Industrial cleaning fluid for oil removal

Abstract

A multiphase system comprising: (A) a polar solvent comprising a C1-10 alkylene glycol ether; (B) one or more apolar solvents 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; (E) optionally one or more tensides; and (F) optionally one or more additives.

Description

intelligent fluids GmbH December 19, 2025 120899P1328PCINDUSTRIAL CLEANING FLUID FOR OIL REMOVALFIELD OF THE DISCLOSURE

[0001] The present disclosure is generally related to solutions for cleaning of surfaces, and more specifically related to ecological cleaning systems for removing contaminants from surfaces and devices in industrial and commercial applications, without using water in the process.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 other microorganisms. These surfaces or devices must also be cleaned by applying a cleaning solution and then scrubbing or wiping the surface or device.

[0004] In addition, in the oil industry, viscous or even solid oil sludges accumulate in crude oil tanks over continued use (i.e., pumping crude oil into and out of the tank). It is known in the art that such viscous oil sludges are hardly pumpable. In general, to clean the crude oil tanks, said oil sludges need to be liquefied. In conventional techniques, the oil sludges are liquefied using refined oil such as naphtha. However, refined oil does not liquefy the oil sludge completely, necessitating additional manual rework such as sludge shoveling.

[0005] 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, oily contaminants are in general not removed completely by conventional techniques. Further, microorganisms and biofilms derived from not removed contaminants 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.

[0006] In addition, the cleaning agents that are conventionally used can themselves cause serious quality, health, and / or safety issues.

[0007] In addition, some cleaning agents may cause environmental or health damage if used in sufficient quantity.

[0008] EP 4146410 Bl discloses an agent for liquefying crude oil and / or for removing oil residues. EP 0853651 Bl discloses cleaning compositions for oil and gas wells, lines, casings, formations and equipment and methods of use. EP 3601501 Bl discloses a composition for reducing theviscosity of crude oil and crude oil residues as well as for loosening and separating crude oil and / or crude oil residues from other liquid and / or soil solid substances.

[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.

[0010] In addition, there is a need for cleaning solutions which do not use water and are non- corrosive.

[0011] The object of the present invention, therefore, is to provide such agents and to use such agents for removing contaminants, for example oily contaminants such as grease, cooking oils, oil sludges, in particular viscous oil sludges, or photoresist coatings, from surfaces.

[0012] These agents are intended to be used as a replacement for currently-used cleaning agents, in particular for removing oily contaminants on surfaces. The use of biodegradable, toxicologically and dermatologically acceptable ingredients would also result in savings in the areas of disposal and work protection. In addition to the safety-relevant aspects, the aim is for the novel cleaning agents to achieve process optimization with regard to time and procedures. It is thus advantageous to use a combined system.DESCRIPTION OF THE FIGURES

[0013] Figure 1: Figure 1 shows a side view of 14 g viscous oil sludge obtained from an industrial oil tank, filled in a petri dish. The petri dish marked with a “2” (hereinafter “petri dish 2”) was later treated with the multiphase system 1, while the petri dish marked with a “4” (hereinafter “petri dish 4”) was later treated with the multiphase system 2.

[0014] Figure 2: Figure 2 shows a top view of petri dishes 2 and 4 of Figure 1.

[0015] Figure 3: Figure 3 shows petri dish 2 after treatment with the multiphase system 1.

[0016] Figure 4: Figure 4 shows petri dish 4 after treatment with the multiphase system 2.

[0017] Figure 5: Figure 5 shows a petri dish marked with a “6” (hereinafter “petri dish 6”), that was filled with viscous oil sludge from an industrial oil tank, after treatment with the commercially available cleaning agent HCR 100 (product code: 16361100002; Chem Rei GmbH & Co. KG).

[0018] Figure 6: Figure 6 shows petri dishes 2 and 4 when treated with multiphase systems 1 and 2, respectively: (A) Each of the two petri dishes was sealed with cling film, which was then punctured with a dropper. Then, about 18 ml of the respective multiphase system 1 or 2 was applied through the puncture and the dishes were stored for 1 hour. (B) Subsequently, the liquid above the dirt (i.e., multiphase system 1 or multiphase system 2, each comprising dissolved and / or suspended sludge therein, residing above the undissolved sludge; “undissolved sludge” and “dirt” may be used interchangeable herein) was, using the puncture, repeatedly sucked in with the dropper and squeezed out over the entire dirt / undissolved sludge surface with pressure. This was repeated every hour for a total of 4 hours. After the last repetition, the respective dish was unsealed, the liquid above the dirt decanted and the remaining dirt photographed. The term “dissolved” as used herein does not exclude the possibility that some material may also be present as a suspension. (C) Afterwards, the decanted liquid was returned, and the respective dish was sealed and stored for the rest of the day. Subsequently, after briefly shaking, the respective dish was unsealed, the liquid above the dirt again decanted and the remaining dirt photographed. (D) This was repeated 1 day later, but without returning the decanted liquid in the beginning (total time by the time of taking (D): 2 days). Afterwards, 15 ml of fresh multiphase system 1 or 2 was added to the respective dish, which was then sealed and stored for 3 days. Finally, the respective dish was briefly swirled, unsealed, the liquid above the dirt was poured off, and the remaining dirt photographed (cf. Figures3 and 4, respectively; Figure 3: treatment with multiphase system 1, Figure 4: treatment with multiphase system 2; total time by the time of taking the photos: 5 days).

[0019] Figure 7: Figure 7 shows the following treatment steps for the commercially available cleaning agent HCR 100 (product code: 16361100002; Chem Rei GmbH & Co. KG; hereinafter: “comparative liquid”): (A) Petri dish 6 filled with viscous oil sludge obtained from an industrial oil tank. (B) The dish was sealed with cling film, which was then punctured with a dropper. Then, about 18 ml of the comparative liquid was applied through the puncture and the dish was stored for 1 hour. Subsequently, the liquid above the dirt (i.e., the comparative liquid comprising dissolved and / or suspended sludge therein, residing above the undissolved sludge) was, using the puncture, repeatedly sucked in with the dropper and squeezed out over the entire dirt surface with pressure. This was repeated every hour for a total of 4 hours. After the last repetition, the dish was unsealed, the liquid above the dirt decanted and the remaining dirt photographed. (C) Afterwards, the decanted liquid was returned, and the dish was sealed and stored for the rest of the day. Subsequently, after briefly shaking, the dish was unsealed, the liquid above the dirt again decanted and the remaining dirt photographed (total time by the time of taking (C): 1 day). This was repeated 1 day later, but without returning the decanted liquid in the beginning. Afterwards, 15 ml of fresh comparative liquid was added to the dish, which was then sealed and stored for 3 days. Finally, the dish was briefly swirled, unsealed, the liquid above the dirt was poured off, and the remaining dirt photographed (cf. Figure 5: treatment with comparative liquid; total time by the time of taking the photo: 5 days).

[0020] Figure 8: In the first two pictures (from top to bottom), a mixture of 5 parts of a solid oil sludge and 4 parts of multiphase system 2 is shown. As can be seen, the treated solid oil sludge hardly adheres to surfaces, such as the surface of a glass jar and a metal spatula. In the third picture(from top to bottom) it is shown that 5 parts of the solid oil sludge mixed with 6 parts of multiphase system 2 resulted in a flowable mixture.

[0021] Figure 9: Figure 9 shows a leaf chain (length: approx. 30 cm) comprising oily contaminants (top picture). The bottom picture shows the same chain, now opened.

[0022] Figure 10: Figure 10 shows the treatment of the opened chain with multiphase system 1 (treatment time: 30 min).

[0023] Figure 11: Figure 11 shows the opened chain before the treatment shown in Figure 10 (first row) and after the treatment and subsequent rinsing with a shower head (second row).DETAILED DESCRIPTION

[0024] The present invention describes novel cleaning agents based on a multiphase system which does not include water. The cleaning agents are preferably directed to remove oily contaminants from a surface.

[0025] The object is achieved according to the invention by a multiphase system comprising two liquids, one of the liquids being a polar solvent 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 or a polar solvent, additionally containing amphiphiles, and optionally: one or more liquid esters, at least one tenside, and additives.

[0026] In a further embodiment, the invention relates to a multiphase system comprising two liquids, one of the liquids being a polar solvent 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 or a polar solvent, additionally containing at least one tenside, amphiphiles, and optionally one ormore liquid esters, and optionally additives, the multiphase system being characterized in that it has a turbidity characteristic greater than 0 to 200 NTU.

[0027] 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

[0028] According to one embodiment of the present invention, the tenside used is a nonionic, cationic, anionic, or amphoteric tenside. The terms “tenside“ and “surfactant” can be used interchangeably.

[0029] Tensides 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 tenside, two liquids which in fact are immiscible with one another, such as oil and water or polar solvents, may be finely blended (dispersed). Tensides 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.” Tensides within the meaning of the invention have an oriented 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.

[0030] Examples of tensides within the meaning of the invention include but are not limited to higher alcohols, in particular those with hydrophilic-lipophilic molecular portions, such as n- and iso-isomers of butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, and dodecanol, or the modified derivatives thereof in the hydrophobic and / or hydrophilic part of the molecule.

[0031] As anionic tensides, for example, alkali or ammonium salts of long-chain fatty acids, alkyl(benzene) sulfonates, paraffin sulfonates, bis(2-ethylhexyl)sulfosuccinate, and alkyl sulfates, primarily 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.

[0032] As nonionic tensides, polyalkylene oxide-modified fatty alcohols, for example Berol® types (Akzo-Nobel) and Hoesch® T types (Julius Hoesch), alkylethoxylates, in particular selected from C9-C13 n-alkyl-ethoxylates or C9-C19 i-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.

[0033] As cationic tensides, coco bis(2-hydroxyethyl)methylammonium chloride or polyoxyethylene-modified talc methylammonium chloride, for example, may be used. The use of various amphoteric tensides may be also possible. If a broader pH range is to be covered, coco dimethyl amine oxide (Aormox® MCD, Akzo-Nobel) has proven to be suitable.

[0034] The tensides 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.

[0035] According to the invention, the water-insoluble substances are those having a solubility in water or the solvent 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-menthane. According to the invention, benzyl acetate is also included in the waterinsoluble substances used. However, 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.

[0036] In a preferred embodiment, the multiphase system has no carbon dioxide, in particular in the form of supercritical CO2.

[0037] 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,Ri and R2 are independently hydrogen or an unbranched or branched C1-C3 alkyl, with the condition that when n=0, Ri cannot 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 C2 alkyl, 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 IV may also be cyclic (cyclohexanedione); or is selected from 2,3-butanedione (diacetyl), 2,4-pentanedione (acetylacetone), 3,4-hexanedione, 2, 5 -hexanedione, 2,3 -pentanedione, 2,3-hexanedione, 1,4-cyclohexanedione, or 1,3- cyclohexanedione; 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 (l-methoxy-2-propyl) acetate, (2-butoxy ethyl) 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-methyl 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-butyro lactone, 3-amino-lH-l,2,4-triazole, gammabutyrolactone, nicotinamide, ascorbic acid, N-acetylamino acids, in particular N-acetylglycine, - alanine, -cysteine, -valine, or -arginine, triethyl phosphate, n-butyl acetate, dimethyl sulfoxide (DMSO), or 2,2,2-trifluoroethanol, preferably DMSO.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.

[0038] Preferably, the amphiphile comprises or consists of DMSO. The use of a polar amphiphile, such as DMSO, may help liquefy oily contaminants, in particular solid and / or viscous oil sludges.DMSO has a relatively high density of 1.10 g / cm3. This may allow multiphase systems comprising DMSO to penetrate and diffuse through oil particles and oil sludge, and thus may liquefy them.

[0039] In one embodiment, the multiphase system is a composition, comprising:(A) a polar solvent;(B) one or more apolar solvents 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;(E) optionally one or more tensides; and(F) optionally one or more additives.

[0040] In another embodiment, the multiphase system is a composition, comprising:(A) a polar solvent;(B) one or more apolar solvents 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;(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.

[0041] Preferably, the multiphase system is a composition, comprising:(A) a polar solvent;(B) one or more apolar solvents 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;(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.

[0042] Further preferably, the multiphase system is a composition, comprising:(A) a polar solvent comprising a Ci-io alkylene glycol ether;(B) one or more apolar solvents 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;(E) optionally one or more tensides; and(F) optionally one or more additives.

[0043] Further preferably, the multiphase system is a composition, comprising:(A) a polar solvent comprising a Ci-io alkylene glycol ether;(B) one or more apolar solvents 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 comprising or consisting of one or more polar aprotic solvents (D5);(E) optionally one or more tensides; and(F) optionally one or more additives.

[0044] Optionally, component (F) comprises or consists of an additional tenside as defined above.

[0045] The term “composition” as used herein encompasses a single-phase composition as well as an emulsion.

[0046] In one embodiment, in particular for very low contents of solvent, 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.

[0047] A composition according to the invention with very low amounts of solvent contained therein may, in the meaning of the invention, also be termed as a “concentrate”. This concentrate may be diluted with solvent according to desired properties and application requirements.

[0048] In another embodiment, preferably for solvent contents above 2% by weight based on the total amount of the composition, the composition according to the invention may exist in the form of an emulsion.

[0049] The emulsion may be a solvent-in-oil emulsion or an oil-in-solvent emulsion.

[0050] In one embodiment, the composition according to the invention is in the form of a microemulsion.

[0051] The term “microemulsion” as used in the art and used herein encompasses a dispersion made of solvent, oil, and tenside(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.

[0052] Thus, the term “microemulsion” encompasses a dispersion wherein the dispersed phase is stabilized by a tenside and / or tenside-cotenside systems.

[0053] According to the invention, the composition comprises a polar solvent (A). In one embodiment, the term “solvent” or “polar solvent” as used herein is generally a water soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25° C. It is preferably selected from Ci-6 alkanol, Ci-6 diols, Ci-io alkylene glycol ethers, and mixtures thereof. Most preferably, the polar solvent (A) comprises Ci-io alkylene glycol ethers. The alkanol can be selected from methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, their various positional isomers, and mixtures of the foregoing. It may also be possible to utilize in addition to, or in place of, said alkanols, the diols such as methylene, ethylene, propylene and butylene glycols, and mixtures thereof.

[0054] It is preferred to use a straight or branched chain alkanol as the coupling agent of the invention. These are methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, pentanol, hexanol and their positional isomers. Especially preferred is isopropanol, also known as isopropyl alcohol and IP A.

[0055] An alkylene glycol ether solvent may be also used in this invention. The alkylene glycol ether solvents may be used in addition to the polar alkanol solvent. They may be added to enhance the cleaning performance and may work well on greasy or oily soils. The alkylene glycol ether solvents may include ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, diethylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-butyl ether (DPNB), and mixturesthereof. In particular, in preferred embodiments, the one or more Ci-io alkylene glycol ether is selected from ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, diethylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-butyl ether, or mixtures thereof. Preferred glycol ethers are ethylene glycol monobutyl ether, also known as butoxyethanol, sold as butyl Cellosolve by Union Carbide, and also sold by Dow Chemical Co., 2-(2-butoxy ethoxy) ethanol, sold as butyl Carbitol, also by Union Carbide, and dipropylene glycol n-butyl ether, available from a variety of sources. Another preferred alkylene glycol ether is propylene glycol t-butyl ether, which is commercially sold as Arcosolve PTB, by Arco Chemical Co. The n-butyl ether of propylene glycol is also preferred. Other suppliers of preferred solvents include Union Carbide. It is preferred to limit the total amount of solvent to preferably no more than about 25%, and most preferably, no more than about 15% of the cleaner. A particularly preferred range is about 1-15%. If any of these organic solvents has a solubility of less than 25% in water (at room temperature, 21 °C), then the amount of such limited water solubility solvents should not exceed about 5%, with the amount of water-soluble solvents (such as IP A) then raised to an amount sufficient to maintain the microemulsion. These amounts of solvents are generally referred to as dispersion-effective or solubilizing effective amounts. The solvents, especially the glycol ethers, are also important as cleaning materials on their own, helping to loosen and solubilize greasy soils for easy removal from the surface to be cleaned.

[0056] The principal classes of organic solvents from which useful organic solvents may be selected include esters, alcohols, ketones, aldehydes, ethers and nitriles. These will generally contain one or more of the desired similar or dissimilar functional groups listed above. Examples of organic solvents containing similar functional groups from among those listed above includediethyl glutarate (2 ester groups), phenacyl acetone (2 keto groups), diethyl ethyl phosphonate (2 phosphonate ester groups), ethylene dipropionate (2 ester groups), decylene glycol (2 hydroxyl groups), m-dimethoxybenzene (2 ether groups), adiponitrile (2 nitrile groups), ethylene glycol dibutyl ether (2 ether groups), and diethyl-o-phthalate (2 ester groups). Among organic solvents containing dissimilar functional groups from among those listed above may be mentioned 2- phenoxy ethanol (hydroxy, ether groups), 1 -phenoxy-2-propanol (hydroxy, ether groups), N- phenyl-morpholine (amino, ether groups), isopropyl acetoacetate (keto, ester groups), o- methoxybenzyl alcohol (ether, hydroxy groups), 4' -methoxy acetophenone (ether, ketone groups), o-nitrophenetole (nitro, ether groups), 2-hexoxyethanol (hydroxy, ether groups), ethylcyanoacetoacetate (cyano, keto, ester groups), p-anisaldehyde (ether, aldehyde groups), polypropylene glycol 1200 (ether, hydroxyl groups), n-butoxy acetate (ether, ester groups), and 2- phenylthioethanol (thioether, hydroxyl groups).

[0057] In addition to the criteria listed above, it is also desirable but not essential that the organic solvents may have a relatively low volatility or high flash point, exhibit a low level of odor, be chemically stable, nontoxic, nonhazardous and commercially available.

[0058] The sparingly water soluble organic solvents which may be employed in the practice of the present invention (and comprising some of the solvents listed above) together with their aqueous ambient temperature solubility in wt.-% include 2-phenoxy ethanol (2.3) (marketed under the trade designation "Dowanol® EPh"), 1 -phenoxy-2-propanol (1.1) (marketed under the trade designation "Dowanol® PPh"), P-phenyl ethanol (1.6), acetophenone (0.5), benzyl alcohol (4.4), benzonitrile (1.0), n-butyl acetate (0.7), n-amyl acetate (0.25), benzaldehyde (0.3), N,N-diethyl aniline (1.4), diethyl adipate (0.43), dimethyl-o-phthalate (0.43), n-amyl alcohol (2.7), N-phenyl morpholine (1.0), n-butoxy ethyl acetate (EB acetate) (1.1), cyclohexanol (4.2), polypropylene glycol 1200(2), cyclohexanone (2.3), isophorone (1.2), methyl isobutyl ketone (2.0), methyl isoamyl ketone (0.5), tri-n-butyl phosphate (0.6), 1 -nitropropane (1.4), nitroethane (4.5), dimethyl esters of mixed succinic, glutaric and adipic acids (5.7) (marketed under the trade designation "DBE ester" by DuPont), diethyl glutarate (0.88), and diethyl malonate (2.08). As will be apparent to those skilled in the art, the above-listed sparingly water-soluble organic solvents are merely illustrative and various other solvents meeting the criteria set out above may also be used in the practice of the invention. Because of their performance characteristics, lack of odor, low volatility / high flash point, chemical stability and availability, 2-phenoxy ethanol and 1 -phenoxy-2-propanol are the preferred organic solvents of choice. N-butoxy ethyl acetate (EB acetate) and the dimethyl esters of mixed succinic, glutaric and adipic acids are also among the preferred organic solvents.

[0059] As indicated, a number of otherwise potent organic solvents having an aqueous solubility of less than 0.2 weight percent such as 2-(2-ethylhexoxy)ethanol (2-ethylhexyl cellosolve) having an aqueous solubility of only 0.095 wt.-%, and 2,6-dimethyl-4-heptanone (diisobutyl ketone) (aq. sol. 0.05 wt..-%), and organic solvents having an aqueous solubility in excess of 6 weight percent such as propylene glycol monomethyl ether acetate (aq. sol. 16.5 wt.- %), ethylene glycol diacetate (aq. sol. 14.3 wt.-%), propylene carbonate (aq. sol. 19.6 wt.-%) and N-methyl pyrrolidone (infinite aq. sol.) may not be useful in the practice of the invention.

[0060] The polar solvent may be a degreaser. Representative examples of suitable degreasers include a wide variety of organic solvents and generally include materials such as ketones, amines, esters, tetrahydrofuran or other heterocycles, alcohols, ethers, glycol ethers, combinations of these, and the like. Of these, one or more glycol ethers may be particularly preferred for a variety of reasons: Firstly, glycol ethers have excellent oil dissolving capabilities, thus, these compounds solubilize oil very quickly, i.e. liquefy oil very quickly. It is believed that glycol ethers are suchexcellent solvents because they combine the solvent characteristics of both alcohols and ethers.Secondly, glycol ethers tend to form compatible, single-phase mixtures with the other components of the cleaning composition, significantly without unduly compromising the cleaning power of those other ingredients. Thus, when glycol ethers may be used as polar solvents, the addition of tensides may not be needed. Glycol ethers contain both polar and nonpolar structural elements. Thus, glycol ethers are not merely polar solvents; instead, they possess amphiphilic properties, which may eliminate the need for adding additional tensides. Consequently, glycol ethers occupy an intermediate position between purely polar solvents and amphiphilic substances. The volatility of glycol ethers is further in a suitable regime so that cleaning compositions incorporating these materials dry at a rate that is not too fast or too slow. In addition, glycols ethers are compatible with a race vehicle environment. When included as a constituent of the present invention, these compounds may not damage LEXAN polycarbonate brand polycarbonate used as windshield components, MYLAR polyester, the silicone seal of such windshields, the paint finish on the vehicles, or many decals.

[0061] Glycol ethers may be made by reaction of alcohols and ethylene oxide in accordance with conventional methods. Glycol ethers are widely available from a number of commercial sources. Specific examples include propylene glycol n-butyl ether (Dow Chemical Company), propylene glycol n-propyl ether (Dow Chemical Company), diethylene glycol monobutyl ether (Eastman Chemical Co.), ethylene glycol monobutyl ether (Eastman Chemical Co.), dipropylene glycol methyl ether, (Dow Chemical Company) propylene glycol methyl ether (Dow Chemical Company) combinations of these, and the like.

[0062] Preferably the amount of polar organic solvent used in the cleaning composition is from 5 to 40 weight percent, preferably from 5-25 weight percent, more preferably from 7-18 weightpercent, and even more preferably from 10-12 weight percent, wherein said weight percent is based upon the total weight of the microemulsion cleaner. In the concentrate, preferably from 10-30 weight percent, more preferably 18 to 25 weight percent of polar organic solvent may be used, where said weight percent is based upon the total weight of the microemulsion cleaner.

[0063] According to the invention, the composition further comprises one or more liquid compounds (water-insoluble liquid oil) (B) represented by one or more liquid olefinic unsaturated compounds or one or more apolar solvents having a water solubility of less than 2 g in 1,000 g of water at 25 °C. Further preferably the solubility in water or solvent of the composition is less than 1 g in 1,000 g of water at 25 °C. The term “apolar solvent” can be used interchangeably with the term “liquid olefinic unsaturated compound”.

[0064] Preferably, the apolar solvents (B) have at least 8 carbon atoms in the backbone, and further preferred at least 10 carbon atoms in the backbone.

[0065] The term “olefinic unsaturated compound” encompasses compounds having one or more olefinic double bonds.

[0066] In one embodiment, the apolar solvents (B) may consist of carbon and hydrogen only, i.e., the compounds may be alkenes such as open-chain alkenes or cyclic 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 may be selected from terpenes such as limonene.

[0067] In a preferred embodiment, the apolar solvents (B) may be selected from alkenes, cyclic alkenes, or mixtures thereof.

[0068] The apolar solvents (B) may be substituted with functional groups. All conceivable functional groups may be possible such as hydroxy groups and ester groups, provided the solubility of (B) in water or solvent is less than 2 g or less than 1 g per 1,000 g of water.

[0069] In a preferred embodiment, (B) is or comprises N,N-dimethyl 9-decenamide (CAS no. 1356964-77-6). The compound is commercially available.

[0070] In another preferred embodiment, (B) is or comprises methyl 9-dodecenoate (CAS no. 39202-17-0). The compound is commercially available.

[0071] Due to their manufacturing process based on natural oils, both N,N-dimethyl 9-decenamide and methyl 9-dodecenoate are regarded as “green” compounds.

[0072] In another preferred embodiment, (B) is or comprises limonene. Limonene is commercially available, e.g. in form of orange oil.

[0073] In a preferred embodiment, (B) comprises N,N-dimethyl 9-decenamide or methyl 9- dodecenoate.

[0074] In another preferred embodiment, (B) comprises N,N-dimethyl 9-decenamide and methyl 9-dodecenoate.

[0075] In another preferred embodiment, (B) comprises N,N-dimethyl 9-decenamide, methyl 9- dodecenoate, and limonene.

[0076] In other preferred embodiment, (B) comprises N,N-dimethyl 9-decenamide and limonene, or methyl 9-dodecenoate and limonene.

[0077] According to the invention, the composition optionally further comprises (C) one or more liquid esters having a water or solvent 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”.

[0078] The composition may comprise 0 to 40 wt.-%; of component (C), based on the total weight of the composition (= 100 wt.-%).

[0079] Basically, all liquid esters may be used provided they have a water or solvent solubility of less than 2 g in 1,000 g of water at 25 °C.

[0080] The esters may be based on aliphatic carboxylic acids such as Ci-6-carboxylic acids, e.g., acetic acid, C?-2o-fatty acids, aromatic acids such as benzoic acid, or mixtures thereof.

[0081] As alcohol component, preferably short chain alcohols such as methanol, ethanol or propanol are used. The use of benzyl alcohol is likewise possible.

[0082] 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.

[0083] In a preferred embodiment, (C) comprises a mixture of benzyl acetate, isopropyl myristate, and methyl salicylate.

[0084] The composition according to the invention further comprises one or more amphiphilic liquid 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 (A) and in non-polar solvents such as (B) and (C).

[0085] 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 the polar solvent (A) and the water-insoluble organic compounds (B) and (C).

[0086] Preferably, the amphiphilic liquid compounds (D) have a water solubility of from 2 to 120 g in 1,000g of water.

[0087] In a preferred 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;(D5) one or more polar aprotic solvents.

[0088] Basically, all liquid ketones, liquid esters, liquid acetoacetates and liquid alcohols may be used, provided they have a water solubility from 2 to 120 g in 1,000 g of water at 25 °C.

[0089] In a preferred embodiment, (DI) to (D4) 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.

[0090] Compound (DI) may be a cyclic ketone such as cyclopentanone or cyclohexanone.

[0091] Compound (DI) may be selected from aliphatic ketones such as butanones, pentanones and hexanones. Preferably, compound (DI) may be selected from 2-pentanone, 3-pentanone, 3- hexanone, 3-methyl butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3- dimethyl-2-butanone, and 2-methy 1-3 -pentanone. Preferably, (DI) may be cyclopentanone.

[0092] Compound (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).

[0093] In a preferred embodiment, (D2) is 3 -methoxy-3 -methylbutylacetate. The compound is commercially available (CAS no. 103429-90-9).

[0094] Compound (D3) may be 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.

[0095] Compound (D4) may be 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.

[0096] Compound (D5) may be selected from one or more of acetone, acetonitrile, di chloromethane, dimethyl acetamide, dimethyl formamide, N-methylpyrrolidone, dimethyl imidazolidone, dimethyl propyleneurea, dimethyl sulfoxide, ethyl acetate, gamma-valerolactone, hexamethyl phosphoramide, propylene carbonate, pyridine, sulfolane, tetrahydrofuran, or mixtures thereof.

[0097] In a preferred embodiment, (D5) is selected from dimethyl sulfoxide, gamma- valerolactone, propylene carbonate, or mixtures thereof.

[0098] In a preferred embodiment, the composition according to the invention contains as amphiphilic compound at least (DI) or (D2) or (DI) and (D2).

[0099] 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).

[0100] If desired, the composition according to the invention comprises further amphiphilic compounds, e.g. as defined above, besides amphiphilic compounds (DI), (D2), (D3), (D4) and / or (D5). It is possible to subsume amphiphilic compounds as for examples defined above again under e.g. (D5) (e.g. like in case of DMSO). 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”.

[0101] In another preferred embodiment, the composition according to the invention comprises as amphiphilic compounds at least (D5).

[0102] In one embodiment, the composition according to the invention comprises besides amphiphilic compound (D5) additionally one or more of (D2) and / or (D3).

[0103] 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..

[0104] 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-ethy 1-1 ,4-hexanediol, 2-methyl-2,4-pentanediol, 2-(n-butyl)-2-ethyl-l,3-pentandiol.

[0105] According to the invention, the composition comprises optionally (E) one or more of an anionic tenside (El), a cationic tenside (E2), a non-ionic tenside (E3) and an amphoteric tenside (E4).

[0106] Thus, in some embodiments, the composition does not comprise any tensides.

[0107] As used herein, the term “tenside” is synonymously used with the term “tenside”. A tenside encompasses any compound which forms micelles at the interface between polar solvent and a water-insoluble organic solvent such as (B).

[0108] Suitable anionic, cationic, non-ionic, and amphoteric tensides are widely known in the art. Such tensides typically are commercially available products.

[0109] Suitable anionic tensides (El) may be selected from: soaps R-CIECOONa, wherein R = Cn-17; alkyl benzenesulfonates R-CelTi-SChNa, wherein R = C10-13; alkane sulfonates R1R2CH- SChNa, 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 acidmethyl esters R-CH(SO3Na)-COOCH3, wherein R = C14-16; alkyl sulfates R-CIE-O-SChNa, wherein R = C11-17; alkyl ether sulfates R1R2CH-O-(C2H4O)2-SO3Na, wherein R1+ R2= C10-14; 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.

[0110] Suitable cationic tensides (E2) may be selected from: quaternary ammonium chlorides such as RJR2R3R4N+Cr, 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.

[0111] Suitable non-ionic tensides (E3) may be selected from: primary and secondary alcohol ethoxylates RR1CH-O-(CH2-CH2-O)nH, wherein R = Cs-is and R1= H, n=3- 15 for primary alcohol ethoxylates, or R+R1=Cio-i4and n=3-12 for secondary alcohol ethoxylates; R-CeH4-O-(CH2-CH2- O)nH, wherein R=Cs-i2 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)niH, wherein R=Cn-i7, n=l; 2; nl=l; amine oxides Ci2H25-N(CH3)2O; hexyl-D-glucoside (CAS no. 54549-24-5), and two or more thereof.

[0112] Suitable amphoteric tensides (E4) may be selected from: sulfobetaines R1R2R3N+-(CH2)3- SO3‘ and betaines R1R2R3N+-CH2-COO', wherein R1=Ci2-i8, R2, R3= Ci, respectively, and two or more thereof.

[0113] The tensides as defined above may contain water or a polar solvent as is known in the art.

[0114] 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.

[0115] Particularly preferred cationic tensides are selected from ethoxylated C12-14 alkyl(hydroxyethyl)dimethyl ammonium chloride.

[0116] Particularly preferred non-ionic tensides are selected from C9-11 alcohol ethoxylates and hexyl-D-glucoside or two or more thereof.

[0117] In a preferred embodiment, the composition according to the invention comprises a mixture of tensides (El), (E2), (E3) and optionally (E4).

[0118] The composition according to the invention may contain (F) one or more additives.

[0119] In a preferred embodiment, the additive (F) is a corrosion inhibitor. A suitable corrosion inhibitor is preferably benzotriazole.

[0120] The additive (F) may comprise a fragrance, if desired.

[0121] In a preferred embodiment, the composition comprises 5 to 40 wt.-% of component (A), based on the total weight of the composition.

[0122] In a further preferred embodiment, the multiphase system comprises 40 to 80 wt% of component (D), based on the total weight of the composition.

[0123] The amount of (A) in the composition can be 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 (A) 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%, 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 5 to 40 wt%, or 15 to 30 wt%, or 25 to 20 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F).

[0124] The amount of (B) in the composition can be at least 1 wt%, or at least 6 wt%, or at least 11 wt%, or at least 16 wt%, or at least 21 wt%, or at least 26 wt%, or at least 31 wt%, or at least 36 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 1 to 40 wt%, or 11 to 30 wt%, or 21 to 20 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F).

[0125] 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 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, (C) is present in an amount of 0 to 40 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).

[0126] The amount of (D) in the composition can be at least 40 wt%, or at least 45 wt%, or at least 50 wt%, or at least 55 wt%, or at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least 75 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 80 wt%, or at most 75 wt%, or 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 most45 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 40 to 80 wt%, or 50 to 70 wt%, or 60 to 60 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F).

[0127] The amount of (E) 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%, 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 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, (E) is present in an amount of 0 to 30 wt%, or 10 to 20 wt%, wherein the wt% are based on the total weight of components (A), (B), (C), (D), (E) and (F).

[0128] 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 present in 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).

[0129] In a preferred embodiment, the composition according to the invention comprises:(A) a polar solvent in an amount of from 5 to 40 wt.-%;(B) one or more apolar solvents having a water solubility of less than 2 g in 1,000 g of water at 25 °C, in an amount of from 1 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, respectively, in an amount of from 0 to 40 wt.-%;(D) one or more amphiphilic liquid compounds in an amount of from 40 to 80 wt.-%;(E) optionally one or more 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 0 to 30 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.-%), respectively.

[0130] In another embodiment, the composition comprises:(A) a polar solvent in an amount of from 10 to 35 wt.-%;(B) one or more apolar solvents having a water solubility of less than 2 g in 1,000 g of water at 25 °C, in an amount of from 1 to 35 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 35 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 45 to 75 wt.-%;(E) optionally 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 5 to 25 wt.-%;(F) optionally one or more additives in an amount of from 0 to 7.5 wt.-%; based on the total amount of the composition (= 100 wt.-%).

[0131] In still another embodiment, the composition comprises:(A) polar solvent in an amount of from 15 to 30 wt.-%;(B) one or more apolar solvents having a water solubility of less than 2 g in 1,000 g of water at 25 °C in an amount of from 1 to 30 wt.-%;(C) 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 1 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 50 to 70 wt.-%;(E) one or more of a tenside 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 10 to 20 wt.- %;(F) one or more additives in an amount of from 2.5 to 7.5 wt.-%; based on the total amount of the composition (= 100 wt.-%).

[0132] 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.

[0133] However, the pH of the composition may also be set to an acidic range.

[0134] In one embodiment, the invention relates to a composition, comprising:(A) polar solvent;(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 non-ionic tenside (E3) and an amphoteric tenside (E4);(F) one or more additives. In this embodiment, component (F) may comprise or consist of an additional tenside as defined above. Compound (A) may be as defined above. In one embodiment of this embodiment, (B) is selected from alkanes, cycloalkanes, and aromatic compounds, optionally substituted. Preferred alkanes and cycloalkanes are based on Ce to C15 alkanes and cycloalkanes. Preferred aromatic compounds are based on benzenes, e.g. benzene, toluene, or xylene. In another preferred embodiment of this embodiment, (B) is selected from Ce to C15 alkenes and cycloalkenes. In one embodiment, the alkene or cycloalkene does not comprise N,N- dimethyl 9-decenamide nor methyl 9-dodecenoate. Compounds (C), (D), (E) and (F) are 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 C1-4 carboxylic acids of formula (CH3O)(CH3)2C-(CH2)2-OC(O)R, wherein R = H, C1-4 alkyl, preferably 3-methoxy-3- methylbutylacetate. Preferably, (E) comprises a mixture of (El), (E2), (E3) and optionally (E4). Accordingly, in one embodiment of this embodiment, the invention relates to a composition, comprising:(A) polar solvent;(B) one or more liquid compounds having a water solubility of less than 2 g in 1,000 g of water at 25 °C; wherein the one or more liquid compounds are selected from alkanes, cycloalkanes, alkenes, cycloalkenes and aromatic compounds, optionally substituted; wherein the alkene does 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):(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 non-ionic tenside (E3) and an amphoteric tenside (E4);(F) one or more additives.Optionally, component (F) may comprise or consist of an additional tenside as defined above. The composition may be a microemulsion.

[0135] A further aspect of the present invention relates to the use of a multiphase system, as described above, for cleaning surfaces, in particular for removing contaminants from surfaces, in particular oily contaminants. 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.

[0136] 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.

[0137] With regard to oily contaminants, such as grease, cooking oil, fats, solid or viscous oil sludges, the multiphase system solubilizes the oily contaminants.

[0138] Multiple contaminants may be stripped at the same time.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] The described operations of coating, illumination, stripping, and etching are often repeated multiple times, using different masks.

[0143] 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.

[0144] In a further aspect, the invention relates to a method of manufacturing the microemulsion. In particular, the method comprises the step: mixing the components (A) to (D). In some embodiments, the method comprises the step: mixing the components (A) to (F).

[0145] This inventive method creates a non-toxic, biodegradable microemulsion designed to replace traditional solvent-based and water-based cleaners. The multiphase system eliminates the need for water, addressing future scarcity and cost concerns, while employing hydrocarbon-based compounds to maintain high cleaning performance. This method includes the combination of specific green ingredients to produce a microemulsion that physically separates contaminants from surfaces without requiring a rinse. The multiphase system according to the invention is particularly suitable for delicate materials, preventing damage commonly associated with conventional waterbased methods.

[0146] The multiphase systems according to the invention may be applicable across various industries, including semiconductor manufacturing and industrial maintenance or the oil industry, offering a safe, environmentally sustainable alternative to not efficient, toxic, corrosive, and flammable cleaning solvents currently prevalent in the market.

[0147] The invention is now explained with reference to exemplary embodiments, which are not to be construed as limiting the scope of protection.Example 1: Preparation of the multiphase system 1

[0148] Dipropylenglykol-n-butylether as polar solvent (A; 20 wt,-%); apolar solvents (B) comprising Cio to C15 alkenes having a water solubility of less than 2 g in 1,000 g of water at 25 °C (1.5 wt.-%); a liquid ester (C) comprising a fatty acid alkyl ester having a water solubility of less than 2 g in 1,000 g of water at 25 °C (20 wt.-%); and acetoacetates as well as dibasic esters as amphiphilic liquid compounds (D; 58.5 wt.-%) were mixed and stirred for a suitable time (e.g., 10 minutes) in order to form the multiphase system 1. The weight ratios are based on the total weight of the composition. The multiphase system 1 is in form of a single-phase composition.Example 2: Preparation of the multiphase system 2

[0149] Dipropylenglykol-n-butylether as polar solvent (A; 17.6 wt,-%); apolar solvents (B) comprising Cio to C15 alkenes having a water solubility of less than 2 g in 1,000 g of water at 25 °C (1.36 wt.-%); a liquid ester (C) comprising a fatty acid alkyl ester having a water solubility of less than 2 g in 1,000 g of water at 25 °C (17.6 wt.-%); and a polar aprotic solvent (DMSO), as well as acetoacetates and dibasic esters as amphiphilic liquid compounds (D; 63.44 wt.-%) were mixed and stirred for a suitable time (e.g., at least 10 minutes) in order to form the multiphase system 2. The weight ratios are based on the total weight of the composition. The multiphase system 2 is in form of a single-phase composition.Example 3 (Comparative): Naphtha-based cleaning system

[0150] The commercially available cleaning liquid for oil tanks HCR 100 (product code: 16361100002; Chem Rei GmbH & Co. KG) was used as comparative liquid. HCR 100 comprises the refined oil naphtha (petroleum; heavy aromatic; >50 wt.-%), 1 ,2,4-trimethylbenzene (5-10 wt.- %), naphthalin (5-10 wt.-%), and 1,3,5-trimethylbenzene (1-5 wt.-%) (the wt.-% are based on the total weight of the composition).Example 4: Cleaning experiment 1: Liquefication of viscous oil sludge from an oil tank

[0151] Liquefication of viscous oil sludge dirt formed in a crude oil tank upon application of multiphase system 1 (cf. Experiment 1), multiphase system 2 (cf. Experiment 2) and the comparative liquid (cf. Experiment 3), respectively, was analyzed.

[0152] Large petri dishes with high walls were used as lab-scale oil tank analogues. Each dish, respectively, was filled with 14 g of viscous oil sludge from a crude oil tank (cf. Figures 1, 2, 6A and 7A). In general, such sludge accumulates in crude oil tanks as it cannot be pumped off with other, flowable crude oil fractions; therefore, removal of the sludge necessitates either liquefaction (thereby making it flowable) or laborious mechanical work (e.g. sludge shoveling).

[0153] Each dish, respectively, was sealed with cling film, which was then punctured with a dropper. Then, about 18 ml of multiphase system 1, multiphase system 2 respectively the comparative liquid was applied through the puncture and the dish for stored for 1 hour (cf. Figure 6A; petri dish 2 had multiphase system 1 applied, petri dish 4 multiphase system 2). Subsequently, the liquid above the dirt (i.e., multiphase system 1 or multiphase system 2, each comprising dissolved and / or suspended sludge therein, residing above the undissolved sludge) was, using the puncture, repeatedly sucked in with the dropper and squeezed out over the entire dirt surface withpressure. This was repeated every hour for a total of 4 hours. After the last repetition, the respective dish was unsealed, the liquid above the dirt decanted and the remaining sludge photographed (cf. Figures 6B and 7B; the latter shows petri dish 6 which had the comparative liquid applied). Afterwards, the decanted liquid was returned, and the respective dish was sealed and stored for the rest of the day. Subsequently, after briefly shaking, the respective dish was unsealed, the liquid above the dirt again decanted and the remaining sludge photographed (cf. Figures 6C and 7C). This was repeated 1 day later, but without returning the decanted liquid in the beginning (cf. Figure 6D; total time by the time of taking the photo: 2 days). Afterwards, 15 ml of fresh multiphase system 1, multiphase system 2 respectively the comparative liquid was added to the respective dish, which was then sealed and stored for 3 days. Finally, the respective dish was briefly swirled, unsealed, the liquid above the dirt was poured off, and the remaining dirt photographed (cf. Figures 3, 4 and 5 respectively; total time by the time of taking the photos: 5 days).

[0154] Results:Although the comparative liquid mixed well with the sludge and a huge portion of it dissolved after 4 hours (cf. Figure 7B), a highly viscous sediment remained in the dish at the end of the cleaning experiment (after 5 days; cf. Figure 5). Multiphase system 1 respectively 2 performed significantly better: Multiphase system 1 dissolved increasingly more sludge over the course of the experiment (cf. Figure 6B-D, first row), and by the end of the experiment, only a few dirt lumps remained in the dish (cf. Figure 3). Multiphase system 2 comprising a polar aprotic solvent dissolved increasingly more sludge over the course of the experiment as well (cf. Figure 6B-D, second row). Compared to multiphase system 1, multiphase system 2 dissolved the sludge faster and also thickened faster. By the end of the experiment, the sludge was almost completely dissolved (cf. Figure 4 in comparison to Figure 3). The polar aprotic solvent used in multiphasesystem 2 has a relatively high density. It is assumed that this promotes better penetration and diffusion into the oil sludge. Also, it is assumed that parts of the oil sludge are polar and thus using of a polar aprotic solvent in the multiphase system 2 further helps liquefying the sludge. In summary, it can be concluded that multiphase system 1 and multiphase system 2 are significantly more capable of liquefying the oil sludge than the naphtha-based comparative liquid that is used in state-of-the-art cleaning applications of oil tanks.

[0155] The use of glycol ether as a polar solvent in the multiphase systems 1 and 2 contributed to the excellent oil sludge liquefaction capabilities, as glycol ethers can solubilize oil very quickly. It is assumed that glycol ethers are such excellent solvents because they combine the solvent characteristics of both alcohols and ethers. In addition, glycol ethers tend to form single-phase mixtures with the other components of multiphase system 1 and 2, respectively. The volatility of glycol ethers is further in a suitable regime so that cleaning compositions incorporating these materials dry at a rate that is not too fast or too slow.Example 5: Cleaning experiment 2: Liquefication of solid oil sludge from an oil tank

[0156] Liquefication of solid (fondant- like) oil sludge dirt formed in a crude oil tank upon application of multiphase system 1 (cf. Experiment 1) respectively multiphase system 2 (cf. Experiment 2) was analyzed. There is demand for a cleaning liquid that can dilute and / or liquefy also a solid oil sludge into a flowable and thereby pumpable form.

[0157] Each of two glass jars were filled with 100 g of solid oil sludge. Multiphase system 1 respectively 2 were added to the respective jar. A spatula was used to mix the multiphase system with the oil sludge, until the sludge was flowable enough to drip from the spatula when removed from the sludge-multiphase system mixture.

[0158] Results:A mixture of 4 parts multiphase system 1 and 5 parts solid oil sludge resulted in a flowable sludge. A mixture of 4 parts multiphase system 2 and 5 parts solid oil sludge didn’t result in a flowable sludge. However, at this point the sludge no longer adhered to the surfaces of the glass jar. At a ratio of 6 parts multiphase system 2 to 5 parts sludge, flowability comparable to that of multiphase system l’s 4 parts was achieved, (cf. Figure 8: first and second picture from top to bottom: no adhesion to surfaces (glass and metal) after the addition of 4 parts multiphase system 2; third picture from top to bottom: a flowable sludge after the addition of 6 parts multiphase system 2). In general, due to the solidity of the oil sludge, the incorporation of multiphase system 1 respectively 2 were associated with high mechanical effort. In summary, Experiment 4 demonstrated liquefaction of a solid oil sludge with multiphase system 1 and 2. Liquefying 100 g of sludge required around 80 g of multiphase system 1, and 120 g of multiphase system 2, respectively. While being less efficient in terms of quantity needed, system 2 stood out due to reaching a state - starting with the addition of just 80 g - where the sludge no longer adhered to surfaces (glass or metal).Example 6: Cleaning experiment 3: Cleaning of an industrial chain

[0159] The aim of this experiment was to test the efficiency of multiphase system 1 with regards to removing oily contaminants from a roughly 30 cm long leaf chain (cf. Figure 9, top picture). In the industry, leaf, conveyor, and roller chains need to be cleaned periodically, ideally without prior removal and / or disassembly.

[0160] The chain was opened (cf. Figure 9, bottom picture), put into a petri dish and sprayed with multiphase system 1 (cf. Figure 10). After 30 min of soaking, the chain was removed from thepetri dish and rinsed with a shower head. Figure 11 shows the opened chain before the treatment shown in Figure 10 (first row) and after the treatment and subsequent rinsing with a shower head (second row).

[0161] Results:A significant cleaning effect has been achieved, confirming multiphase system l’s capability to remove oily contaminants. On closer inspection of cleaned (i.e. soaked and subsequently rinsed) chain, no perfect cleaning of the gaps between the tabs of the chain was found (cf. Figure 11, second row). By moving the chain during soaking (e.g., by letting the chain run in place without prior removal) and using pressurized water to rinse the chain, this deficit was remedied.

Claims

CLAIMS1. A multiphase system comprising:(A) a polar solvent comprising a Ci-io alkylene glycol ether;(B) one or more apolar solvents 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;(E) optionally one or more tensides; and(F) optionally one or more additives.

2. The multiphase system according to claim 1, wherein the multiphase system is a singlephase composition.

3. The multiphase system according to claim 1, wherein the multiphase system is a microemulsion.

4. The multiphase system according to any one of claims 1 to 3, wherein the multiphase system comprises 5 to 40 wt% of component (A), based on the total weight of the composition.

5. The multiphase system according to any one of claims 1 to 4, wherein the one or more Ci- io alkylene glycol ether is selected from ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, diethylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol n-butyl ether, or mixtures thereof.

6. The multiphase system according to any one of claims 1 to 5, wherein the one or more apolar solvents (B) are selected from alkenes, cyclic alkenes, or mixtures thereof.

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

8. The multiphase system according to claim 7, wherein the one or more liquid esters (C) are selected from benzyl acetate, isopropyl myristate, methyl salicylate, or mixtures thereof.

9. The multiphase system according to claim any of claims 1 to 8, wherein the one or more amphiphilic liquid compounds (D) further 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 polar aprotic solvents.

10. The multiphase system according to claim 9, wherein the one or more polar aprotic solvents (D5) are selected from acetone, acetonitrile, dichloromethane, dimethyl acetamide, dimethyl formamide, N-methylpyrrolidone, dimethyl imidazolidone, dimethyl propyleneurea, dimethyl sulfoxide, ethyl acetate, gamma-valerolactone, hexamethyl phosphoramide, propylene carbonate, pyridine, sulfolane, tetrahydrofuran, or mixtures thereof.

11. The multiphase system according to any one of claims 1 to 10, wherein the multiphase system comprises 40 to 80 wt% of component (D), based on the total weight of the composition.

12. The multiphase system according to any one of claims 1 to 11, not comprising any tensides.

13. Use of the multiphase system according to any one of claims 1 to 12 for cleaning surfaces.4314. Use of the multiphase system according to claim 13 for removing oily contaminants from surfaces.

15. Method for the manufacture of the multiphase system according to any one of claims 1 to 12, the method comprising the step: mixing the components (A) to (D), optionally (A) to (F).44

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