Foaming mixed alcohol / water compositions comprising combination of alkyl siloxane and hydrotrope / solubilizer

Abstract

To provide foaming compositions and the like.SOLUTION: The disclosure includes synergistic combinations of pendent alkyl siloxanes and PEG-modified castor oils which can form microemulsions and foam in low surface tension solutions. The foaming compositions may form foam in water, alcohol / water, and hydrocarbon condensates. The foaming compositions may replace surfactants in other compositions and forms stable emulsions or microemulsions with oils, including non-trans fats proteins, and fatty acids. The disclosure also includes sterilizing alcohol compositions, cleaning compositions, such as hard surface cleaners, ware detergents, rinse aids and the like which incorporate the same.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present disclosure relates to foaming and cleaning compositions and methods of use that employ a synergistic combination comprising a solubilizer and a non-surface active alkyl siloxane for use in hand sanitizing and detergent and rinse aid compositions. These foaming compositions have many advantages including the ease of forming microemulsions in both water, alcohol / water solutions, and condensed hydrocarbons. [Background technology]

[0002] Certain foaming compositions can reduce the surface tension of liquids by adsorbing at the liquid-gas interface. Surfactants can also reduce the interfacial tension between oils or alcohols and water by adsorbing at the liquid-liquid interface. These foaming compositions have a hydrophilic portion that is attracted to water molecules and a hydrophobic portion that repels water and at the same time attaches itself to compounds that are mainly composed of hydrocarbons. This reduction in surface tension allows the liquid to foam by making it more energetically favorable to create new surfaces.

[0003] These foaming compositions can be composed of a single compound, such as a surfactant, or two or more compounds that interact with each other to provide the two necessary hydrophobic and hydrophilic regions, such as silicone-based water-insoluble compounds and hydrotropes.Certain liquids, such as alcohol, have very low surface tension and do not dissolve surfactants well due to their hydrophilic regions.In alcohol, for example, there are only two main classes of compounds that can reduce surface tension enough to allow foaming: silicone-based surfactants and fluoride-based surfactants.

[0004] Surfactants are often incorporated into cleaning compositions to clean soiled surfaces due to their hydrophilic and hydrophobic regions. One of the preferred mechanisms is by microemulsifying the soil. Surfactants are also often incorporated into oil-in-water microemulsions to make the oil-containing product appear more uniform. Examples of these oil-containing products include cleaning products that contain oily solvents for degreasing, such as terpenes and other water-immiscible solvents. The surfactant systems commonly used in these cleaning products include mixtures of anionic or nonionic surfactants and short-chain alcohols that help solubilize the oil phase and prevent liquid crystal formation. These surfactants can be replaced with two or more compounds that interact with each other to produce the same microemulsion. Summary of the Invention [Problem to be solved by the invention]

[0005] Availability may be limited because the number of known agents capable of foaming these low surface tension liquids is limited, therefore there is a need to identify additional compounds that can be used to induce foaming in these low surface tension liquids. [Means for solving the problem]

[0006] Applicant has identified a synergistic combination of non-surface active alkylsiloxanes and hydrotropes that work together to generate stable foam in mixtures of water and / or short chain alcohols. Although neither compound works alone, these compositions can be used together to form emulsions for hand and hard surface disinfection, cleaning compositions and stain removal. This combination is effective in reducing the surface tension of water, alcohol / water solutions, and hydrocarbon condensates. Additionally, the foaming composition can form emulsions and therefore remove oily and greasy stains. In one embodiment, the foaming composition can remove non-trans fat and fatty acid stains. In general, non-trans fats are more difficult to remove than trans fats, both from a cleaning and removal standpoint and laundry safety issues due to the heat of polymerization of non-trans fats.

[0007] In one embodiment, the alkyl siloxanes, which must be linear, include those of the general formula: [ka] During the ceremony, n is 0 or more, m is 0 or greater, R and R1 are methyl; R2 is a straight-chain or branched, unsubstituted or substituted, saturated or unsaturated, aliphatic or aromatic C1 to C30 hydrocarbon, and must not be a hydrophilic group.

[0008] In a preferred embodiment, R2 is a C2-C28 hydrocarbon, n is 0, and m is 1.

[0009] In a more preferred embodiment, R2 is a C2-C12 hydrocarbon, n is 0, and m is 1.

[0010] In the most preferred embodiment, R2 is a C8 hydrocarbon, n is 0 and m is 1.

[0011] The combination of alkyl siloxane and coupling agent act together as a surfactant and can be used in many traditional surfactant-based compositions, such as cleaning compositions, rinse aids, pre-soak detergents, and for removing oily stains from energy systems.

[0012] The hydrotrope is an ethoxylated castor oil, either hydrogenated or non-hydrogenated. Importantly, other hydrotropes have been tested in combination with alkylsiloxane compounds but have not proven effective and have not been found to produce the foam or emulsion formation required for cleaning in water / short chain alcohol systems. These include PEG-400, B-cyclodextrin, 1% dioctyl sulfosuccinate solution, lecithin, PEG(20) sorbitan monolaurate (Tween® 20), PEG(80) sorbitan monolaurate (Tween® 80), sodium coco PG-dimonium chloride phosphate (Cola Lipid DCCA), ethanol SDA-40B 190 proof (92.3% active), castor oil, N-octyl-2-pyrrolidone, Sulfadone LP-100, isotridecyloxypropyl-1,3-diaminopropane (Tomamine DA-17), C9-alcohol polyethylene glycol ether carboxylic acid (low foaming Marlowet 4539LF), secondary alcohol ethoxylate (Tergitol 15-5-7), cocoamine oxide (Barlox-12 30%), SLES 60%, and alcohol propoxy sulfate (Alfoterra 123-85). In a preferred embodiment, the composition does not contain one or more of these additional hydrotropes.

[0013] In addition, compositions of alkyl siloxanes and hydrotropes were tested for foaming and emulsion forming ability with additional surfactants, and the inclusion of the additional surfactants did not improve performance. Additional surfactants tested included PEG-40 hydrogenated castor oil, PEG(20) sorbitan monolaurate (Tween® 20), PEG(80) sorbitan monolaurate (Tween® 80), PEG-400, extended CPOEO, SLES (60%), cocoamine oxide (Barlox 12 (30%)), caprylyl methicone, PEG-40 hydrogenated castor oil, t-octylphenoxypolyethoxyethanol (Triton X-100), high foaming 50% active amine oxide (Tomamine AO-728), lecithin, 1% citric acid, 1% alkyl polyglucoside solution, isotridecyloxypropyl-1,3-diaminopropane (Tomamine DA-17), dicyclohexylamine, and polyoxyethylene-polyoxypropylene block copolymer (Pluronic 68).

[0014] In one embodiment, the castor oil has about 20 moles to about 60 moles of PEG. The ratio of the two compositions required depends largely on the amount of alcohol in the composition. For example, in a 62% ethanol solution, the siloxane can be as low as about 0.2% to about 0.3% by weight. The PEG-modified castor oil can be as low as about 0.05% to about 0.07% by weight. Surprisingly, the applicant has demonstrated that the addition of a surfactant to the mixture does not further aid in emulsion formation.

[0015] In a preferred embodiment, the range of alkyl pendant group length and siloxane backbone length is mostly determined by solubility in mixed ethanol / water systems, with C2-C8 trisiloxanes and ethyl methicones being most preferred.

[0016] In a further aspect of the present disclosure, there is provided a cleaning composition comprising a foaming composition having additional conventional ingredients such as builder enzymes, the cleaning product adapted to readily dissolve and disperse non-trans fats in commercial, industrial and personal laundry washing processes or pre-spotting treatments.

[0017] These and other objects, features and attendant advantages of the present disclosure will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiments and the appended claims. [Brief description of the drawings]

[0018] [Figure 1] 1 shows a graphical representation of the results of a dynamic surface tension analysis indicating that caprylyl methicone has no surface activity at either the water, ethanol, or 62 wt % ethanol SDA-40B190 proof (92.3% active) interface. [Diagram 2] A graphical representation of the results of the dynamic surface tension analysis shows that PEG-40 hydrogenated castor oil reduces the surface tension of pure water to 30 mN / m2 at a concentration of 5 wt.%, however, it has no effect on the surface tension for ethanol and a 62 wt.% ethanol SDA-40B190 proof (92.3% active) solution. [Diagram 3] A graphical representation of the results of the dynamic surface tension analysis shows that PEG-40 hydrogenated castor oil in combination with caprylyl methicone can further reduce the surface tension of water and 62 wt% ethanol SDA-40B1 90 proof (92.3% active) solutions. [Figure 4] 1 shows a schematic diagram of the hydrophobic interactions between the alkyl chains of PEG-modified oil and caprylyl methicone, in which the small caprylyl methicone is trapped within the cage structure of the PEG-modified oil. [Diagram 5]The mixtures are shown under fluorescent light. On the left is the mixture of Example 1 with 46 ppm dye without PEG-40, and on the right is Example 1 with 46 ppm dye with PEG-40. As can be seen, the bottom right shows strong and uniform fluorescence indicating that the silicone materials (C8 trisiloxane and silicone fluid) are completely dissolved in the ethanol / water solution to form a microemulsion. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The embodiments of the present disclosure are not limited to the specific applications of use for the surfactant system of the present invention, which may vary and are understood by those skilled in the art.It should be further understood that all terminology used herein is merely for the purpose of describing specific embodiments, and is not intended to be limiting in any manner or scope.For example, when used in this specification and the appended claims, the singular forms "a", "an" and "the" can include plural referents unless the content clearly indicates otherwise.Furthermore, all units, prefixes and symbols can be shown in their SI-recognized forms.

[0020] Numerical ranges recited herein include the numbers within the defined range. Throughout this disclosure, various aspects of the disclosure are presented in range format. Description in range format should be understood to be merely for convenience and brevity, and should not be interpreted as an indefinite limitation on the scope of the disclosure. Thus, the description of a range should be considered to specifically disclose all possible subranges and individual numerical values ​​within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0021] In order to make the present disclosure easier to understand, certain terms are first defined.Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art related to the embodiments of the present disclosure.Many methods and materials similar to, modified or equivalent to those described herein can be used to practice the embodiments of the present disclosure without undue experimentation, and preferred materials and methods are described herein.In describing and claiming the embodiments of the present disclosure, the following terminology will be used according to the definitions set forth below.

[0022] The term "about," as used herein, refers to variations in numerical quantities that may occur, for example, due to typical measuring and liquid handling procedures used in making concentrates or use solutions in the real world, inadvertent errors in those procedures, differences in the make, source, or purity of the ingredients used to make the composition or carry out the method, etc. The term "about" also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about," the claims include the equivalent of the amount.

[0023] "Actives" or "percent actives" or "percent actives by weight" or "actives concentration" are used interchangeably herein and refer to the concentration of the formulation ingredient involved in cleaning expressed as a percentage minus inactive formulation ingredients such as water or salt.

[0024] "Anti-redeposition agents" refer to compounds that help remain suspended in water instead of redepositing on the object being cleaned. Anti-redeposition agents are useful in the present disclosure to help reduce redeposition of removed soils onto the cleaned surface.

[0025] As used herein, the term "cleaning" refers to methods used to promote or aid in soil removal, bleaching, microbial population reduction, and any combination thereof. As used herein, the term "microorganism" refers to any non-cellular or unicellular (including colonial) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, and some algae. As used herein, the term "microbe" is synonymous with microorganism.

[0026] As used herein, the term "cleaning composition" includes detergent compositions, laundry cleaning compositions, hard surface cleaning compositions with pretreatment or rinse aids, and personal care cleaning compositions for use in the health and beauty field, unless otherwise indicated. Cleaning compositions include granular, powder, liquid, gel, paste, bar and / or flake type cleaners, laundry detergent cleaners, laundry soak or spray treatments, fabric treatment compositions, dishwashing detergents and soaps, shampoos, body cleaners and soaps, and other similar cleaning compositions. As used herein, the term "fabric treatment composition" includes fabric softening compositions, fabric strengthening compositions, fabric deodorant compositions, and combinations thereof, unless otherwise indicated. Such compositions may be, but need not be, rinse additive compositions.

[0027] The term "electrolyte" refers to a substance that provides ionic conductivity when dissolved in or in contact with water; such compounds can be either solid or liquid.

[0028] As used herein, the phrase "food processing surfaces" refers to surfaces of tools, machines, equipment, structures, buildings, etc., used as part of food processing, preparation, or preservation activities. Examples of food processing surfaces include surfaces of food processing or preparation equipment (e.g., slicing equipment, canning equipment, or transport equipment, including waterways), surfaces of food processing supplies (e.g., kitchen utensils, dishes, cleaning supplies, and bar glasses), and surfaces of floors, walls, or fixed fixtures of structures in which food processing occurs. Food processing surfaces are found and used in food spoilage prevention air circulation systems, aseptic packaging sanitization, food refrigeration and cooler cleaners and sanitizers, utensil washing sanitization, blancher cleaning and sanitization, food packaging materials, cutting board additives, third-sink sanitization, beverage chillers and warmers, meat cooling or scalding water, automatic dish sanitizers, sanitizing gels, cooling towers, antimicrobial clothing sprays for food processing, and non-aqueous to low-aqueous food preparation lubricants, oils, and rinse additives.

[0029] The term "hard surface" refers to solid, substantially inflexible surfaces such as countertops, tiles, floors, walls, panels, windows, plumbing fixtures, kitchen and bathroom furniture, appliances, engines, circuit boards, and dishes. Hard surfaces may include, for example, health care and food processing surfaces, equipment, and the like.

[0030] The term "soft surface" refers to softer, more flexible materials such as fabrics, carpets, hair, and skin.

[0031] The term "laundry" refers to items or articles that are washed in a laundry washing machine. In general, laundry refers to any item or article made from or including textile materials, woven fabrics, nonwoven fabrics, and knitted fabrics. Textile materials can include natural or synthetic fibers, such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends. The fibers can be treated or untreated.

[0032] Exemplary treated fibers include those that have been treated for flame retardancy. It should be understood that the term "linen" is often used to describe certain types of laundry items, including bed sheets, pillowcases, towels, table linens, tablecloths, bar mops, and uniforms. The present disclosure additionally provides compositions and methods for treating surfaces, including non-laundry items and hard surfaces such as dishes, glasses, and other utensils.

[0033] As used herein, the term "microemulsion" refers to a thermodynamically stable, isotropic dispersion consisting of nanometer-sized domains of water and / or oil stabilized by interfacial films of surfactants characterized by ultra-low interfacial tension.

[0034] As used herein, the term "phosphate-free" refers to a composition, mixture, or formulation that does not contain or has no added phosphate or phosphate-containing compounds. If phosphate or phosphate-containing compounds are present through contamination of a phosphate-free composition, mixture, or formulation, the amount of phosphate should be less than 0.5% by weight. More preferably, the amount of phosphate is less than 0.1% by weight, and most preferably, the amount of phosphate is less than 0.01% by weight.

[0035] As used herein, the term "phosphorus-free" or "substantially phosphorus-free" refers to a composition, mixture, or formulation that does not contain or has no added phosphorus or phosphorus-containing compounds. If phosphorus or phosphorus-containing compounds are present due to contamination of the phosphorus-free composition, mixture, or ingredient, the amount of phosphorus should be less than 0.5% by weight. More preferably, the amount of phosphorus is less than 0.1% by weight, and most preferably, the amount of phosphorus is less than 0.01% by weight.

[0036] As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as block, graft, random, and alternating copolymers, terpolymers, and higher order "x"-mers, further including derivatives, combinations, and blends thereof. Furthermore, unless specifically limited otherwise, the term "polymer" is intended to include all possible isomeric configurations of the molecule, including, but not limited to, isotactic, syndiotactic, and random symmetries, and combinations thereof. Furthermore, unless specifically limited otherwise, the term "polymer" is intended to include all possible geometric configurations of the molecule.

[0037] The term "soil" or "stain" refers to a non-polar, oily substance that may or may not contain certain particulate matter such as mineral clays, sand, natural minerals, carbon black, graphite, kaolin, environmental dust, and the like.

[0038] As used herein, the term "substantially free" refers to a composition that is completely devoid of the component or has such a small amount of the component that it does not affect the performance of the composition. The component may be present as an impurity or contaminant and should be less than 0.5% by weight. In another embodiment, the amount of the component is less than 0.1% by weight, and in yet another embodiment, the amount of the component is less than 0.01% by weight.

[0039] The term "substantially similar cleaning performance" refers to what is generally achieved by a substitute cleaning product or system using generally the same degree of cleaning power (or at least not significantly less) or generally the same effort expenditure (or at least not significantly less).

[0040] The term "surfactant" as used herein is a compound containing lipophilic and hydrophilic segments that, when added to water or a solvent, reduces the surface tension of the system. The lipophilic and hydrophilic segments of a surfactant are large enough to cause spontaneous self-aggregation.

[0041] The term "hydrotrope" as used herein refers to a compound that solubilizes hydrophobic compounds in aqueous solutions. Hydrotropes generally have hydrophilic and hydrophobic regions that are too small to cause spontaneous self-aggregation. Thus, unlike surfactants, hydrotropes generally lack a critical micelle concentration or critical vesicle concentration.

[0042] As used herein, the term "ware" refers to dishware and cooking utensils, tableware, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors. As used herein, the term "ware washing" refers to washing, cleaning, or rinsing of ware. Utensils also refer to items made of plastic. Types of plastics that may be cleaned with compositions according to the present disclosure include, but are not limited to, those including polypropylene polymers (PP), polycarbonate polymers (PC), melamine formaldehyde resins or melamine resins (melamine), acrylonitrile-butadiene-styrene polymers (ABS), and polysulfone polymers (PS). Other exemplary plastics that may be cleaned using the compounds and compositions of the present disclosure include polyethylene terephthalate (PET) and polystyrene polyamide.

[0043] The terms "weight percent," "wt.-%," "percent by weight," "% by weight," and variations thereof, as used herein, refer to the concentration of a substance calculated by dividing the weight of that substance by the total weight of the composition and multiplying by 100. As used herein, it is understood that "percent," "%," and the like are intended to be synonymous with "weight percent," "% by weight," and the like.

[0044] The methods and compositions of the present disclosure may comprise, consist essentially of, or consist of the components and materials of the present disclosure, as well as other components described herein. As used herein, "consisting essentially of" means that the methods and compositions may include additional steps, components, or materials so long as the additional steps, components, or materials do not materially alter the basic and novel characteristics of the claimed methods and compositions.

[0045] Siloxane and castor oil foaming composition The challenge of generating a stable foam at the 62 wt% ethanol solution interface is due to its already low surface tension (-25 mN / m2). Most surfactants, except silicone-based and fluoride-based surfactants, are unable to reduce the surface tension of water to such low values. The range of useful alkyl-modified siloxanes is limited by the capabilities of the hydrotrope system. If the length of the siloxane (PDMS) becomes too long, the hydrotrope can no longer be held in solution in the ethanol / water system. It has been discovered that pendant alkyl siloxanes and PEG-modified castor oil can provide sufficient and stable foam in water, alcohol / water solutions, or hydrocarbon condensates. The pendant alkyl siloxane lacks a hydrophilic region. Without this region, the siloxane would be insoluble in aqueous solutions and would not be able to function as a silicone-based surfactant by itself.

[0046] Alkylsiloxane In one embodiment, the alkyl siloxanes, which must be linear, include those of the general formula: [ka] During the ceremony, n is 0 to 30; m is 1 to 50; R and R1 are methyl; R2 is a straight-chain or branched, unsubstituted or substituted, saturated or unsaturated, aliphatic or aromatic C1 to C30 hydrocarbon, and must not be a hydrophilic group.

[0047] In a preferred embodiment, R2 is a C2-C28 hydrocarbon, n is 0-30, and m is 1-50.

[0048] In a preferred embodiment, R2 is a C2-C28 hydrocarbon, n is 0, and m is 1.

[0049] In a more preferred embodiment, R2 is a C2-C12 hydrocarbon, n is 0, and m is 1. In a most preferred embodiment, R2 is a C8 hydrocarbon, n is 0, and m is 1.

[0050] PEG-modified castor oil The compositions of the present invention may include one or more hydrotropes that aid in the stability of the composition and in the aqueous formulation. Functionally, suitable hydrotrope couplers that can be used are non-toxic and maintain the active ingredients in aqueous solution over the temperature range and concentrations to which the concentrate or any use solution will be exposed.

[0051] Any hydrotrope coupling agent may be used provided that it does not react with other components of the composition or adversely affect the performance properties of the composition. Representative classes of hydrotrope coupling or solubilizing agents that may be used include anionic surfactants such as alkyl sulfates and alkane sulfonates, linear alkyl benzene or naphthalene sulfonates, secondary alkane sulfonates, alkyl ether sulfates or sulfonates, alkyl phosphates or phosphonates, dialkyl sulfosuccinates, sugar esters (e.g., sorbitan esters), amine oxides (mono-, di-, or trialkyl), and C8-C10 alkyl glucosides. Preferred coupling agents include n-octanesulfonate available as NAS8D from Ecolab Inc., n-octyldimethylamine oxide, and commercially available aromatic sulfonates such as alkylbenzenesulfonates (e.g., xylenesulfonates) or naphthalenesulfonates, aryl or alkaryl phosphates, or their alkoxylated analogs having from 1 to about 40 ethylene, propylene or butylene oxide units or mixtures thereof. Other preferred hydrotropes include C6-C24 alcohol alkoxylates (alkoxylates meaning ethoxylates, propoxylates, butoxylates, and copolymer or terpolymer mixtures thereof) having 1 to about 15 alkylene oxide groups (preferably about 4 to about 10 alkylene oxide groups) (preferably C6-C14 alcohol alkoxylates); C6-C24 alkylphenol alkoxylates (preferably C8-C10 alkylphenol alkoxylates) having 1 to about 15 alkylene oxide groups (preferably about 4 to about 10 alkylene oxide groups); C6-C24 alkyl polyglycosides (preferably C6-C24 alkyl phenol alkoxylates) having 1 to about 15 glycoside groups (preferably about 4 to about 10 glycoside groups); 20alkyl polyglycosides; C6-C24 fatty acid ester ethoxylates, propoxylates or glycerides; and C4-C12 mono- or dialkanolamides. A preferred hydrotrope is sodium xylene sulfonate (SXS).

[0052] In a preferred embodiment, the hydrotrope is castor oil. Castor oil is a vegetable-derived oil obtained from the seeds of the castor bean plant (castor bean). It is a mixture of triglycerides made up of several different fatty acids. It is a monounsaturated fat with one double carbon-carbon bond per triglyceride arm. The main component is ricinoleic acid, with the remainder of the oil made up of oleic acid, linoleic acid, stearic acid, and several other organic acids.

[0053] The chemistry of the main component of ricinoleic acid differs among triglycerides. This fatty acid has a hydroxyl (-OH) group on each arm of the molecule, which makes it more polar than other fatty acids. The hydroxyl groups also facilitate the chemical modification of triglycerides, allowing for the creation of derivatives with desirable properties for many different applications.

[0054] One such derivative is PEG-x castor oil (x=number of ethylene glycol units). Ricinoleic acid (castor oil) reacted with ethylene oxide produces polyethylene glycol modified castor oil, where the number of ethylene glycol units varies from as few as 2 to over 100. The ethylene glycol portion of the molecule is hydrophilic (water soluble). This hydrophilic portion is combined with the hydrophobic oil portion of the triglyceride to produce a non-ionic surfactant molecule. These surfactant molecules can be used by formulators as excellent emulsifiers for conditioning agents, stabilizers, and thickeners. The ethylene glycol group enhances the moisturizing properties of the castor oil molecule. PEG-castor oil molecules range from dispersible in aqueous solutions to completely water soluble, depending on the PEG-#. Above about PEG-# 35, the molecule becomes completely water soluble.

[0055] PEG-modified castor oils for use in embodiments of the present disclosure include those of the general formula: [ka] In the formula, l, m, and n are the average numbers of polyethylene glycol (PEG) units ranging from 1 to 100. In a preferred embodiment, the PEG-modified castor oil contains 10 to 60 moles or more, preferably 20 to 60 moles of PEG.

[0056] Without being bound by any particular theory, it is believed that both of the hydrophobic R groups of the pendant alkylsiloxane provide sufficient interaction with the hydrocarbon of the solution to improve its solubility, and interact with the hydrophobic tail of the PEG-modified castor oil.The PEG modification of the castor oil then provides sufficient solubility for both compounds to dissolve in the solution.This interaction allows the two compounds to act synergistically to allow sufficient solubility for both, and to reduce surface tension sufficiently to make it energetically favorable for foam formation.Thus, this synergistic interaction allows these two combined compounds to act as surfactants in many solutions, including water, alcohol / water, and hydrocarbon condensates.

[0057] According to embodiments, the foaming composition is used in cleaning, rinsing, degreasing, and other formulations, and can replace surfactants. The foaming composition of the present disclosure is optimized to form stable microemulsions without co-surfactants. Furthermore, emulsions or microemulsions of different temperature ranges that are stable and irreversible, i.e., emulsions or microemulsions that do not revert to stay within a specific temperature range, can be produced. The foaming composition of the present disclosure can form emulsions or microemulsions with or in cleaning compositions to remove or treat stains caused by oils and fatty acids, including hydrocarbon-based oils, vegetable oils, organic oils, mineral oils, synthetic oils, petrochemical oils, volatile essential oils, including fatty acids, lipids, and triglycerides.

[0058] This functionality can be used for the removal of oil in lubricants, sunscreen lotions, hair products for pharmaceutical applications such as shampoos, gels, conditioners, petroleum products such as diesel fuel (petroleum diesel), ethane (and other short chain alkanes), fuel oil (the heaviest commercial fuel used in ships / furnaces), gasoline (petrol), jet fuel, kerosene, and liquefied petroleum gas, lubrication products for personal and engineering use, cleaning products or any other products requiring oil emulsions or microemulsions such as detergents, fertilizers, pharmaceuticals, paints, plastics, synthetic fibers, and synthetic rubber.

[0059] The pendant alkyl siloxane can be present in the solution at about 0.01% to about 10% by weight, about 0.02% to about 7% by weight, or about 0.05% to about 5% by weight.

[0060] Another angle is the successful formation of a microemulsion where the insoluble material is an alkyl methicone, the hydrotrope is PEG-modified castor oil, and the carrier / vehicle is mixed ethanol. This microemulsion is significantly different from most microemulsions in that the insoluble component contributes to antifoaming, and the insoluble alkyl dimethicone in this particular microemulsion contributes to foaming.

[0061] This composition also works with other short chain alcohols such as methanol and isopropanol. Therefore, this disclosure can be very important for the inhibition / prevention of methane hydrate blockages, since the preferred treatment is to spray a foam containing a short chain alcohol such as methanol.

[0062] Additionally, there are other uses and applications including, but not limited to, laundry washing, mitigating laundry fires with non-trans fats, and hard surface cleaning such as hand washing of pots and pans, machine dishwashing, all-purpose washing, floor washing, CIP cleaning, open facility washing, foam washing, vehicle washing, etc. The present disclosure also relates to non-cleaning related uses and applications such as dry lubricants, tire dressings, polishes, etc., as well as triglyceride-based lotions, sun tanning lotions, potential pharmaceutical emulsions, and microemulsions.

[0063] In certain embodiments, the foaming composition is part of a cleaning composition that further comprises conventional cleaning ingredients such as polyvalent cations such as Mg2+, Ca2+, or other functional electrolytes such as alkalinity sources or chelating agents. The resulting combination is highly effective in forming microemulsions with non-trans fats at relatively low temperatures. This system can be used in formulations for laundry detergents, hard surface cleaners, whether laundry detergents, alkaline-based or acid-based rinses, hard surface cleaners, rinse aids, pre-spotting agents, or even as other emulsions or microemulsions themselves to aid hard surface cleaners.

[0064] In such compositions, the PEG-modified castor oil may be present in solution at about 0.05% to about 10% by weight, about 0.1% to about 7% by weight, or about 0.2% to about 5% by weight.

[0065] Alcohol / Water Solutions Using Siloxane and Castor Oil Foaming Compositions Cleaning Composition Formulations In another embodiment, the foaming composition is formulated into a cleaning composition, such as a dishwashing or laundry detergent, that contains builders and other conventional ingredients such as enzymes. Examples of such standard laundry and utensil cleaning ingredients and formulations well known to those skilled in the art are provided in the following paragraphs.

[0066] The detergent or ware cleaning composition may be provided in solid or liquid form and may, for example, include an alkalinity source, a metal protectant (for ware cleaning), a surfactant or surfactant system of the disclosed water, and a threshold agent, and other optional ingredients. A typical formulation may include about 30% to about 80% by weight of the alkalinity source, about 15% to about 35% by weight of the metal protectant, about 2% to about 10% by weight of the surfactant, about 0.1% to about 20% by weight of the water, and about 0.2% to about 15% by weight of the threshold agent. When present, the scale inhibitor is present in an amount of about 0 to about 15% by weight.

[0067] Yet another embodiment includes hard surface cleaning compositions having a surfactant system of the present disclosure, an acid source or alkalinity source, and optionally a solvent, water conditioner, and water to create a hard surface cleaner that is effective in removing greasy and oily soils from surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, floors, etc. These surfaces may be those that are symbolized as "hard surfaces" (walls, floors, toilets, etc.).

[0068] A typical hard surface formulation with about 18% actives comprises from about 40% to about 80% by weight of the surfactant system of the present disclosure, from about 3% to about 18% by weight of a water conditioner, from about 0.1% to about 0.55% by weight of an acid source or alkali source, from about 0% to about 10% by weight of a solvent, and from about 10% to about 60% by weight of water.

[0069] In particular, the cleaning composition comprises from about 45% to about 75% by weight of the foaming system of the present disclosure, from about 0% to about 10% by weight of an optional co-surfactant, from about 5% to about 15% by weight of a water conditioner, from about 0.3% to about 0.5% by weight of an acid source or alkalinity source, from about 0 to about 6% by weight of a solvent, and from about 15% to about 50% by weight of water. In other embodiments, similar intermediate and use concentrations may also be present in the cleaning compositions of the present disclosure.

[0070] Additional traditional cleaning ingredients.

[0071] Chelating Agents The composition may optionally include a chelating agent. Examples of chelating agents include phosphonic acids and phosphonates, phosphates, aminocarboxylates and their derivatives, pyrophosphates, ethylenediamine and ethylenetriamine derivatives, hydroxy acids, and mono-, di-, and tricarboxylates and their corresponding acids. Other chelating agents include nitroacetates and their derivatives, and mixtures thereof. Examples of aminocarboxylates include aminoacetic acids and their salts. Suitable aminoacetic acids include N-hydroxyethylaminodiacetic acid, hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), tetrasodium ethylenediaminetetraacetate (EDTA), diethylenetriaminepentaacetic acid (DTPA), and alanine-N,N-diacetic acid; n-hydroxyethyliminodiacetic acid and the like, their alkali metal salts, and mixtures thereof. Suitable aminophosphoric acids include nitrilotrismethylenephosphonic acid and other aminophosphoric acids with alkyl or alkaline groups having less than 8 carbon atoms. Exemplary polycarboxylates include iminodisuccinic acid (IDS), sodium polyacrylate, citric acid, gluconic acid, oxalic acid, their salts, mixtures thereof, and the like. Additional polycarboxylates include citric acid or citrate type chelating agents, polymeric polycarboxylates, and acrylic acid or polyacrylic acid type chelating agents. Additional chelating agents include polyaspartic acid or co-condensates of other amino acids with aspartic acid, C4-C25-mono- or dicarboxylic acids, and C4-C25-mono- or diamines. Exemplary polymeric polycarboxylates include polyacrylic acid, maleic acid / olefin copolymers, acrylic / maleic acid copolymers, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, and the like.

[0072] The chelating agent can be present in an amount of from about 0.01 to about 5% by weight, from about 0.05 to about 3% by weight, and from about 0.1 to about 1.5% by weight.

[0073] Preservatives The composition may optionally contain a preservative.Generally, preservatives are classified into specific classes, including phenols, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines, nitro derivatives, biguanides, analides, organic sulfur and sulfur-nitrogen compounds, alkylparabens, and various compounds.Some non-limiting examples of phenolic antibacterial agents include pentachlorophenol, orthophenylphenol, chloroxylenol, p-chloro-m-cresol, p-chlorophenol, chlorothymol, m-cresol, o-cresol, p-cresol, isopropylcresol, mixed cresols, phenoxyethanol, phenoxyethylparaben, phenoxyisopropanol, phenylparaben, resorcinol, and their derivatives. Some non-limiting examples of halogen compounds include trichlorohydroxydiphenyl ether (Triclosan), sodium trichloroisocyanurate, sodium dichloroisocyanurate, iodine-poly(vinylpyrrolidine-onene) complex, and bromine compounds such as 2-bromo-2-nitropropane-1,3-diol, and their derivatives. Some non-limiting examples of quaternary ammonium compounds include benzalkonium chloride, benzethonium chloride, behentrimonium chloride, cetrimonium chloride, and their derivatives. Some non-limiting examples of amine and nitro-containing compounds include hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates such as sodium dimethyldithiocarbamate, and their derivatives. Some non-limiting examples of biguanides include polyaminopropyl biguanide and chlorhexidine gluconate. Some non-limiting examples of alkylparabens include methyl, ethyl, propyl, and butylparaben. The preservative is preferably present in the composition in an amount of from about 0 to about 3% by weight, from about 0.1 to about 2% by weight, and from about 0.2 to about 1% by weight.

[0074] Thickener The composition may optionally include a thickening agent. Examples of thickening agents include (1) cellulose-based thickeners and their derivatives, (2) natural gums, (3) starches, (4) stearates, (5) fatty acid alcohols, and (6) polyethylene oxides. Some non-limiting examples of cellulose thickeners include carboxymethylhydroxyethylcellulose, cellulose, hydroxybutylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, microcrystalline cellulose, sodium cellulose sulfate, and the like. Some non-limiting examples of natural gums include acacia, calcium carrageenan, guar, gelatin, guar gum, hydroxypropyl guar, karaya gum, kelp, locust bean gum, pectin, sodium carrageenan, tragacanth gum, xanthan gum, and the like. Some non-limiting examples of starches include oat flour, potato starch, wheat flour, wheat starch, and the like. Some non-limiting examples of stearates include PEG-150 distearate, methoxy PEG-22 / dodecyl glycol copolymer, etc. Some non-limiting examples of fatty acid alcohols include capryl alcohol, cetearyl alcohol, lauryl alcohol, oleyl alcohol, palm kernel alcohol, etc.

[0075] The amount of thickener in the composition depends on the desired viscosity of the composition. The composition preferably has a low enough viscosity to be pumped through a former, such as a spray former, to allow for foamability.

[0076] Positively charged polymer In certain embodiments, the composition may include a positively charged polymer for further foam stabilization.

[0077] Positively charged polymer According to the present invention, the positively charged class of polymers, such as polyethyleneimine (PEI) and its derivatives, such as alkoxylated and / or ethoxylated (PEI) polymers, polyamines, polyquats, polyglycerolquats, and other PEI derivatives, their salts or mixtures, can be used in the compositions of the present invention. PEI is a polymeric amine or polyamine, which includes polyethyleneimine compounds (PEI) and / or its derivatives. Polyethyleneimine can include primary, secondary, or tertiary amine compounds. Polyethyleneimine compounds and / or its derivatives can include linear and / or branched polyethyleneimine. Still further, polyethyleneimine and / or its derivatives can vary widely in molecular weight, topology, and shape, including, for example, linear, branched, or comb-like structures as a result of ring-opening polymerization of ethyleneimine. See Angelescu et al., Langmuir, 27, 9961-9971 (2011), which is incorporated herein by reference in its entirety. According to one aspect of the invention, the bleach activator may be a linear and / or branched polyethyleneimine.

[0078] According to the present invention, a class of positively charged polymers such as polyethyleneimine (PEI) and its derivatives, such as ethoxylated (PEI) polymers, propoxylated (PEI) polymers, polyamines, polyquats, polyglycerolquats, and other PEI derivatives, their salts or mixtures are used in the foaming composition to provide electrostatic interactions with surfactants present in the foaming composition, with ethoxylated or propoxylated PEI polymers being particularly preferred. In a preferred such embodiment, the PEI(s) are branched, globular polymeric amines, and the molecular weight of the PEI or PEI salt used is from about 800 Daltons to about 2 million Daltons. In addition, the charge density of the PEI or PEI salt used is from about 15 meq / g to about 25 meq / g, more preferably from about 16 meq / g to about 20 meq / g. Examples of such preferred PEIs include the BASF products LUPASOL WF (25 kDa; 16-20 meq / g) and Lupasol® FG (800 Daltons; 16-20 meq / g), as well as the SOKALAN® family of polymers available from BASF, such as SOKALAN® HP20, SOKALAN® HP22G, etc.

[0079] According to the present invention, cleaning compositions are formed using a cleaning amount of anionic surfactant (about 1% to about 75% by weight) and about 0.01% to about 5.0% by weight of ethoxylated PEI or other similarly positively charged polymers such as polyamines, polyquats, polyglycerolquats, and commercially available products from Nalco such as VX10035, VX9945, and VX9946, two other Nalco products that are propoxylated PEIs, in which the PEI is first propoxylated and then ethoxylated. Linear polyethyleneimines are made by cationic polymerization of oxazoline and oxazine derivatives. Methods for preparing linear PEI are more fully described in Advances in Polymer Science, Vol. 102, pgs. 171-188, 1992 (references 6-31), which is incorporated herein by reference in its entirety. Polyethylenimines can also be made by the polymerization of aziridines, often resulting in polymeric amines containing primary, secondary, and tertiary amine functional groups. Commercial preparation of PEI is generally an acid-catalyzed ring-opening reaction of ethylenimines, also known as aziridines, as shown below.

[0080] Suitable polyethyleneimine compounds useful in the present invention may contain a mixture of primary, secondary, and tertiary amine substituents. The mixture of primary, secondary, and tertiary amine substituents may be in any ratio, including, for example, a ratio of about 1:1:1 to about 1:2:1, with branches every 3 to 3.5 nitrogen atoms along the chain segment. Alternatively, suitable polyethyleneimine compounds may be predominantly one of primary, secondary, or tertiary amine substituents.

[0081] An exemplary PEI product has the following formula (-(CH-CH-NH)) with a molecular weight (as a repeating unit) of 43.07. n In certain embodiments, the polyfunctional cationic polyethyleneimine has a branched polymer structure according to the formula (-(CH2-CH2-NH) n -) is at least 10~10 5and the nitrogen to carbon ratio is 1:2. PEI polymers have the general polymer structure: [ka]

[0082] The PEI products may also be represented by the following general formula, which may vary by substitution, size, molecular weight, branching, etc.: [ka] In the formula, x is an integer of 1 or more, and y is an integer of 1 or more. Preferably, x is an integer of about 1 to about 120,000, preferably about 2 to about 60,000, more preferably about 3 to about 24,000, and y is an integer of about 1 to about 60,000, preferably about 2 to about 30,000, more preferably about 3 to about 12,000.

[0083] A variety of commercially available polyethyleneimines are available, including those sold under the trade name Lupasol® (BASF), including, for example, Lupasol® FG, Lupasol® G, Lupasol® PR8515, Lupasol® WF, Lupasol® G20 / 35 / 100, Lupasol® HF, Lupasol® P, Lupasol® PS, Lupasol® PO100, Lupasol® PN50 / 60, and Lupasol® SK. Such exemplary polyethyleneimines are available as anhydrous polyethyleneimine and / or modified polyethyleneimine provided in aqueous solution or methoxypropanol (Lupasol® PO100). The molar mass of polyethyleneimine, including modified polyethyleneimine, can vary from about 800 g / mol to at least 2,000,000 g / mol.

[0084] In certain embodiments, the polymeric amine bleach activator, preferably the PEI bleach activator, may be a branched spherical polymeric amine. In further embodiments, the molecular weight of the polymeric amine bleach activator or PEI bleach is from about 100 Daltons to about 2 million Daltons (PEI-2,000,000), more preferably from about 100 Daltons to about 1 million Daltons (PEI-1,000,000), more preferably from about 500 Daltons to about 500 kDa (PEI-500,000), more preferably from about 500 Daltons to about 50 kDa (PEI-50,000), more preferably from about 800 Daltons to about 50 kDa (PEI-50,000), more preferably from about 800 Daltons to about 10 kDa (PEI-10,000). In further embodiments, the charge density of the PEI or PEI salt is from about 15 meq / g to about 25 meq / g, more preferably from about 16 meq / g to about 20 meq / g. Commercially available examples of such preferred PEIs include the BASF products LUPASOL® WF (25 kDa; 16-20 meq / g) and Lupasol® FG (800 Daltons; 16-20 meq / g), and BASF products in the SOKALAN® family of polymers, e.g., SOKALAN® HP20, SOKALAN® HP22G, etc.

[0085] In one aspect, the polymeric amine may include other substituents and / or copolymers. For example, the polymeric amines may also include substituents, including, for example, ethoxylates and propoxylates. In one aspect of the invention, the polymeric amines, such as polyethyleneimine, are derivatized with ethylene oxide (EO) and / or propylene oxide (PO) side chains. In accordance with the invention, the PEI does not contain propylene oxide side chains. In an exemplary aspect of the invention, the ethoxylated PEI may be highly branched, with the replaceable hydrogens on the primary and secondary nitrogens being replaced with ethoxylated chains containing various degrees of repeat units, such as the following polymer structure (collectively PEI20EO): [ka]

[0086] In one embodiment, the positively charged polymer is a polyethyleneimine polymer having ethylene oxide chains. Ethoxylation of PEI increases the solubility of the bleach activator according to the present invention.

[0087] The polymeric amine may also include copolymers, for example with ethylenediamine. Various substituents and / or copolymers may be included to modify the solubility or any other physical properties of the particular polymeric amine used as a bleach activator according to the present invention.

[0088] Due to the presence of amine groups, PEI can be protonated with acid to form PEI salts from the surrounding medium, resulting in a partially or fully ionized product depending on the pH. For example, about 73% of PEI is protonated at pH 2, about 50% of PEI is protonated at pH 4, about 33% of PEI is protonated at pH 5, about 25% of PEI is protonated at pH 8, and about 4% of PEI is protonated at pH 10. In general, PEI can be purchased in protonated or unprotonated forms with or without water. Examples of segments of branched protonated polyethyleneimine (PEI salt) are shown below. [ka]

[0089] The counterion of each protonated nitrogen center is in equilibrium with the anion of the acid obtained during neutralization. Examples of protonated PEI salts include, but are not limited to, PEI-hydrochloride, PEI-sulfate, PEI-nitrate, PEI-acetate, PEI fatty acid salts, etc. In fact, any acid can be used to protonate PEI to form the corresponding PEI salt compound.

[0090] The cationic polymer PEI is present in an amount of about 0.01% to about 5% by weight, with the effect decreasing above 5% by weight, which is the upper critical limit.

[0091] Cleaning Composition The foaming composition of the present disclosure can replace surfactants found in cleaning compositions due to the synergistic hydrophilic regions on the PEG modified castor oil and the hydrophobic regions on both the alkylsiloxane and the PEG modified castor oil.The foaming composition of the present disclosure can be used alone, as a press-spot or pre-treatment composition in combination with conventional detergents or cleaning agents, or can be incorporated into cleaning compositions.The present disclosure includes both hard surface and soft surface cleaning compositions that use the disclosed surfactant system.

[0092] In one embodiment, the present disclosure uses the foaming composition of the present disclosure, an acid source, a solvent, a water conditioner, and water to create a hard surface cleaner that is effective in removing greasy and oily soils from surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, floors, etc. These surfaces may be those that are symbolized as "hard surfaces" (walls, floors, toilets, etc.).

[0093] A typical hard surface formulation of about 18% active includes from about 40% to about 80% by weight of the foaming composition of the present disclosure, from about 3% to about 18% by weight of a water conditioner, from about 0.1% to about 0.55% by weight of an acid source, from about 0% to about 10% by weight of a solvent, and from about 10% to about 60% by weight of water.

[0094] In particular, the cleaning composition includes from about 45% to about 75% by weight of the foaming composition of the present disclosure, from about 0% to about 10% by weight of an optional co-surfactant, from about 5% to about 15% by weight of a water conditioner, from about 0.3% to about 0.5% by weight of an acid source, from about 0 to about 6% by weight of a solvent, and from about 15% to about 50% by weight of water. In other embodiments, similar intermediate and use concentrations may also be present in the cleaning compositions of the present disclosure.

[0095] In laundry detergent formulations, the compositions of the present disclosure typically include the foaming composition of the present disclosure and optionally a builder with an enzyme. Examples of such standard laundry detergent ingredients well known to those skilled in the art are provided in the following paragraphs.

[0096] Although not required for purposes of this disclosure, the non-limiting list of additional ingredients exemplified below are suitable for use in the present compositions and may desirably be incorporated into certain embodiments of the present disclosure to aid or enhance cleaning performance, for example, for treatment of the substrate being cleaned, or to modify the aesthetics of the cleaning composition, as in the case of fragrances, colorants, dyes, etc. The exact nature of these additional ingredients, and their levels of incorporation, will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used. Suitable additional materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibitors, viscosity modifiers, dispersants, additional enzymes and enzyme stabilizers, catalytic materials, bleaching agents, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersants, threshold inhibitors for hard water settling pigments, clay removers / anti-redeposition agents, brighteners, suds suppressors, dyes, fabric hueing agents, fragrances, structural elasticity agents, fabric softeners, carriers, additional hydrotropes, processing aids, solvents, pigment antimicrobial agents, pH buffers, processing aids, active optical brighteners, additional surfactants, and mixtures thereof. In addition to the disclosure below, suitable examples of such other adjuvants and usage levels can be found in U.S. Patent Nos. 5,576,282, 6,306,812 B1, and 6,326,348 B1, which are incorporated by reference.

[0097] As stated, auxiliary components are not essential to the applicant's composition. Thus, certain embodiments of the applicant's composition do not contain additional materials. However, if one or more additional materials are present, such one or more additional components may be present as detailed below.

[0098] The liquid detergents herein have a nominal pH of about 7 to about 13, or about 7 to about 9, or about 7.2 to about 8.5, or about 7.4 to about 8.2. The detergents may contain buffers and / or pH adjusters, including inorganic and / or organic sources of alkalinity and acidifying agents such as water-soluble alkali metal and / or alkaline earth metal salts of hydroxides, oxides, carbonates, bicarbonates, borates, silicates, phosphates, and / or metasilicates; or sodium hydroxide, potassium hydroxide, pyrophosphates, orthophosphates, polyphosphates, and / or phosphonates. Organic sources of alkalinity herein include primary, secondary, and / or tertiary amines. Inorganic acidifying agents herein include HF, HCl, HBr, HI, boric acid, sulfuric acid, phosphoric acid, and / or sulfonic acid, or boric acid. Organic acidifying agents herein include substituted and unsubstituted, branched, linear and / or cyclic C 1-30 Contains carboxylic acids.

[0099] Bleach The cleaning compositions of the present disclosure may include one or more bleaching agents. Suitable bleaching agents other than bleach catalysts include photobleaches, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, and mixtures thereof. In general, when a bleaching agent is used, the compositions of the present disclosure may include from about 0.1% to about 50%, or even from about 0.1% to about 25% by weight of the subject cleaning composition of the bleaching agent. Examples of suitable bleaching agents include: (1) Preformed peracids: Suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, periodic acids and salts, persulfuric acids and salts, such as Oxzone®, and mixtures thereof. Suitable percarboxylic acids include hydrophobic and hydrophilic peracids having the formula R--(C--O)O--OM, where R is an optionally branched alkyl group having 6-14 carbon atoms, or 8-12 carbon atoms, when the peracid is hydrophobic, and less than 6 carbon atoms, or even less than 4 carbon atoms, when the peracid is hydrophilic, and M is a counterion, such as sodium, potassium, or hydrogen, and (2) sources of hydrogen peroxide, such as inorganic perhydrate salts, including alkali metal salts, such as the sodium salts (usually monohydrate or tetrahydrate), of perborates, percarbonates, persulfates, perphosphates, persilicates, and mixtures thereof. In one embodiment of the present disclosure, the inorganic perhydrate salt is selected from the group consisting of sodium salts of perborates, percarbonates, and mixtures thereof. When used, the inorganic perhydrate salt is typically present in an amount of 0.05-40% by weight, or 1-30% by weight of the total composition, and is typically incorporated into such compositions as a crystalline solid that can be coated. Suitable coatings include inorganic salts such as alkali metal silicates, carbonates, or borates, or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils, or fatty soaps, and (3) bleach activators having R--(C--O)-L, where R is an optionally branched alkyl group having 6-14 carbon atoms, or 8-12 carbon atoms, when the bleach activator is hydrophobic, and less than 6 carbon atoms, or even less than 4 carbon atoms, when the bleach activator is hydrophilic, and L is a leaving group. Examples of suitable leaving groups are benzoic acid and its derivatives, especially benzenesulfonate.Suitable bleach activators include dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or salts thereof, 3,5,5-trimethylhexanoyloxybenzenesulfonate, tetraacetylethylenediamine (TAED) and nonanoyloxybenzenesulfonate (NOBS). Suitable bleach activators are also disclosed in WO98 / 17767. While any suitable bleach activator may be used, in one aspect of the present disclosure, the subject cleaning composition may include NOBS, TAED, or a mixture thereof.

[0100] When present, the peracids and / or bleach activators are generally present in the composition in an amount of from about 0.1 to about 60%, from about 0.5 to about 40%, or even from about 0.6 to about 10% by weight based on the composition. One or more hydrophobic peracids or precursors thereof may be used in combination with one or more hydrophilic peracids or precursors thereof.

[0101] The amount of hydrogen peroxide source and peracid or bleach activator may be selected such that the molar ratio of available oxygen (from the peroxide source) to peracid is from 1:1 to 35:1, or even from 2:1 to 10:1.

[0102] Additional Surfactants In some embodiments, the composition may include an additional surfactant, which may be anionic, nonionic, cationic zwitterionic, and may also include additional extended chain surfactants as discussed herein.

[0103] The cleaning composition can contain an additional anionic surfactant component, including a cleaning amount of an anionic surfactant or a mixture of anionic surfactants. Anionic surfactants are desirable in cleaning compositions due to their wetting and cleaning properties. The anionic surfactants that can be used according to the present disclosure include any anionic surfactant available in the cleaning industry. Suitable groups of anionic surfactants include sulfonates and sulfates. Suitable surfactants that can be provided in the anionic surfactant component include alkylarylsulfonates, secondary alkane sulfonates, alkyl methyl ester sulfonates, alpha olefin sulfonates, alkyl ether sulfates, alkyl sulfates, and alcohol sulfates.

[0104] Suitable alkylaryl sulfonates that can be used in the cleaning composition can have an alkyl group containing 6 to 24 carbon atoms, and the aryl group can be at least one of benzene, toluene, and xylene.Suitable alkylaryl sulfonates include linear alkylbenzene sulfonates.Suitable linear alkylbenzene sulfonates include linear dodecyl benzyl sulfonates, which can be provided as an acid that is neutralized to form a sulfonate.Additionally suitable alkylaryl sulfonates include xylene sulfonates and cumene sulfonates.

[0105] Suitable alkane sulfonates that can be used in the cleaning composition can have an alkane group having 6 to 24 carbon atoms. Suitable alkane sulfonates that can be used include secondary alkane sulfonates. Suitable secondary alkane sulfonates include C 2 -methyl-2-propane sulfonates, available commercially as Hostapur SAS from Clariant. 14 ~C 17 Examples include secondary alkyl sodium sulfonates.

[0106] Suitable alkyl methyl ester sulfonates that can be used in the cleaning composition include those having an alkyl group containing from 6 to 24 carbon atoms. Suitable alpha olefin sulfonates that can be used in the cleaning composition include those having an alpha olefin group containing from 6 to 24 carbon atoms.

[0107] Suitable alkyl ether sulfates that can be used in the cleaning compositions include those having from about 1 to about 10 repeating alkoxy groups, from about 1 to about 5 repeating alkoxy groups. Generally, the alkoxy groups contain from about 2 to about 4 carbon atoms. A suitable alkoxy group is ethoxy. A suitable alkyl ether sulfate is sodium lauryl ether sulfate, available under the designation Steol CS-460.

[0108] Suitable alkyl sulfates that can be used in the cleaning compositions include those having an alkyl group containing from 6 to 24 carbon atoms. Suitable alkyl sulfates include, but are not limited to, sodium lauryl sulfate and sodium lauryl / myristyl sulfate.

[0109] Suitable alcohol sulfates that can be used in the cleaning compositions include those having an alcohol group containing from about 6 to about 24 carbon atoms.

[0110] The anionic surfactant can be neutralized with an alkali metal salt, an amine, or a mixture thereof. Suitable alkali metal salts include sodium, potassium, and magnesium. Suitable amines include monoethanolamine, triethanolamine, and monoisopropanolamine. When using a mixture of salts, a suitable mixture of alkali metal salts can be sodium and magnesium, and the molar ratio of sodium to magnesium can be about 3:1 to about 1:1.

[0111] When provided as a concentrate, the cleaning composition can include additional anionic surfactant components in an amount sufficient to provide a use composition having desired wetting and cleaning properties after dilution with water. Concentrates can include from about 0.1% to about 0.5%, from about 0.1% to about 1.0%, from about 1.0% to about 5%, from about 5% to about 10%, from about 10% to about 20%, 30%, from about 0.5% to about 25%, and from about 1% to about 15% by weight of anionic surfactant, and similar intermediate concentrations.

[0112] The cleaning composition may contain a nonionic co-surfactant component comprising a cleaning amount of a nonionic surfactant or a mixture of nonionic surfactants. The nonionic co-surfactant may be included in the cleaning composition to improve grease removal properties. It should be understood that the surfactant component may include a nonionic surfactant component, but the nonionic surfactant component may be excluded from the cleaning composition.

[0113] Additional nonionic surfactants that can be used in the composition include polyalkylene oxide surfactants (also known as polyoxyalkylene surfactants or polyalkylene glycol surfactants). Suitable polyalkylene oxide surfactants include polyoxypropylene surfactants and polyoxyethylene glycol surfactants. Suitable surfactants of this type are synthetic organic polyoxypropylene (PO)-polyoxyethylene (EO) block copolymers. These surfactants include diblock polymers containing an EO block and a PO block, i.e., a central block of polyoxypropylene units (PO), and diblock polymers having a block of polyoxyethylene grafted onto the polyoxypropylene units or a central block of EO to which a PO block is attached. Additionally, the surfactants can have additional blocks of either polyoxyethylene or polyoxypropylene in the molecule. The suitable average molecular weight range of useful surfactants can be from about 1,000 to about 40,000, and the weight percent content of ethylene oxide can be from about 10 to 80% by weight.

[0114] Other nonionic surfactants include alcohol alkoxylates. Suitable alcohol alkoxylates include linear alcohol ethoxylates such as Tomadol™ 1-5, which is a surfactant containing an alkyl group with 11 carbon atoms and 5 moles of ethylene oxide. Additional alcohol alkoxylates include alkylphenol ethoxylates, branched alcohol ethoxylates, secondary alcohol ethoxylates (e.g., Tergitol 15-S-7 from Dow Chemical), castor oil ethoxylates, alkylamine ethoxylates, tallowamine ethoxylates, fatty acid ethoxylates, sorbitol oleate ethoxylates, end-capped ethoxylates, or mixtures thereof. Additional nonionic surfactants include amides such as fatty acid alkanolamides, alkyl diethanolamides, coconut diethanolamides, lauric acid diethanolamides, polyethylene glycol cocoamides (e.g., PEG-6 cocoamide), oleic acid diethanolamide, or mixtures thereof. Additional suitable nonionic surfactants include polyalkoxylated fatty bases, polyalkoxylated amides, glycol esters, glycerol esters, amine oxides, phosphate esters, alcohol phosphates, fatty triglycerides, fatty triglyceride esters, alkyl ether phosphates, alkyl esters, alkylphenol ethoxylate phosphate esters, alkyl polysaccharides, block copolymers, alkyl polyglucosides, or mixtures thereof.

[0115] When nonionic surfactants are included in the cleaning composition concentrates, they may be included in an amount of at least about 0.1% by weight and may be included in an amount of up to about 15% by weight. The concentrates may contain about 0.1-1.0%, about 0.5% to about 12%, or about 2% to about 10% by weight of nonionic surfactant.

[0116] Amphoteric surfactants can also be used to provide desirable cleaning properties.Suitable amphoteric surfactants that can be used include, but are not limited to, betaines, imidazolines, and propionates.Suitable amphoteric surfactants include, but are not limited to, sultaines, amphopropionates, amphodipropionates, aminopropionates, aminodipropionates, amphoacetates, amphodiacetates, and amphohydroxypropylsulfonates.

[0117] When the cleaning composition includes an amphoteric surfactant, the amphoteric surfactant may be included in an amount of about 0.1% to about 15% by weight. Concentrates can include about 0.1% to about 1.0%, 0.5% to about 12%, or about 2% to about 10% by weight of the amphoteric surfactant.

[0118] The cleaning composition may include a cationic surfactant component comprising a cleaning amount of a cationic surfactant or mixture of cationic surfactants. Cationic co-surfactants that may be used in the cleaning composition include C 18 Amines such as primary, secondary, and tertiary monoamines with alkyl or alkenyl chains, ethoxylated alkylamines, alkoxylates of ethylenediamine, imidazoles such as 1-(2-hydroxyethyl)-2-imidazoline, 2-alkyl-1-(2-hydroxyethyl)-2-imidazoline, and n-alkyl (C 12 -C 18 ) quaternary ammonium salts, such as alkyl quaternary ammonium chloride surfactants, such as dimethylbenzyl ammonium chloride, n-tetradecyldimethylbenzyl ammonium chloride monohydrate, and naphthalene substituted quaternary ammonium chlorides, such as dimethyl-1-naphthylmethyl ammonium chloride.

[0119] In some embodiments, the additional surfactant may be a lengthening surfactant. The extending surfactant comprises a linker polyalkylene glycol link. The general formula for the non-ionic extending surfactant is: R-[L] x -[O-CH2--CH2] y where R is a lipophilic moiety, e.g., a linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radical having about 8 to 20 carbon atoms, L is a linking group such as a block of polyalkylene oxide, preferably a block of polypropylene oxide, x is the chain length of the linking group ranging from 2 to 25, and y is the average degree of ethoxylation ranging from 1 to 18. In a preferred embodiment, applicants have found that liquid single-phase microemulsions can be formed using nonionic surfactants with sufficient PO extension as the primary (and only) surfactant. The PO length is optimized at about 5 to about 8 moles of PO. This length of PO extension provides a lower foam profile. Applicants have further found that R groups that are branched hydrophobes, such as Guerbet alcohols, are suitable for defoaming proteinaceous soils.

[0120] Preferred extending surfactants include branched Guerbet alcohol alkoxylates, such as C y (PO)8(EO) x (x=3, 6, 8, 10) (y=10-12), and C( 12-14 )(PO) 16 (EO) x (x=6, 12, 17) are also included.

[0121] Branched Alcohol Alkoxylates Preferred branched alcohol alkoxylates include Guerbet ethoxylates. Guerbet ethoxylates suitable for use herein have the formula: [ka]

[0122] In one embodiment, the Guerbet ethoxylate is R 1 is C2-C20 alkyl, R 2is H or C1-C4 alkyl. In a further aspect, the Guerbet ethoxylates are defined where "n" is an integer from 2 to 20 and "m" is an integer from 1 to 40.

[0123] In a preferred embodiment, the branched alcohol alkoxylates are Guerbet ethoxylates prepared from Guerbet alcohols by dimerization of an alkene (eg, butane).

[0124] Branched alcohol alkoxylates, including Guerbet ethoxylates, can be prepared according to U.S. Patent Nos. 6,906,320, 6,737,553, and 5,977,048, the disclosures of which are incorporated herein by reference in their entirety.Exemplary branched alcohol alkoxylates include those available under the trade names Lutensol XP-30 and Lutensol XP-50 (BASF Corporation).In general, Lutensol XP-30 can be considered to have three repeating ethoxy groups, and Lutensol XP-50 can be considered to have five repeating ethoxy groups.

[0125] Branched alcohol alkoxylates can be classified as relatively water-insoluble or relatively water-soluble. In general, water-insoluble branched alcohol alkoxylates can be considered as alkoxylates that tend to phase separate when provided as a composition containing 5% by weight of branched alcohol alkoxylate and 95% by weight of water. Lutensol XP-30 and Lutensol XP-50 from BASF Corporation are examples of water-insoluble branched alcohol alkoxylates.

[0126] According to an embodiment, the branched alcohol alkoxylate, preferably the water-insoluble Guerbet ethoxylate, has from about 10% to about 90% by weight ethylene oxide, from about 20% to about 70% by weight ethylene oxide, preferably from about 30% to about 60% by weight ethylene oxide.

[0127] Applicants have further discovered that the use of capped extended nonionic surfactants reduces the lather profile of the composition and lather from proteinaceous soils.

[0128] Capped extended nonionic surfactants include: R-[PO] x -[EO] y [N]z

[0129] where N is a capping group such as an alkyl group such as methyl, benzyl, butyl, etc., and in length a PO group of 1 to 5 in length. These capped nonionic surfactants reduce foam profile, etc., and are effective for rinse aid formulations and detergents.

[0130] builder The cleaning compositions of the present disclosure may include one or more detergent builders or builder systems. When builders are used, the subject compositions typically include at least about 1 wt. %, about 5 wt. % to about 60 wt. %, or even about 10 wt. % to about 40 wt. % of builders by weight of the subject composition. The detergent may contain calcium, or other ion, inorganic or organic detergent builders that counteract the effects of water hardness. Examples include alkali metal citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates, and polyacetyl carboxylates; or sodium, potassium, lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, and citric acid; or citric acid and citrate salts. Organic phosphonate-type sequestering agents such as Monsanto's DEQUEST® and alkane hydroxyphosphonates are useful. Other organic builders include higher molecular weight polymers and copolymers such as polyacrylic acid, polymaleic acid, and polyacrylic / polymaleic acid copolymers and their salts, such as SOKALAN® from BASF. Generally, the builders can be up to 30%, or from about 1% to about 20%, or from about 3% to about 10%.

[0131] The composition also contains about 0.01% to about 10%, or about 2% to about 7%, or about 3% to about 5% C 8~20 Fatty acids may be included as builders. The fatty acids may also contain from about 1 to about 10 EO units. Suitable fatty acids are saturated and / or unsaturated and may be obtained from natural sources such as vegetable or animal esters (e.g., palm kernel oil, palm oil, coconut oil, babassu oil, safflower oil, tall oil, tallow oil and fish oils, greases, and mixtures thereof) or may be synthetically prepared (e.g., by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Useful fatty acids include saturated C 12 fatty acids, saturated C 12~14 Fatty acids, saturated or unsaturated C 12~18 Fatty acids and mixtures thereof. Examples of suitable saturated fatty acids include captonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid. Suitable unsaturated fatty acids include palmitoleic acid, oleic acid, linoleic acid, linolenic acid and ricinoleic acid.

[0132] Dye transfer inhibitor The cleaning compositions of the present disclosure may also include one or more dye transfer inhibitors. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone and polyvinylimidazole, or mixtures thereof. When present in the subject compositions, dye transfer inhibitors may be present at levels of about 0.0001% to about 10%, about 0.01% to about 5%, or even about 0.1% to about 3% by weight of the composition.

[0133] Optical brightener In some embodiments, optical brightener components can be present in the composition of the present disclosure.Optical brighteners can include any whitening agent that can eliminate graying and yellowing of fabrics.Typically, these substances attach to fibers and produce lightening and simulated bleaching effects by converting invisible ultraviolet light into visible longer wavelength light, and the ultraviolet light absorbed from sunlight is emitted as a pale bluish fluorescent light, which adds yellow tones to graying or yellowing laundry, making it pure white.

[0134] Fluorescent compounds belonging to the optical brightener family are typically aromatic or heteroaromatic materials, often containing fused ring systems. An important feature of these compounds is the presence of an uninterrupted chain of conjugated double bonds associated with the aromatic rings. The number of such conjugated double bonds depends on the substituents and the planarity of the fluorescent part of the molecule. Most brightener compounds are derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, 5-membered heterocycles (triazoles, oxazoles, imidazoles, etc.), or 6-membered heterocycles (coumarins, naphthalamides, triazines, etc.).

[0135] Fluorescent brightening agents useful in the present disclosure are known and commercially available. Exemplary commercially available fluorescent brightening agents that may be useful in the present invention can be classified into subgroups, including, but not necessarily limited to, stilbenes, pyrazolines, coumarins, carboxylic acids, methine cyanines, dibenzothiophene-5,5-dioxides, azoles, 5- and 6-membered heterocycles, and derivatives of other various agents. Examples of these types of brightening agents are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982), the disclosure of which is incorporated herein by reference.

[0136] Stilbene derivatives that may be useful in the present disclosure include, but are not limited to, derivatives of bis(triazinyl)amino-stilbene, bisacylamino derivatives of stilbene, triazole derivatives of stilbene, oxadiazole derivatives of stilbene, oxazole derivatives of stilbene, and styryl derivatives of stilbene. In one embodiment, the optical brightener comprises a stilbene derivative.

[0137] In some embodiments, the optical brightener comprises Tinopal UNPA, available through Ciba Geigy Corporation, located in Switzerland.

[0138] Additional optical brighteners for use in the present disclosure include, but are not limited to, 4,4'-diamino-2,2'-stilbenedisulfonic acid (flavonic acid), 4,4'-distyrylbiphenyl, methylumbelliferone, coumarin, dihydroquinolinone, 1,3-diarylpyrazolines, naphthalimides, benzoxazoles, benzisoxazoles and benzimidazoles, and heterocyclic substituted pyrene derivatives, etc. Suitable optical brightener levels include lower levels of about 0.01, about 0.05, about 0.1 or even about 0.2% by weight, to upper levels of 0.5 or even 0.75% by weight.

[0139] Dispersants The compositions of the present disclosure can also include a dispersant. Suitable water-soluble organic materials include homopolymeric or copolymeric acids or salts thereof, in which the polycarboxylic acid contains at least two carboxyl radicals separated from each other by no more than two carbon atoms.

[0140] enzyme The cleaning composition may include one or more enzymes that provide cleaning performance and / or fabric care benefits. Enzymes may be included herein for a wide variety of fabric laundry purposes, including, for example, removal of protein-based, carbohydrate-based, or triglyceride-based stains, and / or fabric repair. Examples of suitable enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, amylase, or combinations thereof, and may be of any suitable origin. The selection of enzymes takes into account factors such as pH activity, stability optimum, thermal stability, stability vs. active detergent, chelating agents, builders, etc. The cleaning enzyme mixtures useful herein are proteases, lipases, cutinases and / or cellulases in combination with amylases. Sample cleaning enzymes are described in U.S. Patent No. 6,579,839.

[0141] The enzymes are typically present at up to about 5 mg, more typically about 0.01 mg to about 3 mg, by weight of active enzyme per gram of detergent. Stated differently, the detergents herein typically contain from about 0.001% to about 5%, or from about 0.01% to about 2%, or from about 0.05% to about 1% by weight of a commercial enzyme preparation. The protease enzymes are present at an activity of about 0.005 to about 0.1 AU per gram of detergent. Proteases useful herein include subtilisins from Bacillus [e.g., subtilis, lentus, licheniformis, amyloliquefaciens (BPN, BPN'), Alcalophilus], such as Esperase®, Alcalase®, Everlase®, and Savinase® (Novozymes), BLAP and variants (Henkel). Further proteases are described in EP 130756, WO 91 / 06637, WO 95 / 10591 and WO 99 / 20726.

[0142] Amylases are described in GB Pat.#1296839, WO94 / 02597 and WO96 / 23873 and are available as Purafect Ox Am® (Genencor), Termamyl®, Natalase®, Ban®, Fungamyl®, Duramyl® (all Novozymes), and RAPIDASE (International Bio-Synthetics, Inc.).

[0143] Cellulases herein include bacterial and / or fungal cellulases having an optimum pH of 5 to 9.5. Suitable cellulases are disclosed in US Patent No. 4,435,307, issued March 6, 1984 to Barbesgoard et al. Cellulases useful herein include, for example, bacterial or fungal cellulases produced by Humicola insolens, particularly DSM 1800, e.g., 50 kD and about 43 kD (Carezyyme®). Further suitable cellulases are EGIII cellulases from Trichoderma longibrachiatum. WO 02 / 099091 by Novozymes describes enzymes exhibiting endo-beta-glucanase activity (EC 3.2.1.4) intrinsic to Bacillus sp. DSM 12648 for use in detergent and textile applications, and anti-redeposition endoglucanases in WO 04 / 053039. Kao in EP 265832 describes alkaline cellulase K, CMCase I, and CMCase II isolated from the fermentation product of Bacillus sp. KSM-635. Kao further discloses in EP1350843 (KSM S237, 1139, KSM64, KSM N131), EP265832A (KSM635, FERM BP1485) and EP0271044A (KSM534, FERM BP1508, KSM539, FERM BP1509, KSM577, FERM BP1510, KSM521, FERM BP1507, KSM580, FERM BP1511, KSM588, FERM BP1513, KSM597, FERM BP1514, KSM522, FERM BP1512, KSM3445, FERM BP1506, KSM425.FERM In the paper entitled "Bacillus subtilis var. cerevisiae", entitled "Bacillus subtilis var. cerevisiae", published in the journal Proc. Sci. 1999, 1441-1454 (BP1505), easy to mass produce, highly active alkaline cellulases / endoglucanases for alkaline environments are described. Such endoglucanases may comprise a polypeptide endogenous to one of the Bacillus genera listed above (or a variant thereof). Other suitable cellulases are family 44 glycosyl hydrolase enzymes exhibiting endo-beta-1,4-glucanase activity from Paenibacillus porixima (wild type), such as XYG1006 described in WO01 / 062903, or variants thereof.Carbohydrases useful herein include, for example, mannanases (see, e.g., U.S. Pat. No. 6,060,299), pectate lyases (see, e.g., WO 99 / 27083), cyclomaltodextrin glucanotransferases (see, e.g., WO 96 / 33267), and / or xyloglucanases (see, e.g., WO 99 / 02663). Bleaching enzymes useful herein with enhancers include, for example, peroxidases, laccases, oxygenases, lipoxygenases (see, e.g., WO 95 / 26393), and / or (non-heme) haloperoxidases.

[0144] Suitable endoglucanases include: 1) enzymes exhibiting endo-beta-1,4-glucanase activity (EC 3.2.1.4) with a sequence identity of at least 90%, or at least 94%, or at least 97%, or at least 99%, or 100% to the amino acid sequence of positions 1 to 773 of SEQ ID NO: 2 in WO02 / 099091; or fragments thereof with endo-beta-1,4-glucanase activity. GAP in the GCG program uses a GAP creation penalty of 3.0 and a GAP extension penalty of 0.1 to determine identity. See WO02 / 099091 of Dec. 12, 2002 by Novozymes A / S, e.g., Celluclean™ by Novozymes A / S. GCG refers to a sequence analysis software package (Accelrys, San Diego, Calif., USA). GCG includes a program called GAP, which uses the Needleman and Wunsch algorithm to find an alignment of two complete sequences that maximizes the number of matches and minimizes the number of gaps, and 2) the alkaline endoglucanase enzyme described in EP 1350843 A published by Kao on October 8, 2003 (

[0011] to

[0039] and Examples 1 to 4).

[0145] Suitable lipases include those produced by Pseudomonas and Chromobacter, as well as LIPOLASE®, LIPOLASE ULTRA®, LIPOPRIME® and LIPEX® from Novozymes. See also Japanese Patent Application No. 53-20487, published Feb. 24, 1978. This is available under the trade name Lipase P "Amano" from Aleario Pharmaceuticals, Nagoya, Japan. Other commercially available lipases include Amano-CES, available from Toyo Jozo Co., Tagata-gun, Japan, lipase ex Chromobacter viscosum, and Chromobacter viscosum lipase from USBiochemical Corp., USA and Diosynth Co., The Netherlands, as well as lipase ex Pseudomonas gladioli. Cutinases [EC 3.1.1.50] and esterases are also suitable.

[0146] Enzymes useful in liquid detergent formulations and their incorporation into such formulations are disclosed in U.S. Patent No. 4,261,868, issued April 14, 1981 to Hora et al. In one embodiment, the liquid compositions herein are substantially free (i.e., contain no measurable amount) of wild-type protease enzymes. A typical combination is an enzyme cocktail that may include, for example, a protease and a lipase in combination with an amylase. When present in the cleaning composition, the aforementioned additional enzymes may be present at a level of about 0.00001% to about 2%, about 0.0001% to about 1%, or even about 0.001% to about 0.5% enzyme protein by weight of the composition.

[0147] Enzyme Stabilizers Enzymes used in detergents can be stabilized in various ways. The enzymes used herein can be stabilized by the presence of a water-soluble source of calcium and / or magnesium ions in the final composition, such ions being provided to the enzyme. In the case of aqueous compositions containing proteases, reversible protease inhibitors such as boron compounds can be added to further improve stability.

[0148] Useful enzyme stabilizer systems are calcium and / or magnesium compounds, boron compounds and substituted boric acids, aromatic boric acid esters, peptides and peptide derivatives, polyols, low molecular weight carboxylates, relatively hydrophobic organic compounds [e.g., certain esters, dialkyl glycol ethers, alcohols or alcohol alkoxylates], alkyl ether carboxylates added to a calcium ion source, benzamidine hypochlorite, lower aliphatic alcohols and carboxylic acids, N,N-bis(carboxymethyl)serine salts; (meth)acrylic acid-(meth)acrylic acid ester copolymers and PEG; lignin compounds, polyamide oligomers, glycolic acid or its salts; polyhexamethylene biguanide or N,N-bis-3-amino-propyl-dodecylamine or salts; and mixtures thereof. The detergent may contain reversible protease inhibitors, such as peptide or protein type or modified subtilisin inhibitors of family VI and plasminostrepin, leupeptin, peptide trifluoromethyl ketones, or peptide aldehydes. The enzyme stabilizer is present at about 1 to about 30 millimoles, or about 2 to about 20 millimoles, or about 5 to about 15 millimoles, or about 8 to about 12 millimoles of stabilizer ion per liter.

[0149] Catalytic Metal Complexes Applicant's cleaning composition may contain catalytic metal complex.One type of metal-containing bleach catalyst is a catalyst system that includes transition metal cations with defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, auxiliary metal cations with little or no bleach catalytic activity, such as zinc or aluminum cations, and sequestrates with defined stability constants for catalyst and auxiliary metal cations, in particular ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and their water-soluble salts.Such catalysts are disclosed in US Patent No. 4,430,243.

[0150] Optionally, the compositions herein may be catalyzed by a manganese compound. Such compounds and usage levels are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent No. 5,576,282.

[0151] Cobalt bleach catalysts useful herein are known and are described, for example, in U.S. Patent Nos. 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, for example, as taught in U.S. Patent Nos. 5,597,936 and 5,595,967.

[0152] The compositions herein may also suitably include transition metal complexes of ligands such as bispidones (WO05 / 042532A1) and / or macropolycyclic rigid ligands (MRLs). As a practical matter, but without being limited thereto, the compositions and processes herein may be tailored to provide active MRL species in the aqueous cleaning medium on the order of at least some per billion, typically providing from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm of MRL in the cleaning solution.

[0153] Suitable transition metals in the transition metal bleach catalyst of the present invention include, for example, manganese, iron and chromium. Suitable MRLs include 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.

[0154] Suitable transition metal MRLs are readily prepared by known procedures, such as those taught in WO 00 / 32601 and US Pat. No. 6,225,464.

[0155] solvent Suitable solvents include water and other solvents such as lipophilic fluids. Examples of suitable lipophilic fluids include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerin derivatives such as glycerin ethers, perfluorinated amines, perfluorinated and hydrofluoroether solvents, low volatility non-fluorinated organic solvents, diol solvents, other environmentally friendly solvents, and mixtures thereof. In some embodiments, the solvent comprises water. The water may include water from any source, including deionized water, tap water, soft water, and combinations thereof. The solvent is typically present at about 0.1% to about 50% by weight, or about 0.5% to about 35% by weight, or about 1% to about 15% by weight.

[0156] In some embodiments, the composition comprises less than about 10%, less than about 5%, or less than about 1% of any additional surfactant. Because the selected foaming composition is capable of producing and maintaining foam without the aid of additional surfactant, the use of additional surfactant may be limited.

[0157] In some embodiments, the composition comprises less than about 10%, less than about 5%, or less than about 1% of any additional silicone material.

[0158] In some embodiments, the composition comprises less than about 10%, less than about 5%, or less than about 1% of any foam stabilizer.

[0159] In some embodiments, the composition may be free or substantially free of additional surfactants, additional silicone materials, or foam stabilizers.

[0160] Form of the composition The detergent composition may be in any suitable form including paste, liquid, solid (tablet, powder / granule, etc.), foam or gel, with powder and tablet being preferred. The composition may be in the form of a unit dose product, i.e. a form designed to be used as a single portion of the detergent composition in a cleaning operation. Of course, one or more such doses may be used in a cleaning operation.

[0161] Solid forms include, for example, tablets, rods, balls, or diamonds. The composition may be in granular form, loose or compressed shape, or may be formed by injection molding or casting or extrusion. The composition may be encapsulated in a water-soluble wrapping, for example, of PVOH or cellulosic material. The solid product may be provided as a divided product, if desired.

[0162] The composition may also be in the form of a paste, gel or liquid, including a unit dose product (portioned product). Examples include paste, gel or liquid products that are at least partially surrounded, preferably substantially surrounded, by a water-soluble coating, such as a polyvinyl alcohol package. The package can take the form of, for example, a capsule, a pouch, or a molded casing (such as an injection molded casing). Preferably, the composition is substantially surrounded by such a package, and most preferably, is completely surrounded by such a package. Any such package can include one or more product formats mentioned herein, and the package can include one or more compartments, for example, two, three or four compartments, as needed.

[0163] If the composition is a foam, liquid or gel, any suitable solvent can be used, but it is preferably an aqueous composition. According to a particularly preferred embodiment of the present disclosure, the composition is in the form of a tablet, in particular a tablet made from compressed granular material.

[0164] When the composition is in the form of a viscous liquid or gel, it preferably has a viscosity of at least 50 mPas when measured at 25° C. using a Brookfield RV viscometer with spindle 1 at 30 rpm.

[0165] The composition of the present disclosure is typically used by placing it in a detergent dispenser, such as in a dishwasher drawer or in a free-standing dispensing device in an automatic dishwasher. However, if the composition is in the form of a foam, liquid or gel, it can be applied to the dishwasher by any additional suitable means, such as by a trigger spray, squeeze bottle or aerosol.

[0166] Process for making cleaning compositions The composition of the present disclosure can be prepared by any suitable method according to its format.Suitable manufacturing methods for detergent compositions are well known in the art, and non-limiting examples thereof are described in U.S. Patent Nos. 5,879,584, 5,691,297, 5,574,005, 5,569,645, 5,565,422, 5,516,448, 5,489,392 and 5,486,303.Various techniques for forming detergent compositions in solid form are also well known in the art, for example, detergent tablets can be prepared by compressing granular / specific materials and can be used herein.

[0167] In one aspect, the liquid detergent composition disclosed herein can be prepared by combining the components in any convenient order and mixing, e.g., stirring, the resulting combination of components to form a phase-stable liquid detergent composition. In one aspect, a liquid matrix is ​​formed containing at least a majority or substantially all of the liquid components, and the liquid components are thoroughly mixed by applying shear agitation to the liquid combination. For example, rapid stirring with a mechanical stirrer can be effectively used. Substantially all of the anionic surfactant and solid components can be added while maintaining shear agitation. Stirring of the mixture can be continued and, if necessary, increased at this point to form a solution or uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solid form material is added to the stirred mixture, any included enzyme material particles, e.g., enzyme granules, are incorporated. As a variation of the above-mentioned composition preparation procedure, one or more solid components can be added to the stirred mixture as a solution or slurry of particles premixed with a minor portion of one or more liquid components. After all of the composition components have been added, stirring of the mixture is continued for a period of time sufficient to form a composition having the requisite viscosity and phase stability characteristics, which often involves stirring for about 30 to 60 minutes.

[0168] This is more particularly described in the following examples, which are for illustrative purposes only, since numerous modifications and variations within the scope of this disclosure will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples were obtained or are available from the chemical suppliers listed below. All references cited herein are incorporated herein by reference in their entirety. EXAMPLES

[0169] The embodiments of the present invention are further defined in the following non-limiting examples. Although these examples show certain embodiments of the present disclosure, it should be understood that they are given merely as illustrations. From the above discussion and these examples, those skilled in the art can ascertain the essential features of the present disclosure, and can make various changes and modifications to the embodiments of the present disclosure to adapt it to various usages and conditions without departing from the spirit and scope thereof. Thus, various modifications of the embodiments of the present disclosure will be apparent to those skilled in the art from the foregoing description, in addition to those shown and described herein. Such modifications are also intended to be included within the scope of the appended claims. The materials used in the following examples are provided herein. Silicone 350cst: Polydimethylsiloxane with a viscosity of 350cSt at 25℃ Silicone 150cst: Polydimethylsiloxane with a viscosity of 150cSt at 25°C Silicone 0.65cst: Hexamethyldisiloxane Silicone 1cst: Octamethyltrisiloxane Tween® 20: Polysorbate 20 Tween® 80: Polysorbate 80 SLES: Sodium lauryl ether sulfate Barlox 12: Cocoamine oxide surfactant Triton X-100: Polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether Tomamine AO-728: Amine oxide Tomamine DA-17: Isotridecyclopropyl-1,3-diaminopropane Pluronic 68:EO PO block copolymer Marlowet 4539LF: Oxirane, methyl-, polymer with oxirane, carboxymethyl nonyl ether, branched Tergitol 15-S-7: C12 to C14 secondary ethoxylated alcohol Alfoterra 123-8S: Alcohol propoxy sulfate Cola Lipid DCCA: Coco PG-Dimonium Chloridophosphate Sodium

[0170] Example 1 Alkyl-modified siloxanes and siloxanes alone are not known to be able to form foam in organic solvents such as ethanol and in polar solvent solutions such as water. Without being bound to a particular theory, it is believed that siloxanes do not have surface activity in ethanol, water, or ethanol / water solutions and cannot reduce the surface tension of these solutions, as shown in Figure 1. Due to this lack of surface activity and lack of reduction in surface tension, siloxanes should not be able to function as foaming agents by themselves.

[0171] To screen for foaming potential in ethanol / water solutions, manual foaming tests were performed on alkyl-modified siloxanes or siloxanes alone. To test, 20 mL of each of the compositions shown in Table 1 was placed in a 1" x 4.5" glass cylindrical bottle and shaken for about 10 seconds. After shaking, all compositions lost all foam within about 10 seconds. This indicates that a wide variety of alkyl-modified polysiloxanes alone are unable to produce a stable foam.

[0172] This lack of foaming is probably due to a lack of surface activity. Without being bound to a particular theory, the lack of surface activity may be due to the low surface tension of ethanol. Few surfactants, such as silicone-based or fluoride-based, can reduce the surface tension of water to the same level as that of ethanol, making it energetically beneficial to create new surface area through foaming action. However, without surface activity, siloxanes cannot function as silicone surfactants to form foam, so they behave differently from silicone surfactants, even though both are silicone-based and the surface tension of siloxanes is lower than ethanol.

[0173] The lack of surfactant ability of siloxanes may be due to their insolubility in water and / or ethanol.Some, such as C8 methicone, are soluble in ethanol, but ethanol / water solution reduces their solubility, so siloxanes may not dissolve, and therefore may not have any surfactant.Therefore, unlike other silicone-based compounds, siloxanes may not function as surfactants and produce stable foam in water / ethanol solution when used alone. [Table 1-1] [Table 1-2] [Table 1-3]

[0174] Example 2 It is not known that modified castor oil can generate stable foam in a solution of an organic solvent such as pure ethanol or in a solution of an organic solvent mixed with a polar solvent such as an ethanol / water solution. Without being bound to a particular theory, as shown in FIG. 2, PEG-modified castor oil can reduce the surface tension of pure water, but may not be surface active in alcohols such as pure ethanol or water / ethanol solutions. Furthermore, not all castor oils are soluble in alcohol. Modified castor oil alone cannot form stable foam in an ethanol / water solution due to lack of surface activity and / or insolubility in organic solvents or solutions containing organic solvents.

[0175] To screen the possibility of forming modified castor oil in ethanol / water solution when used alone, manual foam test was performed on various modified castor oils. To screen various modified castor oils, 20 mL of each of the compositions listed in Table 2 was placed in a 1" x 4.5" glass cylinder bottle and then shaken for about 10 seconds. After shaking, all compositions lost all foaming within about 20 seconds. This indicates that PEG modified castor oil alone could not generate stable foam in ethanol / water solution.

[0176] The lack of foaming seen with PEG-modified castor oil is likely due to the lack of surface activity of ethanol, which is energetically unfavorable for increasing the surface area of ​​the solution. However, even if castor oil is surface active, it cannot reduce the surface tension of a pure ethanol solution or a 62% ethanol / water solution. In addition, this lack of foaming may also be due to a lack of solubility for some modifications. For example, a 10 mole EO modification was insoluble in a 62% ethanol / water solution. However, when increased to 20 to 60 mole EO modifications, the modified castor oil is soluble enough to enter the solution. As shown in Table 2, even when soluble enough to enter the solution, the PEG-modified castor oil still could not form a stable foam when used alone.

[0177] Thus, neither the pendant alkylsiloxanes nor the PEG-modified castor oil alone are capable of producing stable foams in ethanol / water solutions and may not be able to replace known surfactants in these solutions. [Table 2-1] [Table 2-2]

[0178] Example 3 Since neither the alkyl-modified siloxane nor the PEG-modified castor oil alone were able to sufficiently reduce the surface tension of the water / alcohol solution, collectively it was not expected that they would act synergistically to reduce the surface tension sufficiently to form a foam.

[0179] To screen for foaming of PEG-modified castor oil with alkyl-modified siloxane or siloxane / polydimethylsiloxane, a manual foaming test was conducted. 20 mL of each of the compositions shown in Table 3 was placed in a 1" x 4.5" glass cylinder and then shaken for about 10 seconds.

[0180] After shaking, the composition with the combination of PEG-modified castor oil and caprylyl methicone was able to produce a stable foam. When a small amount of C26-C28 alkyl dimethicone was dissolved with PEG-modified castor oil in 62% ethanol solution, it produced a stable foam. Furthermore, cyclotetrasiloxane (D4) combined with EG-modified castor oil produced a stable foam. However, this combination required a higher concentration compared to caprylyl methicone. In addition, a fresh solution of silicone oil (150cst and 350cst) with PEG-modified castor oil produced low foam that lasted for 10 minutes. The silicone droplet phase separated from the solution and no foam came out of the solution overnight. These results surprisingly show that PEG-40 hydrogenated castor oil can function with a wide range of hydrophobic siloxanes over a range of concentrations as a foaming composition when both were used alone, which failed. Additionally, as shown in FIG. 3, the foaming composition can reduce the surface tension of water, indicating that PEG-40 hydrogenated castor oil in combination with caprylyl methicone can function as a surfactant in water-based solutions.

[0181] Thus, this combination produced stable foam, unlike PEG-modified castor oil or alkyl-modified siloxane or siloxane / polymethylsiloxane alone, which failed to produce foam. Without being bound to a particular theory, the pendant alkyl chain of siloxane may interact with the hydrophobic region of castor oil tail. Furthermore, the PEG-modified region of castor oil increases the solubility of the composition in the aqueous part of the solution. This may also allow more adsorption at the liquid-liquid interface of the water / alcohol solution. This interaction may increase the surface activity of the composition in the water / alcohol solution, allowing the composition to lower the surface tension of the solution enough to make it energetically favorable to produce foam and allow the composition to act as a surfactant.

[0182] Furthermore, the hydrophobic nature of both castor oil and siloxanes allows the foaming composition to act as a surfactant in other water / organic solvent based solutions or in other hydrophobic solutions such as hydrocarbon condensates, etc. Additionally, the ability of PEG-40 hydrogenated castor oil to increase the solubility of hydrophobic siloxanes may allow for the solubilization of other hydrophobic compounds such as unmodified triglycerides and trans fats in water-based systems. [Table 3-1] [Table 3-2] [Table 3-3] [Table 3-4]

[0183] Example 4 Since PEG-40 hydrogenated castor oil was sufficient for various siloxanes to foam the alcohol / water solution, various other PEG substitutions were tested with caprylyl methicone using a manual foaming test. 20 mL of each of the compositions shown in Table 4 was placed in a 1" x 4.5" glass cylinder and then shaken for approximately 10 seconds.

[0184] After shaking, the composition with the combination of PEG-modified castor oil and caprylyl methicone can generate stable foam in 62 wt% ethanol solution. 20, 50 and 60 EO moles of PEG-modified castor oil generate stable foam close to the initial height of 40 EO moles of castor oil. 20 moles of oil generate lower but stable foam, and 10 moles of oil generate unstable foam. Therefore, the longer hydrophilic region does not interfere with the hydrophobic interaction between castor oil and siloxane.

[0185] However, insufficient length of hydrophilic region may not allow sufficient solubilization of the siloxane, as shown by the 10 EO molar modification, and higher concentrations of PEG-modified castor oil with alkyl-modified polysiloxanes do not increase initial foam height, so additional hydrotropes or surfactants do not hinder foam height.

[0186] The lower but stable height of the 20 mole modification compared to the longer modifications of the cast oil also indicates that the foam height can be controlled, which is important for some systems requiring low sudsing or in rinse aids.

[0187] When PEG-40 hydrogenated castor oil was compared to PEG-40 castor oil, the PEG-40 castor oil produced a less stable foam with a lower initial height. Without being bound to any particular theory, this is likely due to the backbone of PEG-40 being stiffer with unsaturated double bonds. This may prevent the tails of PEG-40 castor oil from interacting sufficiently with the pendant alkyl groups of caprylyl methicone to fully solubilize it in the water present in the solution.

[0188] In addition, the addition of salt does not appear to affect foam height. The addition of potassium chloride or 5 grain water has been shown to have no effect on foam height or foam stability. Thus, the foaming composition may be resistant to hard water and additional agents.

[0189] Thus, depending on the PEG modified castor oil when used in combination with a siloxane such as caprylyl methicone, the foam height and stability can be adjusted to the desired level, which may allow the composition to be further tailored for detergents where high foaming is desired, or rinse aids where low foaming is desired. [Table 4-1] [Table 4-2] [Table 4-3]

[0190] Example 5 To further characterize the foaming properties of the synergistic compositions, the concentrations of PEG-modified castor oil and caprylyl methicone were varied over their lower ranges. In addition, the amount of ethanol in some compositions was increased to test foaming at higher concentrations of ethanol. 20 mL of each of the compositions shown in Tables 5-7 was placed in a 1" x 4.5" glass cylinder bottle and then shaken for about 10 seconds.

[0191] After shaking, it is possible to generate foam in up to 74 wt% ethanol solution with sufficient PEG modified castor oil and caprylyl methicone, as shown in Table 5. The combination of 1.3% PEG-40 hydrogenated castor oil and 0.4% caprylyl methicone can form a stable foam in 80 wt% ethanol solution for more than 12 minutes (see Table 5). Since ethanol has a very low surface tension, this indicates that the foaming composition works over a range of solutions, as shown above that the composition can also foam water, which has a high surface tension given by its polar nature. However, PEG-40 hydrogenated castor oil is too hydrophilic to act completely as a foam generator with caprylyl methicone in almost pure ethanol, but the composition can still function as a surfactant replacement composition in mixed solutions.

[0192] In 62 wt% ethanol, the lowest concentration of PEG-modified castor oil capable of producing a stable foam was 0.2%-0.3% in combination with 0.7% caprylyl methicone (see Table 6). For caprylyl methicone, the lowest concentration to produce a stable foam in 62 wt% ethanol solution was 0.05%-0.07% in combination with 3% PEG-40 hydrogenated castor oil (see Table 7). Thus, small amounts of both compounds are sufficient to cause foaming in low surface tension solutions. [Table 5] [Table 6] [Table 7]

[0193] Example 6 Excess PEG-40 hydrogenated castor oil did not appear to affect foaming, so other hydrotropes and surfactants could be added to the composition without interfering with foaming. To test foaming with additional compounds in the composition, additional surfactants were added to a composition containing 0.2% caprylyl methicone, 3%-4% PEG-40 hydrogenated castor oil, and 62% ethanol by weight. 20 mL of each of the compositions found in Tables 8 and 9 was placed in a 1" x 4.5" glass cylinder bottle and then shaken for approximately 10 seconds.

[0194] Depending on the surfactant, the addition of additional surfactant either had no effect on the initial foam height or, at high enough concentrations, the additional surfactant reduced the initial foam height and stability. For example, Bartox 12 at 2% had no effect on the initial foam height and stability, but at 6% the foam disappeared within 20 seconds (see Table 8). Similarly, as the concentration of Tomamine AO-728 was increased from 1% to 5%, the higher concentration resulted in a lack of foaming within 20 seconds (see Table 9). However, the stretch C 10 For some surfactants, such as PO8EO6, increasing the concentration did not affect foam height or stability (see Table 8).

[0195] Thus, additional surfactants, even in large amounts, can be added to the composition to enhance cleaning power without losing foam stability.Furthermore, surfactants can be added to control foam height for specific applications, such as use in rinse aids. [Table 8-1] [Table 8-2] [Table 9-1] [Table 9-2]

[0196] Example 7 In addition, because the surfactant did not seem to affect the foaming of the composition in ethanol / water solution, it may be possible to use it in place of PEG-modified castor oil to produce other foaming compositions. To determine whether surfactants other than PEG-modified castor oil would produce foam in ethanol solution, various other surfactants were added to the 0.2% caprylyl methicone composition in 62% by weight ethanol solution. 20 mL of each of the compositions found in Tables 10 and 11 was placed in a 1" x 4.5" glass cylinder bottle and then shaken for about 10 seconds. The results show that none of the other surfactants can produce foam in the 62% by weight ethanol solution with caprylyl methicone and can replace modified castor oil.

[0197] In Table 12, the mixer was pumped 10 times into an 80 ml beaker via an in-line pump. In the PEG-castor oil foaming formula, C8 trisiloxane produced stable foam. With the optional low molecular weight silicone oil, the bubbles were smaller and denser. PolyOX produced denser foam, but increased pump resistance due to higher viscosity. PEI made the foam more stable without increasing the viscosity of the mixer. VX10035 formed a microemulsion with better foam stability compared to HP20.

[0198] This may be due to the PEG-modified castor oil structure. Without being bound to a particular theory, it is possible that the PEG-modified castor oil structure can form a cage around the siloxane, as shown in Figure 4. The hydrophobic ends of the three arms may provide sufficient interaction with the pendant alkyl group of the alkyl siloxane to enhance solubility in ethanol / water solutions. Other surfactants may not be able to interact sufficiently with the pendant alkyl group of the alkyl siloxane to provide sufficient solubility, as many only have a single hydrophobic region. This also indicates that other modified triglyceride hydrotropes or surfactants may provide sufficient interaction with the pendant alkyl siloxane to generate a foaming composition.

[0199] Finally, Figure 5 shows the mixtures under fluorescent light. On the left is Example 1 with 46 ppm dye without PEG-40, and on the right is Example 1 with 46 ppm dye. As can be seen, the bottle on the right shows strong and uniform fluorescence, indicating that the silicone materials (C8 trisiloxane and silicone fluid) were completely dissolved in the ethanol / water solution to form a microemulsion. [Table 10-1] [Table 10-2] [Table 11-1] [Table 11-2] [Table 12-1] [Table 12-2]

[0200] See Figure 5, on the left is Example 1 46 ppm dye without PEG-40 and on the right is Example 1 with 46 ppm dye. The vial on the right shows strong uniform fluorescence indicating that the silicone materials (C8 trisiloxane and silicone fluid) were completely dissolved in the ethanol / water solution to form a microemulsion.

[0201] The invention being thus described, it will be apparent that the same may be varied in many ways. Such variations should not be regarded as departures from the spirit and scope of the disclosure, and all such modifications are intended to be included within the scope of the following claims. The above specification provides an explanation of the manufacture and use of the disclosed compositions and methods. Since many embodiments may be made without departing from the spirit and scope of the disclosure, the disclosure resides in the claims.

Claims

1. 1. A foaming composition for use in water, alcohol / water, and hydrocarbon condensate solutions, comprising: a) a pendant alkyl siloxane; b) PEG-modified castor oil.

2. The pendant alkyl siloxane conforms to the general formula: 【Chemistry 1】 During the ceremony, n is 0 to 30; m is 1 to 50; R and R1 are methyl; 2. The foamable composition of claim 1, wherein R2 is a linear or branched, unsubstituted or substituted, saturated or unsaturated, aliphatic or aromatic C1-C30 hydrocarbon and is not a hydrophilic group.

3. 3. The foaming composition of claim 2, wherein R2 of said pendant alkyl siloxane is a C2 to C28 hydrocarbon, n is 0, and m is 1.

4. 3. The foaming composition of claim 2, wherein R2 of said pendant alkyl siloxane is a C2 to C12 hydrocarbon, n is 0, and m is 1.

5. 3. The foaming composition of claim 2, wherein R2 of said pendant alkyl siloxane is a C8 hydrocarbon, n is 0, and m is 1.

6. 3. The foaming composition of claim 2, wherein R2 of said pendant alkyl siloxane is a C2-C28 hydrocarbon, n is 1-30, and m is 1-50.

7. The foamable composition according to any one of claims 1 to 6, wherein the PEG-modified castor oil is hydrogenated.

8. 8. The foaming composition of any one of claims 1 to 7, wherein the PEG modified castor oil has about 20 to about 100 moles of EO.

9. The foamable composition of any one of claims 1 to 8, wherein the composition is sufficiently free of silicone-based surfactants.

10. 10. The foamable composition of any one of claims 1 to 9, further comprising PolyOX, at a preferred concentration of 0.05% to 0.5%.

11. A foamable composition according to any one of claims 1 to 10, further comprising a positively charged polyethyleneimine polymer at a preferred concentration of 0.1% to 5%.

12. 12. The foaming composition of claim 11, wherein said polyethyleneimine polymer is alkoxylated.

13. 13. The foaming composition of claim 12, wherein said polyethyleneimine polymer is ethoxylated.

14. 14. The foamable composition of any one of claims 1 to 13, further comprising a dimethylsiloxane having from 2 to 5 Si-O repeat units.

15. The foamable composition of any one of claims 1 to 14, wherein the dimethyl siloxane is linear.

16. The foamable composition of any one of claims 1 to 15, wherein the dimethyl siloxane is cyclic.

17. 1. A method for hand and hard surface disinfection and surface cleaning, including rinsing and removal of proteins and / or non-trans fats by forming an emulsion or microemulsion, the method comprising: On the surface having the protein or non-trans fat, a) a pendant alkyl siloxane; b) PEG-modified castor oil; applying a cleaning composition / rinse aid comprising:

18. 18. The method of claim 17, further comprising rinsing or wiping the surface so that the surfactant and proteins or trans fats are removed.

19. The pendant alkyl siloxane conforms to the general formula: 【Chemistry 2】 During the ceremony, n is 0 to 30; m is 1 to 50; R and R1 are methyl; The method according to claim 17 or 18, wherein R2 is a linear or branched, unsubstituted or substituted, saturated or unsaturated, aliphatic or aromatic C1 to C30 hydrocarbon, and is not a hydrophilic group.

20. 20. The pendant alkyl siloxane of claim 19, wherein the pendant alkyl siloxane is caprylyl (C8) methicone.

21. 21. The method of any one of claims 17 to 20, wherein R2 is a C2 to C28 hydrocarbon, n is 0, and m is 1.

22. 22. The method of any one of claims 17 to 21, wherein R2 is a C2 to C12 hydrocarbon, n is 0, and m is 1.

23. 23. The method of any one of claims 17 to 22, wherein R2 is a C8 hydrocarbon, n is 0, and m is 1.

24. 24. The method of any one of claims 17 to 23, wherein R2 is a C2 to C28 hydrocarbon, n is 1 to 30, and m is 1 to 50.

25. The method according to any one of claims 17 to 24, wherein the PEG-modified castor oil is hydrogenated.

26. 26. The method of any one of claims 17 to 25, wherein the PEG modified castor oil has about 20 to about 100 moles of EO.

27. 27. The method of any one of claims 17 to 26, further comprising PolyOX, at a preferred concentration of 0.05% to 0.5%.

28. 28. The method of any one of claims 17 to 27, further comprising a positively charged polyethyleneimine polymer, at a preferred concentration of 0.1% to 5%.

29. 30. The method of claim 28, wherein the polyethyleneimine polymer is alkoxylated.

30. 30. The method of claim 28, wherein the polyethyleneimine polymer is ethoxylated.

31. The method of any one of claims 17 to 30, wherein the composition further comprises a dimethylsiloxane having from 2 to 5 Si-O repeat units.

32. The method of any one of claims 17 to 31, wherein the dimethylsiloxane is linear.

33. The method of any one of claims 17 to 32, wherein the dimethylsiloxane is cyclic.

34. A hand sanitizer, hard surface sanitizer or surface cleaning composition having a foaming component, the foaming component comprising: a) a pendant alkyl siloxane; b) a PEG-modified castor oil; and

35. The pendant alkyl siloxane conforms to the general formula: 【Chemistry 3】 During the ceremony, n is 0 to 30; m is 1 to 50; R and R1 are methyl; R2 is linear or branched, unsubstituted or substituted, saturated or unsaturated; 35. The hand sanitizer, hard surface sanitizer or surface cleaning composition of claim 34, wherein the group is an aliphatic or aromatic C1-C30 hydrocarbon and is not a hydrophilic group.

36. 36. The hand sanitizer, hard surface sanitizer or surface cleaning composition of claim 35, wherein R2 is a C2 to C28 hydrocarbon, n is 0 and m is 1.

37. 36. The hand sanitizer, hard surface sanitizer or surface cleaning composition of claim 35, wherein R2 is a C2 to C12 hydrocarbon, n is 0 and m is 1.

38. 36. The hand sanitizer, hard surface sanitizer or surface cleaning composition of claim 35, wherein R2 is a C8 hydrocarbon, n is 0 and m is 1.

39. 36. The hand sanitizer, hard surface sanitizer or surface cleaning composition of claim 35, wherein the pendant alkyl siloxane is caprylyl (C8) methicone.

40. 36. The hand sanitizer, hard surface sanitizer or surface cleaning composition of claim 35, wherein R2 of the pendant alkyl siloxane is a C2-C28 hydrocarbon, n is 1-30, and m is 1-50.

41. The hand sanitizer, hard surface sanitizer or surface cleaning composition of any one of claims 28 to 34, wherein the PEG modified castor oil is hydrogenated.

42. 42. The hand sanitizer, hard surface sanitizer or surface cleaning composition of any one of claims 34 to 41, wherein the PEG modified castor oil has from about 20 to about 100 moles of EO.

43. 43. The hand sanitizer, hard surface sanitizer or surface cleaning composition of any one of claims 34 to 42, wherein the composition is substantially free of silicone-based surfactants.

44. 44. The hand sanitizer, hard surface sanitizer or surface cleaning composition of any one of claims 34 to 43, further comprising PolyOX at a preferred concentration of 0.05% to 0.5%.

45. 45. The hand sanitizer, hard surface sanitizer or surface cleanser composition of any one of claims 34 to 44, further comprising a positively charged polyethyleneimine polymer at a preferred concentration of 0.1% to 5%.

46. 46. ​​The hand sanitizer, hard surface sanitizer or surface cleaning composition of any one of claims 34 to 45, wherein the polyethyleneimine polymer is alkoxylated.

47. 47. The hand sanitizer, hard surface sanitizer or surface cleaning composition of any one of claims 34 to 46, wherein the polyethyleneimine polymer is ethoxylated.

48. 48. The hand sanitizer, hard surface sanitizer or surface cleaning composition of any one of claims 34 to 47 further comprising surfactants, builders, chelating agents, dye transfer inhibitors, viscosity modifiers, dispersants, additional enzymes and enzyme stabilizers, catalytic materials, bleaching agents, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersants, threshold inhibitors for hard water settling pigments, clay removers / anti-redeposition agents, brighteners, suds suppressors, dyes, fabric hueing agents, fragrances, structure elasticizing agents, fabric softeners, carriers, additional hydrotropes, processing aids, solvents, pigment antimicrobial agents, pH buffers, processing aids, active optical brightening components, additional surfactants, and mixtures thereof.

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