispensing apparatus, causing the compressed gas to flow through the one or more nozzles under conditions such that the multiphase system forms a spray of atomized droplets at a nozzle exit.

15. Use of a multiphase system manufactured according to any one of the claims 10 to 14 for cleaning surfaces.51

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