WO2025053993A1 - Additives for improving the clarity of hard water - Google Patents
Additives for improving the clarity of hard water Download PDFInfo
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- WO2025053993A1 WO2025053993A1 PCT/US2024/042990 US2024042990W WO2025053993A1 WO 2025053993 A1 WO2025053993 A1 WO 2025053993A1 US 2024042990 W US2024042990 W US 2024042990W WO 2025053993 A1 WO2025053993 A1 WO 2025053993A1
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- Prior art keywords
- oil
- ppm
- liquid
- clarifying
- sophorolipids
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
Definitions
- Hard water is water that contains elevated levels of certain common impurities such as calcium (Ca) and magnesium (Mg). Hard water is known to reduce cleaning efficacy both by forming films on surfaces and reacting with detergents and other cleaning components, making them less functional in the cleaning process.
- Ca calcium
- Mg magnesium
- Ca calcium
- Mg magnesium
- Ca calcium
- Mg magnesium
- Ca calcium
- Mg magnesium
- Ca calcium
- Mg magnesium
- anionic surfactants e.g., fatty acid carboxylates (soap), sodium lauryl sulfonate (SLS) and Triton GR-5M (an anionic sulfosuccinate
- chelating agents or sequestrants into detersive compositions in amounts sufficient to handle the hardness.
- all calcium must be removed from the solution for there to be enough free surfactant available for cleaning; otherwise, more surfactant must be utilized.
- chelators used for these purposes are sometimes referred to as “builders,” as they help build upon the performance of the surfactant.
- chelating agents are associated with various risks.
- the common chelator ethylenediaminetetraacetic acid (EDTA) is not readily biodegradable, particularly once complexed with metal ions. This may lead to environmental accumulation, which could cause toxicity to plants and animals.
- Phosphonates another category of chelating agents, are associated with cancer, and accumulate in water sources, which can result in eutrophication. Safer chelating alternatives are known, such as citric acid; however, this readily biodegradable ingredient is not as effective as EDTA and is not compatible with certain cleaning products due to its characterization as a weak acid.
- Another method for addressing water hardness issues is to soften water via ion exchange, e.g., by exchanging the calcium and magnesium ions in the water with sodium associated with a resin bed in a water softening unit.
- the calcium and magnesium adhere to a resin in the softener.
- the sodium displaces the calcium and magnesium, which is flushed out in a briny solution along with the chloride from the added sodium chloride.
- water softeners regenerate they produce a waste stream that contains significant amounts of chloride, creating a burden on the system, e.g., sewer system, in which they are disposed of — including a multitude of downstream water re-use applications such as potable water usages and agriculture.
- traditional water softeners add to the salt content in discharge surface waters, which can be disruptive to the ecosystems where they are discharged.
- the current invention addresses needs for improved consumer products that rely upon hardwater, which are safer for human exposure and for the environment but do not sacrifice functional attributes across a wide range of applications.
- This invention provides safe ingredients having surprising and unexpected clarifying attributes comparable to, or better than, existing formulation additives and methods of reducing the negative effects of dissolved minerals in water.
- the subject invention relates generally to the use of biosurfactants as additives in a variety of industries, products, and activities, including, for example, household, industrial and institutional (HI&I) cleaning, personal care, cosmetics, and water treatment. More specifically, the subject invention provides environmentally-friendly compositions and methods for improving the formulation of products through the remediation of haze caused by the precipitation of metals, minerals, or elements, such as, for example, calcium, magnesium, iron, copper, nickel, gold, silver, molybdenum, aluminum, lead, tungsten, chromium, cadmium, zinc and arsenic, from liquids.
- metals, minerals, or elements such as, for example, calcium, magnesium, iron, copper, nickel, gold, silver, molybdenum, aluminum, lead, tungsten, chromium, cadmium, zinc and arsenic, from liquids.
- the subject invention provides advantageous clarifying additives for improving the clarity of formulations that are diluted with a liquid, as well as their use in enhancing the performance of such formulations by remediating and/or preventing the precipitation of contaminating and/or otherwise undesirable components in the liquid, such as, for example, metals, minerals, and elements.
- the clarifying additive according to the subject invention can help improve the appearance and functioning of solutions by reducing haziness and preventing the precipitation of haze-causing salts, e.g., calcium carbonate, calcium bicarbonate, calcium chloride, calcium sulfate, magnesium carbonate, magnesium bicarbonate, magnesium chloride and magnesium sulfate.
- haze-causing salts e.g., calcium carbonate, calcium bicarbonate, calcium chloride, calcium sulfate, magnesium carbonate, magnesium bicarbonate, magnesium chloride and magnesium sulfate.
- This can be particularly useful in formulations that contain surfactants known to react with the ions in hardwater, e.g., SLS or sulfosuccinates.
- the clarifying additive comprises components that are derived from microorganisms.
- the clarifying additives comprise a microbial biosurfactant or a mixture of multiples biosurfactants.
- the biosurfactant can be utilized in crude form, which can comprise, in addition to the biosurfactant, fermentation broth in which a biosurfactant-producing microorganism was cultivated, residual microbial cell material or live or inactive microbial cells, residual nutrients, and/or other microbial growth by-products.
- the biosurfactant is utilized after being extracted and/or isolated from a fermentation broth and, optionally, purified. In some embodiments, the biosurfactant is subjected to further chemical derivatization.
- the biosurfactant can be, e.g., a glycolipid (e.g., sophorolipid, rhamnolipids, cellobiose lipid, mannosylerythritol lipid and trehalose lipid), lipopeptide (e.g., surfactin, iturin, fengycin, arthrofactin, and lichenysin), flavolipid, phospholipid (e.g., cardiolipin), fatty acid ester compound, fatty acid ether compound, and/or high molecular weight polymer, such as lipoproteins, lipopolysaccharide-protein complexes, and polysaccharide-protein-fatty acid complexes.
- a glycolipid e.g., sophorolipid, rhamnolipids, cellobiose lipid, mannosylerythritol lipid and trehalose lipid
- lipopeptide e.g., surfactin, iturin, f
- the biosurfactant is a sophorolipid (SLP), including linear SLP, lactonic SLP, acetylated SLP, de-acetylated SLP, salt-form SLP, esterified SLP derivatives, amino acid-SLP conjugates, and other SLP derivatives or isomers that exist in nature and/or are produced synthetically.
- SLP sophorolipid
- the SLP comprises a majority, i.e., greater than 50%, linear SLP with respect to the total SLP in the composition.
- the clarifying additive can comprise additional components, including carriers, chelators, builders, surfactants and water, including water characterized as hardwater.
- the subject invention further provides methods for remediating and/or preventing the precipitation of salts in hardwater, as well as formulations diluted with a liquid, such as hardwater.
- the method comprises contacting a clarifying additive according to the subject invention with the liquid for a period of time to yield a mixture comprising a treated liquid. If necessary, multiple applications of the clarifying additive may be applied.
- the liquid is water, more preferably, water that is characterized as hardwater.
- the treated liquid can be added to a formulation in need of dilution in an amount suitable for achieving a desired level of dilution.
- the methods comprise pre-mixing the clarifying additive with one or more other components of the formulation, for example, a surfactant, prior to diluting the formulation with the liquid.
- the clarifying additive, liquid, and other formulation components can all be mixed together simultaneously.
- formulation components can include, but are not limited to, synthetic chelating agents, naturally-derived chelating agents, chemical surfactants, essential oils, botanical extracts, crosslinking agents, fatty acids, alcohols, pH adjusting agents, reducing agents, builders, syndetics, buffers, enzymes, dyes, colorants, fragrances, preservatives, emulsifiers, foaming agents, polymers, thickeners and/or viscosity modifiers.
- the components are dependent upon the particular formulation and use thereof.
- the biosurfactants according to the subject invention function according to a surprising mechanism of action, that is, a mechanism other than chelation.
- the subject invention can be used for remediating and/or preventing the occurrence of haze in solutions, even when standard chelators, such as EDTA, do not.
- compositions and methods of the subject invention can reduce the amount of precipitation in a formulation by at least 25%, preferably by at least 50%, compared with formulations that do not contain the clarifying additive.
- the subject invention further provides improved formulations, such as, for example, improved surface cleaners, laundry detergents, dishwashing liquids, auto-dish detergents, and personal care products, comprising a clarifying additive according to the subject invention.
- improved formulations such as, for example, improved surface cleaners, laundry detergents, dishwashing liquids, auto-dish detergents, and personal care products.
- the compositions can be formulated for reduced skin and eye sensitivity for users.
- compositions and methods according to the subject invention can be effective at minimizing buildup of contaminants during, for example, household cleaning and industrial processes, and avoids and/or reduces the use of toxic chelating compounds. Furthermore, the methods of the subject invention do not require complicated equipment or high energy consumption, and production of the composition can be performed on site, for example, at an industrial site.
- the subject invention has utility in a variety of industries, products, and activities, including, for example, metalworking, oil and gas production, polymerization, pulp and paper production, household, industrial and institutional (HI&I) cleaning and descaling, textiles, mining, pharmaceuticals, agriculture, food and beverage production, cosmetics, and water treatment.
- Figure 1 shows surface tension of sodium lauryl sulfate (SDS/SLS) before and after lOum filtration when mixed with increasing concentrations of hardwater.
- Figure 2 shows a comparison of haze (precipitated salts) in a formulation comprising 1000 ppm SLS in 250 ppm hardwater (HW) (left) and a formulation comprising 1000 ppm SLS, 1000 ppm sophorolipids (SLP) and 250 ppm HW (right).
- Figure 3 shows time (s) of scale calcite precipitation for two treatments, treatment A (80% lactonic SLP / 20% linear SLP) and treatment B (100% linear SLP), at various concentrations (ppm) compared to a control (blank).
- the subject invention provides advantageous clarifying additives for improving the clarity of formulations that are diluted with a liquid, as well as their use in enhancing the performance of such formulations by remediating and/or preventing the precipitation of contaminating and/or otherwise undesirable components in the liquid, such as, for example, metals, minerals, and elements.
- the clarifying additive according to the subject invention can help improve the appearance and functioning of solutions by reducing haziness and preventing the precipitation of haze-causing salts, such as, e.g., carbonates, chlorides and sulfates, from hardwater.
- haze-causing salts such as, e.g., carbonates, chlorides and sulfates
- the invention provides numerous unexpected downstream benefits, including for example, improving water quality and cleaning results, reducing consumption of detergents, other polymers and/or cleaning components in various cleaning applications, and preventing scale buildup, spotting and/or filming on treated surfaces.
- applying refers to contacting it with a target or site such that the composition or product can have an effect on that target or site.
- biofilm is a complex aggregate of microorganisms, such as bacteria, yeast, or fungi, wherein the cells adhere to each other and/or to a surface using an extracellular matrix.
- the cells in biofilms are physiologically distinct from planktonic cells of the same organism, which are single cells that can float or swim in liquid medium.
- an “isolated” or “purified” nucleic acid molecule, polynucleotide, polypeptide, protein or organic compound such as a small molecule (e.g., those described below), is substantially free of other compounds, such as cellular material, with which it is associated in nature.
- a purified or isolated polynucleotide ribonucleic acid (RNA) or deoxyribonucleic acid (DNA)
- RNA ribonucleic acid
- DNA deoxyribonucleic acid
- a purified or isolated polypeptide is free of the amino acids or sequences that flank it in its naturally-occurring state.
- An isolated microbial strain means that the strain is removed from the environment in which it exists in nature. Thus, the isolated strain may exist as, for example, a biologically pure culture, or as spores (or other forms of the strain) in association with a carrier.
- purified compounds are at least 60% by weight the compound of interest.
- the preparation is at least 75%, more preferably at least 90%, and most preferably at least 98%, by weight the compound of interest.
- a purified compound is one that is at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 98%, 99%, or 100% (w/w) of the desired compound by weight. Purity is measured by any appropriate standard method, for example, by column chromatography, thin layer chromatography, or high-performance liquid chromatography (HPLC) analysis.
- a “metabolite” refers to any substance produced by metabolism or a substance necessary for taking part in a particular metabolic process.
- a metabolite can be an organic compound that is a starting material, an intermediate in, or an end product of metabolism.
- Examples of metabolites include, but are not limited to, enzymes, acids, solvents, alcohols, proteins, vitamins, minerals, microelements, amino acids, biopolymers and biosurfactants.
- Ranges provided herein are understood to be shorthand for all of the values within the range.
- a range of 1 to 20 is understood to include any number, combination of numbers, or subrange from the group consisting 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20, as well as all intervening decimal values between the aforementioned integers such as, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9.
- “nested sub-ranges” that extend from either end point of the range are specifically contemplated.
- a nested subrange of an exemplary range of 1 to 50 may comprise 1 to 10, 1 to 20, 1 to 30, and 1 to 40 in one direction, or 50 to 40, 50 to 30, 50 to 20, and 50 to 10 in the other direction.
- a “reduction” means a negative alteration
- an “increase” means a positive alteration, wherein the negative or positive alteration is at least 0.001%, 0.01%, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%.
- surfactant means a compound that lowers the surface tension (or interfacial tension) between phases. Surfactants act as, e.g., detergents, wetting agents, emulsifiers, foaming agents, and/or dispersants.
- a “biosurfactant” is a surface-active substance produced by a living cell and/or using naturally-derived substrates. Biosurfactants are a structurally diverse group of surface-active substances consisting of two parts: a polar (hydrophilic) moiety and non-polar (hydrophobic) group.
- biosurfactants Due to their amphiphilic structure, biosurfactants can, for example, increase the surface area of hydrophobic water-insoluble substances, increase the water bioavailability of such substances, and change the properties of bacterial cell surfaces. Biosurfactants can also reduce the interfacial tension between water and oil and, therefore, lower the hydrostatic pressure required to move entrapped liquid to overcome the capillary effect. Biosurfactants accumulate at interfaces, thus reducing interfacial tension and leading to the formation of aggregated micellar structures in solution. The formation of micelles provides a physical mechanism to mobilize, for example, oil in a moving aqueous phase.
- biosurfactants to form pores and destabilize biological membranes also permits their use as antibacterial, antifungal, and hemolytic agents to, for example, control pests and/or microbial growth.
- the hydrophilic group of a biosurfactant is a sugar (e.g., a mono-, di-, or polysaccharide) or a peptide
- the hydrophobic group is typically a fatty acid.
- biosurfactant molecules based on, for example, type of sugar, number of sugars, size of peptides, which amino acids are present in the peptides, fatty acid length, saturation of fatty acids, additional acetylation, additional functional groups, esterification, polarity and charge of the molecule.
- glycolipids e.g., sophorolipids, rhamnolipids, cellobiose lipids, mannosylerythritol lipids and trehalose lipids
- lipopeptides e.g., surfactin, iturin, fengycin, arthrofactin and lichenysin
- flavolipids e.g., phospholipids (e.g., cardiolipins)
- phospholipids e.g., cardiolipins
- fatty acid ester compounds e.g., and high molecular weight polymers such as lipoproteins, lipopolysaccharide -protein complexes, and polysaccharide-protein- fatty acid complexes.
- Each type of biosurfactant within each class can further comprise subtypes having further modified structures.
- each biosurfactant molecule has its own HLB value depending on its structure; however, unlike production of chemical surfactants, which results in a single molecule with a single HLB value or range, one cycle of biosurfactant production typically results in a mixture of biosurfactant molecules (e.g., subtypes and isomers thereof).
- biosurfactant and “biosurfactant molecule” include all forms, analogs, orthologs, isomers, and natural and/or anthropogenic modifications of any biosurfactant class (e.g., glycolipid) and/or subtype thereof (e.g., sophorolipid).
- biosurfactant class e.g., glycolipid
- subtype thereof e.g., sophorolipid
- a biosurfactant group of interest is the sophorolipid group.
- “Sophorolipids” are glycolipid biosurfactants produced by, for example, various yeasts of the Starmerella clade.
- SLP consist of a disaccharide sophorose linked to long chain hydroxy fatty acids. They can comprise a partially acetylated 2-O-P-D-glucopyranosyl-D-glucopyranose unit attached P-glycosidically to 17-L- hydroxyoctadecanoic or 17-L-hydroxy-A9-octadecenoic acid.
- the hydroxy fatty acid can have, for example, 11 to 20 carbon atoms, and may contain one or more unsaturated bonds.
- sophorose residue can be acetylated on the 6- and/or 6’-position(s).
- the fatty acid carboxyl group can be free (acidic or linear form) or internally esterified at the 4"-position (lactonic form).
- fermentation of SLP results in a mixture of hydrophobic (water-insoluble) SLP, including, e.g., lactonic SLP, mono-acetylated linear SLP and di-acetylated linear SLP, and hydrophilic (water- soluble) SLP, including, e.g., non-acetylated linear SLP.
- the term “sophorolipid,” “sophorolipid molecule,” “SLP” or “SLP molecule” includes all forms, and isomers thereof, of SLP molecules, including, for example, acidic (linear) SLP and lactonic SLP. Further included are mono-acetylated SLP, di-acetylated SLP, esterified SLP, SLP with varying hydrophobic chain lengths, SLP with fatty acid-amino acid complexes attached, and other, including those that are and/or are not described within in this disclosure.
- SLP can be represented by General Formula (A) and/or General Formula (B), and are obtained as a collection of multiple structural homologues:
- R 1 and R 1 independently represent saturated hydrocarbon chains or single or multiple, in particular single, unsaturated hydrocarbon chains having 8 to 20, in particular 12 to 18 carbon atoms, more preferably 14 to 18 carbon atoms, which can be linear or branched and can comprise one or more hydroxy groups
- R 2 and R 2 independently represent a hydrogen atom or a saturated alkyl functional group or a single or multiple, in particular single, unsaturated alkyl functional group having 1 to 9 carbon atoms, more preferably 1 to 4 carbon atoms, which can be linear or branched and can comprise one or more hydroxy groups
- R 3 , R 3 , R 4 and R 4 independently represent a hydrogen atom or -COCH3.
- R 5 can be, but is not limited to, —OH or -H.
- these biosurfactants Due to the structure and composition of SLP, these biosurfactants have excellent surface and interfacial tension reduction properties, as well as other beneficial biochemical properties, which can be useful in applications such as large scale industrial and agriculture uses, cosmetics, household products, health, medical and pharmaceutical fields, and oil and gas recovery.
- SLP are typically produced by yeasts, such as Starmerella spp. yeasts and/or Candida spp. yeasts, e.g., Starmerella (Candida) bombicola, Candida apicola, Candida batistae, Candida floricola, Candida riodocensis, Candida stellate and/or Candida kuoi.
- the microorganism is Starmerella bombicola, e.g., strain ATCC 22214.
- SLP have environmental compatibility, high biodegradability, low toxicity, high selectivity and specific activity in a broad range of temperature, pH and salinity conditions. Additionally, in some embodiments, SLP can be advantageous due to their small micelle size, which can help facilitate the movement of the micelle, and compounds enclosed therein, through nanoscale pores and spaces. In certain embodiments, the micelle size of a SLP is less than 100 nm, less than 50 nm, less than 20 nm, less than 15 nm, less than 10 nm, or less than 5 nm.
- the terms “builder,” “chelating agent,” and “sequestrant” refer to a compound that forms a complex (soluble or not) with ions in a specific molar ratio.
- Chelating agents include, for example, sodium tripolyphosphate, EDTA, DEDTA, DTPA, NTA, citrate, and the like.
- Sequestrants include, for example, sodium triphosphate, zeolite A, and the like.
- transitional term “comprising,” which is synonymous with “including,” or “containing,” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps.
- the transitional phrase “consisting of’ excludes any element, step, or ingredient not specified in the claim.
- the transitional phrase “consisting essentially of’ limits the scope of a claim to the specified materials or steps “and those that do not materially affect the basic and novel characteristic(s)” of the claimed invention.
- Use of the term “comprising” contemplates other embodiments that “consist” or “consist essentially of’ the recited component(s).
- the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. About can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from context, all numerical values provided herein are modified by the term about.
- the subject invention provides advantageous clarifying additives for improving the clarity of formulations that are diluted with a liquid, as well as their use in enhancing the performance of such formulations by remediating and/or preventing the precipitation of contaminating and/or otherwise undesirable components in the liquid, such as, for example, metals, minerals, and elements.
- the clarifying additive according to the subject invention can help improve the appearance and functioning of solutions by reducing haziness and preventing the precipitation of haze-causing salts from hardwater.
- This can be particularly useful in formulations that contain surfactants known to react with the ions in hardwater, e.g., SLS or sulfosuccinates.
- the clarifying additive comprises a biosurfactant.
- the biosurfactant can be utilized in crude form, which can comprise, in addition to the biosurfactant, fermentation broth in which a biosurfactant-producing microorganism was cultivated, residual microbial cell material or live or inactive microbial cells, residual nutrients, and/or other microbial growth by-products.
- the product may be, for example, at least, by weight, 1%, 5%, 10%, 25%, 50%, 75%, or 100% broth.
- the amount of biomass in the product, by weight may be, for example, anywhere from 0% to 100% inclusive of all percentages therebetween.
- the biosurfactant is utilized after being extracted and/or isolated from a fermentation broth and, optionally, purified. In some embodiments, the biosurfactant is subjected to further chemical derivatization.
- the biosurfactants according to the present invention can serve as additives in environmentally-friendly formulations for use in personal care, household and industrial uses.
- the biosurfactants serve as enhancers for traditional components, such as surfactants and/or chelators, that are utilized in these formulations.
- the biosurfactant according to the subject invention can be a glycolipid (e.g., sophorolipids, rhamnolipids, cellobiose lipids, mannosylerythritol lipids and trehalose lipids), lipopeptide (e.g., surfactin, iturin, fengycin, arthrofactin and lichenysin), flavolipid, phospholipid (e.g., cardiolipins), fatty acid ester compound, fatty acid ether compound, and/or high molecular weight polymers such as lipoproteins, lipopolysaccharide -protein complexes, and polysaccharide -protein-fatty acid complexes.
- a glycolipid e.g., sophorolipids, rhamnolipids, cellobiose lipids, mannosylerythritol lipids and trehalose lipids
- lipopeptide e.g., surfactin
- the biosurfactant can be included in the composition at, for example, 0.01 to 100,000 ppm, 0.05 to 10,000 ppm, 0.1 to 5,000 ppm, 0.5 to 2500 ppm, 1.0 to 1000 ppm, 2.0 to 750 ppm, 3.0 to 500 ppm, 4.0 to 250 ppm, 50 to 200 ppm, or 100 ppm with respect to the amount of liquid being treated or with respect to the total amount of the formulation in which the additive is utilized.
- the biosurfactant is a sophorolipid (SLP), including linear SLP, lactonic SLP, acetylated SLP, de-acetylated SLP, salt-form SLP, esterified SLP derivatives, amino acid-SLP conjugates, and other SLP derivatives or isomers that exist in nature and/or are produced synthetically.
- SLP sophorolipid
- Mixtures of different types of SLP can also be used, for example, a mixture of linear and lactonic SLP at varying ratios.
- the ratio of linear to lactonic SLP ranges from 99: 1 to 1:99, 95:5 to 5:95, 90: 10 to 10:90; 80:20 to 20:80; 70:30 to 30:70; to 50:50.
- the SLP comprises a majority, i.e., greater than 50%, linear SLP with respect to the total SLP in the composition. In certain embodiments, the SLP comprises 20% or greater linear SLP with respect to the total SLP in the composition.
- the clarifying additive can also comprise other mixtures of biosurfactants, for example, more than one glycolipid can be included, or a glycolipid and a lipopeptide.
- the clarifying additive comprises sophorolipids and mannosylerythritol lipids.
- the clarifying additive comprises sophorolipids and rhamnolipids. Other combinations are also envisioned.
- the subject invention further provides methods for remediating and/or preventing the precipitation of salts in hardwater and/or formulations diluted with a liquid containing dissolved minerals.
- the term “hardwater” refers to water containing any amount of minerals dissolved in ionic form, e.g., Ca++ and Mg++.
- the dissolved mineral is calcium, magnesium, iron, copper, nickel, gold, silver, molybdenum, aluminum, lead, tungsten, chromium, cadmium, zinc, or arsenic.
- the biosurfactants according to the subject invention function according to a surprising mechanism of action, that is, a mechanism other than chelation.
- the subject invention can be used for remediating and/or preventing the occurrence of haze that results when calcium and magnesium compounds precipitate as various salts such as, for example, calcium carbonate, calcium bicarbonate, calcium chloride, calcium sulfate, magnesium carbonate, magnesium bicarbonate, magnesium chloride and magnesium sulfate — even when standard chelators, such as EDTA, do not.
- the method comprises contacting a clarifying additive according to the subject invention with the liquid for a period of time to yield a mixture comprising a treated liquid.
- the liquid is water, more preferably, water that is characterized as hardwater.
- the treated liquid can be added to a formulation in need of dilution in an amount suitable for achieving a desired level of dilution.
- compositions can be applied to liquids or vessels that contain liquids that reside at a range of temperatures and aquatic environments, such as, for example, a stream, river, waterway, ocean, sea, lake, pond, runoff area, containment ponds, piping, fdter, press, membrane, column, screen, cone, dewaterer, classifier, scraper, hydrocyclone, agitator, drum, disk, or industrial wastewater treatment/holding tank.
- the clarifying additive can be added to vessels that contain liquids before the liquid is added to the vessel.
- the time period in which the clarifying additive can be contacted with a liquid containing the metal, mineral, or element, or a solid with the metal, mineral, or element on the surface of said solid is about 1 second to about 1 year, about 1 minute to about 1 year, about 1 minute to about 6 months, about 1 minute to about 1 month, about 1 minute to about 1 week, about 1 minute to about 48 hours, about 30 minutes to 40 hours, or preferably about 12 hours to 24 hours.
- the methods comprise pre-mixing the clarifying additive with one or more other components of the formulation, for example, a surfactant, prior to diluting the formulation with the liquid.
- the clarifying additive, liquid, and other formulation components can all be mixed together simultaneously.
- formulation components can include, but are not limited to, synthetic chelating agents, naturally-derived chelating agents, sequestrants, synthetic surfactants, essential oils, botanical extracts, cross-linking agents, fatty acids, alcohols, pH adjusting agents, reducing agents, builders, syndetics, buffers, enzymes, dyes, colorants, fragrances, preservatives, emulsifiers, foaming agents, polymers, thickeners, viscosity modifiers, and/or others as described herein.
- the components are dependent upon the particular formulation and use thereof.
- the clarifying additive can be added at, for example, 0.01 to 100,000 ppm, 0.05 to 10,000 ppm, 0.1 to 5,000 ppm, 0.5 to 2500 ppm, 1.0 to 1000 ppm, 2.0 to 750 ppm, 3.0 to 500 ppm, 4.0 to 250 ppm, 50 to 200 ppm, or 100 ppm with respect to the amount of liquid being treated or with respect to the total amount of the formulation in which the additive is utilized.
- the clarifying additive can be added at, for example, about 0.1 to 15%, about 0.1 to 10%, about 0.1 to 5%, about 0. 1 to 3%, about 0. 1%, or about 1 vol % with respect to the amount of liquid being treated or with respect to the total amount of the formulation in which the additive is utilized.
- the methods comprise applying the clarifying additive to the liquid, component or formulation for a period of time until the amount of precipitated metals, minerals, or elements therein have been remediated is determined to be satisfactory. Keeping dissolved ions in solution can reduce maintenance and processing costs, often resulting from the need to remove buildup or add additional surfactants, chelators or other additives, and allow for efficient industrial production.
- compositions and methods of the subject invention can reduce the amount of precipitation in a formulation by at least 25%, preferably by at least 50%, compared with formulations that do not contain the clarifying additive.
- the methods of the subject invention can be carried out at ambient temperature, and/or at a temperature of about 15°C to about 50°C, about 20°C to about 40°C, about 20°C to about 35°C, about 20°C to about 30° C, about 25° C, about 40°C to I20°C, about 50°C to about I00°C, about 60°C to about I00°C, about 70°C to about I00°C, about 80°C to about I00°C, or about I00°C.
- a temperature higher than ambient temperature can be provided using a microwave, ultrasound, induction heating, plasma, electricity, or any combination thereof.
- the methods of the subject invention can be carried out at ambient pressure, and/or at a pressure of about 50 bars, 75 bars, 100 bars, or greater than 100 bars.
- the clarifying additive can be used in various products, including, for example, cleaners, personal care products, cosmetics, foods, beverages, and pharmaceuticals.
- the clarifying additive can remediate and/or prevent precipitates that can alter the taste, color, clarity, and stability of these products.
- the subject invention further provides methods for reducing the amount of a traditional surfactant needed to achieve a desired function.
- the clarifying additive can be used for HI&I cleaning, e.g., in laundry detergents, dishwashing detergents, dish soaps, bathroom and kitchen surface cleaners, toilet cleaners, all-purpose cleaners, floor cleaners, and glass cleaners.
- the clarifying additive can, for example, remove and/or prevent scale deposits, water spots, biofilms, soap scum, mold and mildew.
- the compositions can be used in rinse-aid formulations for reducing dullness on glass and dishes.
- the clarifying additive can be used in personal care products, to prevent precipitation of metallic compounds that would otherwise interfere with the stability and appearance of the formulations.
- personal care products can include, for example, cosmetics, hand soaps, skin care, cleansers, deodorants, hair care, oral care, and ear and eye care products.
- the clarifying additive can be utilized in a clarifying shampoo for remediating and/or preventing the accumulation of mineral deposits on the scalp and hair.
- the clarifying additive can be used in water softening processes to reduce hardwater (i.e., minerals, including dissolved calcium and magnesium) in the water, including, for example, reducing buildup on surfaces of the hardwater deposits.
- hardwater i.e., minerals, including dissolved calcium and magnesium
- the clarifying additives can be used to remove existing scale deposits particularly on surfaces of equipment used to heat materials, that include, for example, boilers, evaporators, heat exchanger, filters, and kettles.
- the clarifying additives can be used to prevent and/or remove existing scale deposits in oil wells and on oil and gas industry equipment.
- CaCOs calcium carbonate
- the clarifying additives can be used to prevent and/or remove existing scale deposits in oil wells and on oil and gas industry equipment.
- CaCOs calcium carbonate
- brines, frac water and crude oil fluids being subject to extreme pressure and heat conditions associated with oil and gas recovery.
- compositions and methods can also be utilized in a variety of industries, products, and activities, including, for example, metalworking, polymerization, pulp and paper production, descaling, textiles, mining, pharmaceuticals, agriculture, food and beverage production, and cosmetics, to name a few.
- the clarifying additive according to the subject invention provides enhanced or increased efficiency at remediating and/or preventing the precipitation of metals, minerals, or elements from liquids or surfaces with limited negative environmental impacts.
- the methods of the subject invention do not require complicated equipment or high energy consumption, and production of the clarifying additive can be performed on site, for example, at an industrial site.
- the subject clarifying additive can result in a decreased use of synthetic chelating agents or other potentially harmful chemicals during the sequestration and/or dissolution of metals, minerals, or elements.
- the clarifying additive can comprise, and/or be added to formulations comprising additional components, including, but not limited to, synthetic chelating agents, naturally-derived chelating agents, sequestrants, synthetic surfactants, essential oils, botanical extracts, cross-linking agents, fatty acids, alcohols, pH adjusting agents, reducing agents, builders, syndetics, buffers, enzymes, dyes, colorants, fragrances, preservatives, emulsifiers, foaming agents, polymers, thickeners, viscosity modifiers, essential oils, botanical extracts, salts, acids, lubricants, stabilizers, UV light resistant agents, foaming agents, biocides, and water, including water characterized as hardwater.
- the additives are dependent upon the particular formulation and use thereof.
- the additional components can be utilized at, for example, 0.001 to 99.9%, 0.01 to 90%, 0.05 to 80%, 0.1 to 70%, 1.0 to 50%, 1.5 to 25%, or 2.0 to 15% by weight, with respect to the total formulation.
- the clarifying additive comprises and/or is formulated with a composition comprising a surfactant.
- the secondary surfactant(s) can be of non-biological origin and/or they can be biosurfactants, meaning surfactants produced by a living cell and/or using naturally-derived substrates.
- Surfactants can be, for example, anionic, cationic, zwitterionic and/or nonionic.
- Surfactants are surface active agents having two functional groups, namely a hydrophilic (water-soluble) or polar group and a hydrophobic (oil-soluble) or non-polar group.
- the hydrophobic group is usually a long hydrocarbon chain (C8-C18), which may or may not be branched, while the hydrophilic group is formed by moieties such as carboxylates, sulfates, sulfonates (anionic), alcohols, poly oxy ethylenated chains (nonionic) and quaternary ammonium salts (cationic).
- Surfactants according to the subject compositions and methods include, but are not limited to: alkyl polyglycosides, methyl glucoside esters, polyglycol esters, alcohol ethoxylates, alkali metal alkyl sulfates, alkyl alkylaryl sulfonates, linear or branched alkyl ether sulfates, sulfonates, alcohol polypropoxylated sulfates, alcohol polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinate, alkyl ether sulfates, linear and branched ether sulfates, arginine methyl esters, alkanolamines, alkylenedilamides, propoxylated surfactants, ethoxylated surfactants, ethoxylated nonyl phenol phosphate esters, alkyl glucoside, alky
- hexadecyl trimethyl ammonium bromide cetyl trimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), 5-Bromo-5-nitro-l,3-dioxane, dimethyldioctadecylammonium chloride, cetrimonium bromide, dioctadecyldi-methylammonium bromide (DODAB); zwitterionic (amphoteric) surfactants, sultaines CHAPS (3-[(3- Cholamidopropyl)dimethylammonio] - 1 -propanesulfonate), cocamidopropyl hydroxysultaine, betaines, cocamidopropyl betaine, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, sphingomyelin
- Anionic surfactants contain anionic functional groups at their head, such as sulfate, sulfonate, phosphate, and carboxylates.
- Prominent alkyl sulfates include ammonium lauryl sulfate, sodium lauryl sulfate (also called SDS, sodium dodecyl sulfate) and the related alkyl-ether sulfates sodium laureth sulfate, also known as sodium lauryl ether sulfate (SLES), and sodium myreth sulfate.
- Carboxylates are the most common surfactants and comprise the alkyl carboxylates (soaps), such as sodium stearate.
- Surfactants with cationic head groups include: pH-dependent primary, secondary, or tertiary amines; octenidine dihydrochloride; permanently charged quaternary ammonium cations such as alkyltrimethylammonium salts: cetyl trimethylammonium bromide (CTAB) a.k.a.
- CAB cetyl trimethylammonium bromide
- CTAC cetyl trimethylammonium chloride
- CPC cetylpyridinium chloride
- BAC benzalkonium chloride
- BZT benzethonium chloride
- DODAB dioctadecyldimethylammonium bromide
- Zwiterionic (amphoteric) surfactants have both cationic and anionic centers attached to the same molecule.
- the cationic part is based on primary, secondary, or tertiary amines or quaternary ammonium cations.
- the anionic part can be more variable and include sulfonates.
- Zwiterionic surfactants commonly have a phosphate anion with an amine or ammonium, such as is found in the phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelins.
- a surfactant with a non-charged hydrophilic part e.g., ethoxylate, is non-ionic. Many long chain alcohols also exhibit some surfactant properties.
- the chemical or non-biological surfactant is a detergent, weting agent, emulsifier, foaming agent, and/or dispersant.
- the chemical surfactant can be included at, for example, 0.01 to 100,000 ppm, 0.05 to 10,000 ppm, 0.1 to 5,000 ppm, 0.5 to 2500 ppm, 1.0 to 1000 ppm, 2.0 to 750 ppm, 3.0 to 500 ppm, 4.0 to 250 ppm, 50 to 200 ppm, or 100 ppm with respect to the total amount of the formulation in which the additive is utilized.
- the chemical surfactant can be included at 0.01 to 99.9%, 0.1 to 90%, 0.5 to 80%, 0.75 to 70%, 1.0 to 50%, 1.5 to 25%, or 2.0 to 15% by weight, with respect to the total formulation.
- the clarifying agent can comprise and/or be formulated into a composition comprising a synthetic chelating agent, including but not limited to, EDTA, nitrilotriacetic acid (NTA), a phosphonate, succimer (DMSA), diethylenetriaminepentaacetate (DTP A), A-acctylcystcinc. n-hydroxyethylethylenediaminetriacetic acid (HEDTA), organic acids with more than one coordination group (e.g., rubeanic acid), STPP (sodiumtripolyphosphate, Na5P3O10), trisodium phosphate (TSP) or any combination thereof.
- a synthetic chelating agent including but not limited to, EDTA, nitrilotriacetic acid (NTA), a phosphonate, succimer (DMSA), diethylenetriaminepentaacetate (DTP A), A-acctylcystcinc. n-hydroxyethylethylenedi
- naturally-derived and/or biodegradable chelating agents can be utilized, including, but not limited to, water, carbohydrates, organic acids with more than one coordination group (e.g., citric acid), lipids, steroids, amino acids or related compounds (e.g., glutathione), peptides, phosphates, nucleotides, tetrapyrrols, ferrioxamines, ionophores, orphenolics, sodium citrate, sodium gluconate, ethylenediamine disuccinic acid (EDDS), iminodisuccinic acid (IDS), L-glutamic acid diacetic Acid (GLDA), GLDA-Na4, methyl glycindiacetic acid (MGDA), polyaspartic acid (PASA), hemoglobin, chlorophyll, lipophilic -diketone, and (14,16)- hentriacontanedione, ethylenediamine-N,N'-diglutaric acid (EDDG),
- EDDG
- the synthetic and/or natural/biodegradable chelating agent can be included at, for example, 0.01 to 100,000 ppm, 0.05 to 10,000 ppm, 0.1 to 5,000 ppm, 0.5 to 2500 ppm, 1.0 to 1000 ppm, 2.0 to 750 ppm, 3.0 to 500 ppm, 4.0 to 250 ppm, 50 to 200 ppm, or 100 ppm with respect to the total amount of the formulation in which the additive is utilized.
- the chelating agent can be included at 0.01 to 99.9%, 0.1 to 90%, 0.5 to 80%, 0.75 to 70%, 1.0 to 50%, 1.5 to 25%, or 2.0 to 15% by weight, with respect to the total formulation.
- the biosurfactants according to the present invention can serve as clarifying additives in environmentally-friendly cleaning compositions, such as, for example, dishwasher (auto-dish) detergents, laundry detergents, and bathroom and kitchen surface cleaners.
- the clarifying additives comprising the biosurfactant(s) can help with, for example, preventing and/or removing water spots and soap scum, lifting stains, dissolving food particles, and disrupting biofilms, among other uses.
- the biosurfactants serve as enhancers or builders for traditional surfactants.
- the clarifying additives can be formulated into a cleaning composition, wherein the cleaning composition can comprise additional surfactants, for example, alkyl polyglucoside surfactants.
- alkyl polyglucosides for use herein include alkylpolyglucosides having a hydrophobic group containing from about 6 to about 30 carbon atoms, or from about 10 to about 16 carbon atoms, and polysaccharide units.
- alkylglycosides include, but are not limited to, Glucopon 425® (a Cs-Cie alkyl polyglycoside available from Cognis Corporation), Glucopon 625® (a C12- Cie alkyl polyglycoside available from Cognis Corporation), Dow Triton® CG-110 (a Cs-Cio alkyl polyglycoside available from Dow Chemical Company), AG6202® (a Cs alkyl polyglycoside available from Akzo Nobel) and Alkadet 35® (a Cs-Cio alkyl polyglycoside available from Huntsman Corporation).
- Glucopon 425® a Cs-Cie alkyl polyglycoside available from Cognis Corporation
- Glucopon 625® a C12- Cie alkyl polyglycoside available from Cognis Corporation
- Dow Triton® CG-110 a Cs-Cio alkyl polyglycoside available from Dow Chemical Company
- a C8 to CIO alkylpolyglucoside includes alkylpolyglucosides wherein the alkyl group is substantially C8 alkyl, substantially CIO alkyl, or a mixture of substantially C8 and CIO alkyl.
- a C6 to C8 alkylpolyglucoside includes alkylpolyglucosides wherein the alkyl group is substantially C6 alkyl, substantially C8 alkyl, or a mixture of substantially C6 and C8 alkyl.
- a C6 alkylpolyglucoside can be used in the present invention.
- An exemplary embodiment of a C6 alkylpolyglucoside is AG 6206® (a Ce alkyl polyglycoside available from Akzo Nobel).
- the composition comprises one or more of: caprylyl/capryl glucoside, lauryl glucoside, decyl glucoside and/or myristyl glucoside.
- the cleaning composition can contain a fatty alcohol sulfate as an additional surfactant.
- the fatty alcohol sulfate is one in which the higher alcohol or alkyl group is normally in the range of 10 to 18 carbon atoms.
- the cation can include sodium, triethanolamine, potassium, ammonium, magnesium and/or calcium.
- Preferred fatty alcohol sulfates are those wherein the fatty alcohol is essentially saturated and has a carbon content of 10 to 18 carbon atoms, preferably 10 or 12 to 14 or 16 carbon atoms, such as 12 to 16, or that is derived from coconut oil (coco), palm oil, or palm kernel oil.
- Lauryl sulfates, and particularly, sodium lauryl sulfate are preferred primary detergents but such designation also may apply to such detergents wherein the carbon chain length of the alcohol is not limited to 12 carbon atoms, but is primarily (over 50% and normally over 70 or 75%) of 12 to 14 carbon atoms.
- Such materials may be obtained from natural sources, such as coconut oil and palm kernel oil.
- the fatty alcohol sulfate is a C12-C18 fatty alcohol sulfate. In another embodiment, the fatty alcohol sulfate is a C12-C16 fatty alcohol sulfate. In another embodiment, the fatty alcohol sulfate is a C12-C14 fatty alcohol sulfate. In another embodiment, the fatty alcohol is a C12 fatty alcohol sulfate. In another embodiment, the fatty alcohol sulfate is sodium lauryl sulfate.
- the cleaning composition comprises an amine oxide-based surfactant, such as, for example, layrtldimethylamine oxide (LDAO), dodecyldimethylamine oxide (DDA)), lauramine oxide and/or myristamine oxide.
- amine oxide-based surfactant such as, for example, layrtldimethylamine oxide (LDAO), dodecyldimethylamine oxide (DDA)), lauramine oxide and/or myristamine oxide.
- hydrophilic and/or hydrophobic syndetics can be beneficial in delivering formulations that can decrease the interfacial tension between an aqueous solution and oily substances commonly encountered as “soils” on materials and/or surfaces.
- the cleaning composition can comprise a hydrophilic syndetic, which can rapidly adsorb at the interface between a water-immiscible oil and water, together with the surfactant(s), resulting in very low interfacial tension values.
- the short-chain hydrophilic syndetic can be a Ce alkyl polyglucoside, a Ceto Cs alkyl polyglucoside, or a Cs alkyl polyglucoside.
- Alternative suitable hydrophilic syndetics are Ce alkyl sulfate or Ceto Cs alkyl sulfate.
- Another alternative suitable hydrophilic syndetic is a CL to Cs alkyl polypentoside, an example of which is Radia®Easysurf 6505.
- the alkyl polypentosides are materials of desirably high RCI in which the hydrophilic groups are derived from raw material sources such as wheat bran and straw. Such biomass-based sources, when refined, yield syrups that are enriched in pentoses, or 5 carbon sugars, such as arabinose and xylose. Glycosylation of pentoses with alcohols is readily accomplished, adding the hydrophobic alkyl groups, which provide the resulting materials with interfacial activity.
- the alkyl chains are derived from fatty alcohols which are derived from a natural source, such as coconut or palm oil, or sugar beets, or distilled cuts of fatty alcohols from such plantbased raw materials. Condensation reactions between the hydrophilic pentoses may occur during synthesis of the interfacially active materials, thus producing practical final materials that can be described as alkyl polypentosides.
- glycosylated pentoses and their mixtures are referred to as alkyl pentosides, alkyl xylosides or alkyl polypentosides.
- the alkyl chains should be relatively short, that is the average length of the chain should be from about 4 to 8 carbon atoms.
- the cleaning composition comprises a hydrophobic syndetic, which can interact with the other components, including oils and surfactants.
- hydrophobic syndetic can interact with the other components, including oils and surfactants.
- the incorporation of both hydrophilic and hydrophobic syndetics in formulations can help achieve rapid reduction of interfacial tension.
- the removal of oily substances from surfaces by cleaning formulations proceeds via either the so-called “roll-up” of oil, or “snap-off’ of oil, or true “solubilization” of oil. The efficiency of all of these processes is improved by the reduction of interfacial tension.
- the cleaning compositions can include one or more solvents, including but not limited to water, alcohols, plant derived alcohols, glycols, mineral spirits, alkylaromatics, terpenoids, terpenoid derivatives, terpenes, and terpenes derivatives and/or vegetable oils.
- Water insoluble solvents can be mixed with a water-soluble solvent when employed.
- the cleaning compositions can comprise one or more solvents such as, for example, ethanol, methanol, n-propanol, isopropyl alcohol, 2-methyl-2-propanol, hexanol, isopropanol, sorbitol, 1,3-propanediol, glycerine, octoxyglycerin, glycerol, propylene glycol, diglycerol, dipropylene glycol, phenoxyethanol, benzyl alcohol or its derivatives (e.g., hydroxylbenzyl alcohol, nitro benzyl alcohol, or other derivatives), l-phenoxy-2-propanol, phenethyl alcohol, isopropyl myristate, denatured alcohol (SDA 40B and SDA 3C), pinene, limonene, d- limonene, and/or mixtures thereof.
- solvents such as, for example, ethanol, methanol, n-propano
- the solvents are used at amounts ranging from about 0.001% to about 25% by weight with respect to the total cleaning composition, about 0.01% to about 30%, about 0.05% to about 35%, about 0.1% to about 40%, about 0.5% to about 45%, about 0.75% to about 50%, about 1.0% to about 55%, about 1.5% to about 60%, about 2.0% to about 65%, about 3.0% to about 70%, about 4.0% to about 75%, about 5.0% to about 80%, about 6.0% to about 85%, about 7.0% to about 90%, or about 10% to about 99%.
- the composition is an aqueous composition
- water can be, along with the solvent, a predominant ingredient.
- the water should be present at a level of less than 99.9%, more preferably less than about 99%, and most preferably, less than about 98%. Deionized water is preferred.
- the cleaning composition is concentrated, the water may be present in the composition at a concentration of less than about 85% by weight.
- the cleaning composition comprises a builder, which can help increase the effectiveness of surfactants.
- Builders can include, for example, a softener, a sequestering agent, a chelator, a buffering agent, an emulsifier, and/or a pH adjusting agent.
- a variety of builders can be used, including, but not limited to, phosphate-silicate compounds, zeolites, alkali metal, ammonium and substituted ammonium polyacetates, trialkali salts of nitrilotriacetic acid, carboxylates, polycarboxylates, carbonates, bicarbonates, polyphosphates, aminopolycarboxylates, polyhydroxy-sulfonates, and starch derivatives.
- Builders when used, include, but are not limited to, organic acids, mineral acids, alkali metal and alkaline earth salts of silicate, metasilicate, polysilicate, borate, hydroxide, carbonate, carbamate, phosphate, polyphosphate, pyrophosphates, triphosphates, tetraphosphates, ammonia, hydroxide, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, and 2- amino-2 -methylpropanol.
- Preferred buffering agents for compositions of this invention are nitrogencontaining materials. Some examples are amino acids such as lysine or lower alcohol amines like mono-, di-, and tri -ethanolamine.
- nitrogen-containing buffering agents are tri(hydroxymethyl)amino methane (TRIS), 2-amino-2 -ethyl- 1,3 -propanediol, 2-amino-2-methyl- propanol, 2-amino-2-methyl-l,3-propanol, disodium glutamate, N-methyl diethanolamide, 2- dimethylamino-2-methylpropanol (DMAMP), l,3-bis(methylamine)-cyclohexane, 1,3-diamino- propanol N,N'-tetra-methyl-l, 3 -diamino-2 -propanol, N,N-bis(2-hydroxyethyl)glycine (bicine) andN- tris(hydroxymethyl)methyl glycine (tricine). Mixtures of any of the above are also acceptable.
- TMS tri(hydroxymethyl)amino methane
- silicate is meant to encompass silicate, metasilicate, polysilicate, aluminosilicate and similar compounds.
- the buffer/builder is sodium silicate, sodium carbonate, sodium polyphosphate, or potassium carbonate. In certain embodiments, the composition contains essentially no phosphates.
- the builder can be a sequestrant, which can hold, or sequester, metal ions in solution.
- Sequestrants can be useful in the presence of hard water, which contains calcium and magnesium ions that bind to anionic surfactants and reduce the efficacy of a detergent.
- sequestrant builders can be used, including, but not limited to, ammonium and substituted ammonium polyacetates, trialkali salts of nitrilotriacetic acid, carboxylates, polycarboxylates, polyphosphates, aminopolycarboxylates, polyhydroxy-sulfonates, and starch derivatives. Specific examples include, but are not limited to, carbamate, phosphate, polyphosphate, pyrophosphates, triphosphates, tetraphosphates, ammonia, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, and 2-amino-2 -methylpropanol.
- nitrogen-containing materials such as, for example, amino acids such as lysine or lower alcohol amines like mono-, di-, and tri-ethanolamine.
- nitrogen-containing buffering agents are tri(hydroxymethyl)amino methane (TRIS), 2-amino-2-ethyl- 1,3 -propanediol, 2-amino-2 -methyl -propanol, 2-amino-2 -methyl- 1,3 -propanol, disodium glutamate, N-methyl diethanolamide, 2-dimethylamino-2-methylpropanol (DMAMP), l,3-bis(methylamine)- cyclohexane, 1,3 -diamino-propanol N,N'-tetra-methyl-l, 3 -diamino-2 -propanol, N,N-bis(2- hydroxyethyl)glycine (bicine) and N-tris(hydroxymethyl)methyl glycine (TRIS), 2-amino
- a rhamnolipid biosurfactant can, in addition to and/or as an alternative to being used as a detersive surfactant, serve as a water softener and/or sequestrant by binding metals, such as calcium and magnesium, which are present in hard water.
- the builder is a pH adjuster.
- the pH is adjusted to about 0.5 to 5.0 for use in, for example, toilet bowl and/or drain cleaners, where the removal of deposits such as limescale, rust or other mineral deposits is needed.
- the pH is adjusted to about 5.0 to about 8.0 for use in, for example, hand soaps, dish liquids, and all-purpose surface cleaners, where more neutral pH is needed to avoid corrosion of surfaces and/or skin irritation.
- the composition comprises sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, as a pH adjuster.
- the composition comprises citric acid, lactic acid, or another organic acid as a pH adjusting agent.
- the cleaning composition can comprise one or more organic acids.
- organic acids can serve as builders (e.g., sequestrants, softeners and/or pH adjusters), solvents, and even disinfectants.
- Organic acids include but are not limited to sulfonic acids, acetic acid, formic acid, oxalic acid, fruit acid, citric acid, glycolic acid, lactic acid, malic acid, tartaric acid, benzoic acid and its derivatives (e.g., salt forms, for example, a benzyl benzoate, paramino benzoic acid, nitro benzoic acid, hydroxyl benzoic acid, fluorobenzoic acid, and benzyl salicylate), salicylic acid and 2- hydroxy carboxylic acids.
- 2-hydroxycarboxylic acids include, but are not limited to, tartaric acid, citric acid, malic acid, mandelic acid, acetic acid, oxalic acid, glycolic acid and lactic acid.
- the amount of organic acid ranges from about 0% to about 2.5% by weight, about 0.001% to about 3.0%, about 0.01% to about 3.5%, about 0.05% to about 4.0%, about 0.1% to about 4.5%, about 0.5% to about 5.0%, about 0.75% to about 5.5%, about 1.0% to about 10%, or about 1.5% to about 25%.
- Hydrogen peroxide sources include any compound that generates active oxygen when in contact with water. Suitable water-soluble sources of hydrogen peroxide include, for example, percarbonates, perborates, preformed percarboxylic acids, persilicates, persulphates, organic and inorganic peroxides and/or hydroperoxides. In one embodiment, the hydrogen peroxide source is sodium percarbonate. In another embodiment, the hydrogen peroxide source is sodium perborate.
- peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof.
- Suitable classes include dialkylperoxides, diacylperoxide, performed percarboxylic acids, organic and inorganic peroxides and/or hydroperoxides.
- Suitable organic peroxides/hydroperoxides include diacyl and dialkyl peroxides/hydro-peroxides such as dibenzoyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, dicumyl peroxide, and mixtures thereof.
- Suitable preformed peroxyacids for use in the compositions according to the present invention include diperoxydodecandioic acid DPDA, magnesium perphthalic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
- the oxidant is present in the cleaning composition in an amount ranging from about 0.01% to about 15% by weight, or about 0.1% to about 25% by weight, or about 0.5% to about 35%, or about 0.75% to about 45%, or about 1.0% to about 55%, or about 2.0% to about 65%, or about 3.0% to about 75%, or about 4.0% to about 85%, or about 5.0% to about 95%.
- the cleaning composition comprises an antioxidant.
- Suitable antioxidants include, for example, compounds having phenolic hydroxy functions, such as ascorbic acid and its derivatives/esters; omega-3 fatty acids (e.g., DHA, EPA); beta-carotene; catechins; curcumin; ferulic acid derivatives (e.g., ethyl ferulate, sodium ferulate); gallic acid derivatives (e.g., propyl gallate); lycopene; reductic acid; rosmarinic acid; tannic acid; tetrahydrocurcumin; tocopherol and its derivatives, including tocopheryl acetate; uric acid; or any mixtures thereof.
- the alkane diols include, for example, 1,2- alkanediol, a 1,3 -alkanediol, a 2,3-alkanediol, or a 2,4-alkanediol 1,9 nonanediol, 1,2-decanediol, 1,10-decanediol, 1,11 -undecanediol, 1,2-dodecanediol, 1,12 dodecanediol, cyclododecanediol, 1,13- tridecanediol, 1,2-tetradecanediol, 1,14-tetradecanediol, 1,15 -pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecane
- a natural thickener and/or viscosifier is added to the cleaning composition to enhance foaming activity. This counteracts the decrease in viscosity that occurs if temperature increase occurs during cleaning.
- Thickeners and/or viscosifiers can include, for example, cellulose-based polymers, such as xanthan gum, as well as others listed below.
- the cleaning compositions can comprise an auxiliary nonionic or anionic polymeric thickening component, especially cellulose thickening polymers, especially a water-soluble or water dispersible polymeric materials, having a molecular weight greater than about 20,000.
- auxiliary nonionic or anionic polymeric thickening component especially cellulose thickening polymers, especially a water-soluble or water dispersible polymeric materials, having a molecular weight greater than about 20,000.
- water-soluble or water dispersible polymer is meant that the material will form a substantially clear solution in water at a 0.5%to 1% by weight concentration at 25° C. and the material will increase the viscosity of the water either in the presence or absence of surfactant.
- water-soluble polymers that can be used as an additional thickening component, include, but are not limited to, hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, dextrans, for example Dextran purified crude Grade 2P, available from D&O Chemicals, carboxymethyl cellulose, plant exudates such as acacia, ghatti, and tragacanth, seaweed extracts such as sodium alginate, and sodium carrageenan.
- Additional thickeners can include, for example, natural polysaccharide or cellulose materials. Examples of such materials are guar gum, locust bean gum, and xanthan gum. Also suitable herein preferred is hydroxyethyl cellulose having a molecular weight of about 700,000.
- the cleaning composition comprises a thickener at an amount of about 0.05% to 2.0% by weight, or 0.1% to about 2.5% by weight.
- the cleaning compositions can comprise a fragrance and/or essential oil, and/or one or more individual constituents derived from essential oils.
- the essential oil has additional beneficial properties other than providing a fragrance to the cleaning composition.
- some essential oils can have disinfecting properties.
- Epssential oils are volatile oils obtained from plant or animal sources, or their synthetic equivalents, and are composed of complex mixtures of several constituents such as monoterpenes and sesquiterpene hydrocarbons, monoterpene and sesquiterpene alcohols, esters, ethers, aldehydes, ketones, oxides and the like.
- Essential oils include, but are not limited to, those obtained from thyme, lemongrass, citrus, lemons, oranges, anise, clove, aniseed, pine, cinnamon, geranium, roses, mint, lavender, citronella, eucalyptus, peppermint, camphor, sandalwood, rosmarin, vervain, fleagrass, lemongrass, ratanhiae, cedar and mixtures thereof.
- essential oils include, but are not limited to, cinnamon oil (e.g., cinnamon leaf oil or cinnamon bark oil), basil oil, bergamot oil, clary sage oil, ylang-ylang oil, neroli oil, sandalwood oil, frankincense oil, ginger oil, peppermint oil, lavender oil, jasmine absolute, geranium oil bourbon, spearmint oil, clove oil, patchouli oil, rosemary oil, rosewood oil, sandalwood oil, tea tree oil, mint oil, vanilla oil, lemongrass oil, oregano oil, thymol, galangal oil, cedar wood oil, balsam oils, tangerine oil, Hinoki oil, Hiba oil, ginko oil, eucalyptus oil, lemon oil, orange oil, sweet orange oil, pomegranate seed oil, pomegranate oil, manuka oil, citronella oil, curry leaf oil, and Calendula oil.
- cinnamon oil e.g., cinnamon leaf oil or cinnamon bark oil
- oils may be isolated from the oil and used in the cleaning composition, and/or they may be entirely or partially chemically synthetic, and include, but are not limited to, thymol, oregano, curcumin, citronellol, 1-citronellol, citronellal, hydroxycitronellal, a- amylcinnamaldehyde, lyral, geraniol, famesol, isoeugenol, eugenol, methyl isoueugenol, camphor, eucalyptol, linalool, citral, limonene, d-limonene, menthol, alpha-pinene, cinnamaldehyde, cinnamylacetic ester, cinnamic acid, ethyl cinnamate, methyl chavicol, linalool, beta-caryophyllene, geranyl acetate, nerol,
- sesquiterpenoid compounds which may be the active compounds in the essential oils.
- Sesquiterpenoid compounds containing 15 carbons, are formed biosynthetically from three 5-carbon isoprene units.
- Sesquiterpenoid compounds include, but are not limited to, famesol, nerolidol, bisabolol, apritone, chamazulene, santalol, zingiberol, carotol, and caryophyllen.
- the cleaning composition contains essential oils or fragrances including lemon oil and/or d-limonene.
- Lemon oil and d-limonene compositions include mixtures of terpene hydrocarbons obtained from the essence of oranges, e.g., cold-pressed orange terpenes and orange terpene oil phase ex fmit juice, and the mixture of terpene hydrocarbons expressed from lemons and grapefruit.
- the essential oils may contain minor, non-essential amounts of hydrocarbon carriers.
- an essential oil or individual constituent thereof can be present in the cleaning composition in an amount ranging from about 0.001% to about 0.10% by weight, or about 0.01% to about 0.20%, or about 0.10% to about 0.30%, or about 0.15% to about 0.35%, or about 0.20% to about 0.40%, or about 0.25% to about 0.45%, or about 0.30% to about 0.50%, or about 0.40% to about 1.0%, or about 0.50% to about 2.0%.
- the cleaning compositions can contain dyes, colorants and/or enzymes. These dyes and colorants can be natural (occurring in nature or slightly processed from natural materials) or synthetic. Dyes and colorants include synthetic dyes such as Liquitint® Yellow or Blue or natural plant dyes, colored speckles or pigments, such as a natural yellow, orange, red, and/or brown pigment, such as carotenoids, including, for example, beta-carotene and lycopene. In one embodiment, the composition comprises a polyoxyalkylene substituted chromophore colorant. Colored speckles can be synthetic or natural and can include green metso beads, britasel dyed with Milliken dyes, Blue Metso or UMB.
- Enzymes used in the cleaning composition include, but are not limited to, proteases, amylases, lipases, mannanases and mixtures thereof.
- the colorants, dyes and/or enzymes comprise no more than 3.0%, no more than 2.0%, no more than 1.0%, or no more than 0.5% in the cleaning composition.
- the colorants, dyes, enzymes and mixtures thereof can be between 0.1 to 3.0%, 0.1 to 2.0%, 0.1 to 1.0%, 0.5 to 3.0%, 0.5 to 2.0%, 0.5 to 1.0%, 1.0 to 3.0% and 1.0 to 2.0%.
- the cleaning compositions do not contain brighteners and/or preservatives. In alternative embodiments, the cleaning compositions may contain one or more brighteners and/or preservatives.
- Brighteners include, but are not limited to optical brighteners, which for example include stillbene-triazinic derivatives.
- Preservatives when used, can include, for example, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, benzyl alcohol, potassium sorbate, bisabalol, sodium benzoate, 2-phenoxyethanol, mildewstat or bacteriostat, methyl, ethyl and propyl parabens, short chain organic acids (e.g., acetic, lactic and/or glycolic acids), bisguanidine compounds (e.g., Dantagard® and/or Glydant®) and/or short chain alcohols (e.g., ethanol and/or IPA).
- short chain organic acids e.g., acetic, lactic and/or glycolic acids
- bisguanidine compounds e.g., Dantagard® and/or Glydant®
- short chain alcohols e.g., ethanol and/or IPA
- the mildewstat or bacteriostat includes, but is not limited to, mildewstats (including non-isothiazolone compounds) including Kathon GC/ICP®, a 5-chloro-2-methyl-4-isothiazolin-3-one, KATHON ICP, a 2 -methyl - 4-isothiazolin-3-one, and a blend thereof, and KATHON 886, a 5-chloro-2-methyl-4-isothiazolin-3- one, all available from Rohm and Haas Company; BRONOPOL®, a 2-bromo-2-nitropropane 1,3 diol, from Boots Company Ltd., PROXEL CRL, a propyl-p-hydroxybenzoate, from ICI PLC; NIPASOL M, an o-phenyl-phenol, Na + salt, from Nipa Laboratories Ltd., DOWICIDE A, a 1,2- Benzoisothiazolin-3-one, from Dow Chemical Co., and IR
- the cleaning composition may comprise disinfectants and/or sanitizers.
- the biosurfactant can also serve as a green disinfectant and/or sanitizer.
- the essential oil thymol can be used as a green disinfectant and/or sanitizer.
- an organic acid such as citric acid or lactic acid can be used as a green disinfectant.
- an amine oxide can be used as a disinfectant, such as LDAO, DDA, lauramine oxide or myristamine oxide.
- the compositions may contain minor amounts of traditional antimicrobials as preservatives or other uses, in preferred embodiments, the composition comprises no non-natural disinfectants or sanitizers, such as quaternary ammonium antimicrobials, biguanides or phenolics.
- non-limiting examples of these quaternary compounds include benzalkonium chlorides and/or substituted benzalkonium chlorides, di(C6-C14)alkyl di short chain (Cl -4 alkyl and/or hydroxyalkl) quatemaryammonium salts, N-(3-chloroallyl)hexaminium chlorides, benzethonium chloride, methylbenzethonium chloride, and cetylpyridinium chloride.
- Other quaternary compounds include the group consisting of dialkyldimethyl ammonium chlorides, alkyl dimethylbenzylammonium chlorides, dialkylmethyl-enzyhnmonium chlorides, and mixtures thereof.
- Biguanide antimicrobial actives including, but not limited to polyhexamethylene biguanide hydrochloride, p-chloro-henyl biguanide; 4-chlorobenzhydryl biguanide, halogenated hexidine such as, but not limited to, chlorhexidine( 1 , 1 '-hexamethylene-bis-5-(4-chlorophenyl biguanide) (CHG) and its salts are also in this class.
- CMG chlorhexidine( 1 , 1 '-hexamethylene-bis-5-(4-chlorophenyl biguanide)
- compositions contain surfactants, which lower the surface energy during cleaning
- compositions generally contain no surface modifying agents, which provide a lasting modification to the cleaned surface.
- Surface modifying agents are generally polymers other than the cellulosic thickening polymers and the others mentioned above, and provide spreading of the water on the surface or beading of water on the surface. This effect is seen when the surface is rewetted and even when subsequently dried after the rewetting.
- Examples of surface modifying agents include polymers and co-polymers of N,N-dimethyl acrylamide, acrylamide, and certain monomers containing quaternary ammonium groups or amphoteric groups, along with co-monomers that favor adsorption of water, such as, for example, acrylic acid and other acrylate salts, sulfonates, betaines, and ethylene oxides.
- Other examples include organosilanes and organosilicone polymers, hydrophobic amphoteric polymers, nanoparticles and hydrophobic organic polymers, such as waxes derived from petrochemicals.
- the cleaning composition can be used independently from or in conjunction with an absorbent and/or adsorbent material.
- the cleaning composition can be pre-loaded onto an absorbent and/or adsorbent material, post-absorbed and/or post adsorbed by a material during use, and/or be used separately from an absorbent and/or adsorbent material.
- the cleaning composition can be formulated to be used in conjunction with a cleaning wipe, sponge (cellulose, synthetic, etc.), paper towel, napkin, cloth, towel, rag, mop head, squeegee, toilet wand and/or other cleaning device that includes an absorbent and/or adsorbent material.
- the substrate should have sufficient wet strength, abrasivity, loft and porosity.
- nonwoven or nonwoven web means a web having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted web.
- Nonwoven webs have been formed from many processes, such as, for example, meltblowing processes, spunbonding processes, and bonded carded web processes.
- a cleaning wipe upon which the improved cleaning composition can be loaded thereon, can be made of an absorbent/adsorbent material.
- the cleaning wipe has at least one layer of nonwoven material.
- Non-limiting examples of commercially available cleaning wipes that can be used include DuPont 8838, Dexter ZA, Dexter 10180, Dexter M10201, Dexter 8589, Ft. James 836, and Concert STD60LN. All of these cleaning wipes include a blend of polyester and wood pulp.
- Dexter M10201 also includes rayon, a wood pulp derivative.
- the loading ratio of the cleaning composition onto the cleaning wipe can be about 2-5 : 1 , or about 3-4: 1.
- the cleaning composition is loaded onto the cleaning wipe in any number of manufacturing methods. Typically, the cleaning wipe is soaked in the cleaning composition for a period of time until the desired amount of loading is achieved.
- the cleaning wipe loaded with the improved cleaning composition provides excellent cleaning with little or no streaking/fdming.
- the cleaning composition can be loaded into a water-soluble capsule or pod, for example, in the case of auto-dish detergents and laundry detergents.
- the capsule or pod can be formulated out of, for example, a polyvinyl alcohol membrane, or other water-soluble materials.
- the cleaning composition of the subject invention is a dish cleaning composition for use in hand-washing dish formulations and/or in auto-dish formulations.
- the dish formulation is suitable for sensitive skin and eyes.
- the composition can be formulated with antioxidants, which, in combination with SLP and/or other biosurfactants, reduce inflammatory responses to detergents and other additives in the formulation.
- the cleaning composition of the subject invention is a laundry formulation for use in laundry washing machines.
- the laundry formulation is suitable for sensitive skin and eyes.
- SLP and/or other biosurfactants can be useful for reducing the amounts of chemical surfactants used in laundry formulations, while reducing, or even treating, skin and/or eye irritation caused by these surfactants.
- FIG. 1 shows surface tension of sodium lauryl sulfate (SDS) before and after 10pm filtration when mixed with increasing concentrations of hardwater.
- SDS sodium lauryl sulfate
- the clarifying additive can be formulated into an all-purpose cleaner that can be used on a variety of surfaces, such as, for example, counters, drains, sinks, tubs, toys, dishes, windows, faucets, stone and plastic.
- the pH is within a range of about 5.0 to about 8.0 so that the composition may be used on a variety of surfaces and/or materials without damaging or corroding the surface and/or material.
- the clarifying additive can be formulated into a liquid bathroom (glass, tub, tile, toilet) cleaner.
- the pH can range from about 0.5 to about 12.5, depending upon the type of soil to be treated (more alkaline for oils and greases, more acidic for dissolving stains and mineral deposits).
- the formulations can be used as a liquid spray, concentrate and/or loaded onto a substrate, such as a wipe.
- a substrate such as a wipe.
- the clarifying additive can be formulated into a dishwashing (handwashing) liquid.
- the pH is within a range of about 5.0 to about 8.0 so that the composition is not irritating to skin or eyes.
- the pH is preferably within a range of about 8.0 to about 12.5, which is suitable for cleaning fats, oils and greases from dishes.
- the clarifying additive can be formulated into a laundry detergent.
- the pH is within a range of about 8.0 to about 12.5, more preferably about 8.0 to about 11.0, which is suitable for cleaning stains and other soils from fabrics.
- the clarifying additive is formulated into a clarifying shampoo to help reduce the negative effects of hardwater on the scalp and hair.
- the pH is within a range of about 7.0 to 10.0 to aid in the removal of buildup and mineral deposits.
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Abstract
The subject invention provides safe, environmentally-friendly compositions and efficient methods for remediating and/or preventing the precipitation of salts in industrial and consumer products. More specifically, the subject invention provides compositions derived from microorganisms for use as clarifying additives in, e.g., cleaning products, detergents and personal care products.
Description
DESCRIPTION
ADDITIVES FOR IMPROVING THE CLARITY OF HARD WATER
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Patent Application No. 63/581,321, filed September 8, 2023, which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
Detergents and other cleaning agents often contain numerous components to improve their cleaning activity, including for example, components to counteract the effects of water hardness. “Hard” water is water that contains elevated levels of certain common impurities such as calcium (Ca) and magnesium (Mg). Hard water is known to reduce cleaning efficacy both by forming films on surfaces and reacting with detergents and other cleaning components, making them less functional in the cleaning process. For example, calcium and magnesium ions form insoluble precipitates with many anionic surfactants, e.g., fatty acid carboxylates (soap), sodium lauryl sulfonate (SLS) and Triton GR-5M (an anionic sulfosuccinate), in solution. These insoluble salts cause cleansing formulations to become hazy, and salt precipitation can reduce cleaning efficacy and/or interfere with cleaning machines.
Various methods for counteracting and/or eliminating water hardness have been implemented, including for example, adding chelating agents or sequestrants into detersive compositions in amounts sufficient to handle the hardness. Essentially, all calcium must be removed from the solution for there to be enough free surfactant available for cleaning; otherwise, more surfactant must be utilized. Thus, chelators used for these purposes are sometimes referred to as “builders,” as they help build upon the performance of the surfactant.
Nonetheless, in many instances the water hardness exceeds the chelating capacity of the composition. As a result, free calcium ions may be available to attack active components of the composition, to cause corrosion or precipitation, or to cause other deleterious effects, such as poor cleaning effectiveness or lime scale build up. Further, despite their many uses, chelating agents are associated with various risks. The common chelator ethylenediaminetetraacetic acid (EDTA) is not readily biodegradable, particularly once complexed with metal ions. This may lead to environmental accumulation, which could cause toxicity to plants and animals. Phosphonates, another category of chelating agents, are associated with cancer, and accumulate in water sources, which can result in eutrophication. Safer chelating alternatives are known, such as citric acid; however, this readily
biodegradable ingredient is not as effective as EDTA and is not compatible with certain cleaning products due to its characterization as a weak acid.
Another method for addressing water hardness issues is to soften water via ion exchange, e.g., by exchanging the calcium and magnesium ions in the water with sodium associated with a resin bed in a water softening unit. The calcium and magnesium adhere to a resin in the softener. When the resin becomes saturated, it is necessary to regenerate it using large amounts of sodium chloride dissolved in water. The sodium displaces the calcium and magnesium, which is flushed out in a briny solution along with the chloride from the added sodium chloride.
Unfortunately, however, when water softeners regenerate they produce a waste stream that contains significant amounts of chloride, creating a burden on the system, e.g., sewer system, in which they are disposed of — including a multitude of downstream water re-use applications such as potable water usages and agriculture. Further, traditional water softeners add to the salt content in discharge surface waters, which can be disruptive to the ecosystems where they are discharged.
Increasingly, consumers are looking for cleaning products, as well as other household and personal care products, that are non-toxic, non-irritating to the skin and/or eyes, and with a reduced impact on the environment, but these safer and more sustainable products are still expected to deliver performance at parity to traditional products. Due to the limited set of natural or sustainable materials that meet these needs, formulating safe and environmentally-friendly consumer products remains a challenge.
The current invention addresses needs for improved consumer products that rely upon hardwater, which are safer for human exposure and for the environment but do not sacrifice functional attributes across a wide range of applications. This invention provides safe ingredients having surprising and unexpected clarifying attributes comparable to, or better than, existing formulation additives and methods of reducing the negative effects of dissolved minerals in water.
BRIEF SUMMARY OF THE INVENTION
The subject invention relates generally to the use of biosurfactants as additives in a variety of industries, products, and activities, including, for example, household, industrial and institutional (HI&I) cleaning, personal care, cosmetics, and water treatment. More specifically, the subject invention provides environmentally-friendly compositions and methods for improving the formulation of products through the remediation of haze caused by the precipitation of metals, minerals, or elements, such as, for example, calcium, magnesium, iron, copper, nickel, gold, silver, molybdenum, aluminum, lead, tungsten, chromium, cadmium, zinc and arsenic, from liquids.
In preferred embodiments, the subject invention provides advantageous clarifying additives for improving the clarity of formulations that are diluted with a liquid, as well as their use in enhancing
the performance of such formulations by remediating and/or preventing the precipitation of contaminating and/or otherwise undesirable components in the liquid, such as, for example, metals, minerals, and elements.
Advantageously, the clarifying additive according to the subject invention can help improve the appearance and functioning of solutions by reducing haziness and preventing the precipitation of haze-causing salts, e.g., calcium carbonate, calcium bicarbonate, calcium chloride, calcium sulfate, magnesium carbonate, magnesium bicarbonate, magnesium chloride and magnesium sulfate. This can be particularly useful in formulations that contain surfactants known to react with the ions in hardwater, e.g., SLS or sulfosuccinates.
In certain embodiments, the clarifying additive comprises components that are derived from microorganisms. In certain embodiments, the clarifying additives comprise a microbial biosurfactant or a mixture of multiples biosurfactants. The biosurfactant can be utilized in crude form, which can comprise, in addition to the biosurfactant, fermentation broth in which a biosurfactant-producing microorganism was cultivated, residual microbial cell material or live or inactive microbial cells, residual nutrients, and/or other microbial growth by-products.
In some embodiments, the biosurfactant is utilized after being extracted and/or isolated from a fermentation broth and, optionally, purified. In some embodiments, the biosurfactant is subjected to further chemical derivatization.
The biosurfactant can be, e.g., a glycolipid (e.g., sophorolipid, rhamnolipids, cellobiose lipid, mannosylerythritol lipid and trehalose lipid), lipopeptide (e.g., surfactin, iturin, fengycin, arthrofactin, and lichenysin), flavolipid, phospholipid (e.g., cardiolipin), fatty acid ester compound, fatty acid ether compound, and/or high molecular weight polymer, such as lipoproteins, lipopolysaccharide-protein complexes, and polysaccharide-protein-fatty acid complexes.
In certain specific embodiments, the biosurfactant is a sophorolipid (SLP), including linear SLP, lactonic SLP, acetylated SLP, de-acetylated SLP, salt-form SLP, esterified SLP derivatives, amino acid-SLP conjugates, and other SLP derivatives or isomers that exist in nature and/or are produced synthetically. Mixtures of different subtypes of SLP can also be used, for example, a mixture of linear and lactonic SLP at varying ratios. In one embodiment, the SLP comprises a majority, i.e., greater than 50%, linear SLP with respect to the total SLP in the composition.
The clarifying additive can comprise additional components, including carriers, chelators, builders, surfactants and water, including water characterized as hardwater.
The subject invention further provides methods for remediating and/or preventing the precipitation of salts in hardwater, as well as formulations diluted with a liquid, such as hardwater. In certain embodiments, the method comprises contacting a clarifying additive according to the subject
invention with the liquid for a period of time to yield a mixture comprising a treated liquid. If necessary, multiple applications of the clarifying additive may be applied.
In preferred embodiments, the liquid is water, more preferably, water that is characterized as hardwater.
The treated liquid can be added to a formulation in need of dilution in an amount suitable for achieving a desired level of dilution.
In certain embodiments, the methods comprise pre-mixing the clarifying additive with one or more other components of the formulation, for example, a surfactant, prior to diluting the formulation with the liquid.
In certain embodiments, the clarifying additive, liquid, and other formulation components can all be mixed together simultaneously.
Other formulation components can include, but are not limited to, synthetic chelating agents, naturally-derived chelating agents, chemical surfactants, essential oils, botanical extracts, crosslinking agents, fatty acids, alcohols, pH adjusting agents, reducing agents, builders, syndetics, buffers, enzymes, dyes, colorants, fragrances, preservatives, emulsifiers, foaming agents, polymers, thickeners and/or viscosity modifiers. The components are dependent upon the particular formulation and use thereof.
In some embodiments, the biosurfactants according to the subject invention function according to a surprising mechanism of action, that is, a mechanism other than chelation. Thus, the subject invention can be used for remediating and/or preventing the occurrence of haze in solutions, even when standard chelators, such as EDTA, do not.
Advantageously, the compositions and methods of the subject invention can reduce the amount of precipitation in a formulation by at least 25%, preferably by at least 50%, compared with formulations that do not contain the clarifying additive.
In some embodiments, the subject invention further provides improved formulations, such as, for example, improved surface cleaners, laundry detergents, dishwashing liquids, auto-dish detergents, and personal care products, comprising a clarifying additive according to the subject invention. The compositions can be formulated for reduced skin and eye sensitivity for users.
The compositions and methods according to the subject invention can be effective at minimizing buildup of contaminants during, for example, household cleaning and industrial processes, and avoids and/or reduces the use of toxic chelating compounds. Furthermore, the methods of the subject invention do not require complicated equipment or high energy consumption, and production of the composition can be performed on site, for example, at an industrial site. Advantageously, the subject invention has utility in a variety of industries, products, and activities, including, for example, metalworking, oil and gas production, polymerization, pulp and paper production, household,
industrial and institutional (HI&I) cleaning and descaling, textiles, mining, pharmaceuticals, agriculture, food and beverage production, cosmetics, and water treatment.
BRIEF DESCRIPTION OF FIGURES
Figure 1 shows surface tension of sodium lauryl sulfate (SDS/SLS) before and after lOum filtration when mixed with increasing concentrations of hardwater.
Figure 2 shows a comparison of haze (precipitated salts) in a formulation comprising 1000 ppm SLS in 250 ppm hardwater (HW) (left) and a formulation comprising 1000 ppm SLS, 1000 ppm sophorolipids (SLP) and 250 ppm HW (right).
Figure 3 shows time (s) of scale calcite precipitation for two treatments, treatment A (80% lactonic SLP / 20% linear SLP) and treatment B (100% linear SLP), at various concentrations (ppm) compared to a control (blank).
DETAILED DESCRIPTION
The subject invention provides advantageous clarifying additives for improving the clarity of formulations that are diluted with a liquid, as well as their use in enhancing the performance of such formulations by remediating and/or preventing the precipitation of contaminating and/or otherwise undesirable components in the liquid, such as, for example, metals, minerals, and elements.
Advantageously, the clarifying additive according to the subject invention can help improve the appearance and functioning of solutions by reducing haziness and preventing the precipitation of haze-causing salts, such as, e.g., carbonates, chlorides and sulfates, from hardwater. The invention provides numerous unexpected downstream benefits, including for example, improving water quality and cleaning results, reducing consumption of detergents, other polymers and/or cleaning components in various cleaning applications, and preventing scale buildup, spotting and/or filming on treated surfaces.
Selected Definitions
As used herein, “applying” a composition or product refers to contacting it with a target or site such that the composition or product can have an effect on that target or site.
As used herein, a “biofilm” is a complex aggregate of microorganisms, such as bacteria, yeast, or fungi, wherein the cells adhere to each other and/or to a surface using an extracellular matrix. The cells in biofilms are physiologically distinct from planktonic cells of the same organism, which are single cells that can float or swim in liquid medium.
As used herein, an “isolated” or “purified” nucleic acid molecule, polynucleotide, polypeptide, protein or organic compound such as a small molecule (e.g., those described below), is
substantially free of other compounds, such as cellular material, with which it is associated in nature. A purified or isolated polynucleotide (ribonucleic acid (RNA) or deoxyribonucleic acid (DNA)) is free of the genes or sequences that flank it in its naturally-occurring state. A purified or isolated polypeptide is free of the amino acids or sequences that flank it in its naturally-occurring state. An isolated microbial strain means that the strain is removed from the environment in which it exists in nature. Thus, the isolated strain may exist as, for example, a biologically pure culture, or as spores (or other forms of the strain) in association with a carrier.
In certain embodiments, purified compounds are at least 60% by weight the compound of interest. Preferably, the preparation is at least 75%, more preferably at least 90%, and most preferably at least 98%, by weight the compound of interest. For example, a purified compound is one that is at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 98%, 99%, or 100% (w/w) of the desired compound by weight. Purity is measured by any appropriate standard method, for example, by column chromatography, thin layer chromatography, or high-performance liquid chromatography (HPLC) analysis.
A “metabolite” refers to any substance produced by metabolism or a substance necessary for taking part in a particular metabolic process. A metabolite can be an organic compound that is a starting material, an intermediate in, or an end product of metabolism. Examples of metabolites include, but are not limited to, enzymes, acids, solvents, alcohols, proteins, vitamins, minerals, microelements, amino acids, biopolymers and biosurfactants.
Ranges provided herein are understood to be shorthand for all of the values within the range. For example, a range of 1 to 20 is understood to include any number, combination of numbers, or subrange from the group consisting 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20, as well as all intervening decimal values between the aforementioned integers such as, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, “nested sub-ranges” that extend from either end point of the range are specifically contemplated. For example, a nested subrange of an exemplary range of 1 to 50 may comprise 1 to 10, 1 to 20, 1 to 30, and 1 to 40 in one direction, or 50 to 40, 50 to 30, 50 to 20, and 50 to 10 in the other direction.
As used herein a “reduction” means a negative alteration, and an “increase” means a positive alteration, wherein the negative or positive alteration is at least 0.001%, 0.01%, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%.
As used herein, “surfactant” means a compound that lowers the surface tension (or interfacial tension) between phases. Surfactants act as, e.g., detergents, wetting agents, emulsifiers, foaming agents, and/or dispersants. A “biosurfactant” is a surface-active substance produced by a living cell and/or using naturally-derived substrates.
Biosurfactants are a structurally diverse group of surface-active substances consisting of two parts: a polar (hydrophilic) moiety and non-polar (hydrophobic) group. Due to their amphiphilic structure, biosurfactants can, for example, increase the surface area of hydrophobic water-insoluble substances, increase the water bioavailability of such substances, and change the properties of bacterial cell surfaces. Biosurfactants can also reduce the interfacial tension between water and oil and, therefore, lower the hydrostatic pressure required to move entrapped liquid to overcome the capillary effect. Biosurfactants accumulate at interfaces, thus reducing interfacial tension and leading to the formation of aggregated micellar structures in solution. The formation of micelles provides a physical mechanism to mobilize, for example, oil in a moving aqueous phase.
The ability of biosurfactants to form pores and destabilize biological membranes also permits their use as antibacterial, antifungal, and hemolytic agents to, for example, control pests and/or microbial growth.
Typically, the hydrophilic group of a biosurfactant is a sugar (e.g., a mono-, di-, or polysaccharide) or a peptide, while the hydrophobic group is typically a fatty acid. Thus, there are countless potential variations of biosurfactant molecules based on, for example, type of sugar, number of sugars, size of peptides, which amino acids are present in the peptides, fatty acid length, saturation of fatty acids, additional acetylation, additional functional groups, esterification, polarity and charge of the molecule.
These variations lead to a group of molecules comprising a wide variety of classes, including, for example, glycolipids (e.g., sophorolipids, rhamnolipids, cellobiose lipids, mannosylerythritol lipids and trehalose lipids), lipopeptides (e.g., surfactin, iturin, fengycin, arthrofactin and lichenysin), flavolipids, phospholipids (e.g., cardiolipins), fatty acid ester compounds, and high molecular weight polymers such as lipoproteins, lipopolysaccharide -protein complexes, and polysaccharide-protein- fatty acid complexes. Each type of biosurfactant within each class can further comprise subtypes having further modified structures.
Like chemical surfactants, each biosurfactant molecule has its own HLB value depending on its structure; however, unlike production of chemical surfactants, which results in a single molecule with a single HLB value or range, one cycle of biosurfactant production typically results in a mixture of biosurfactant molecules (e.g., subtypes and isomers thereof).
The phrases “biosurfactant” and “biosurfactant molecule” include all forms, analogs, orthologs, isomers, and natural and/or anthropogenic modifications of any biosurfactant class (e.g., glycolipid) and/or subtype thereof (e.g., sophorolipid).
A biosurfactant group of interest is the sophorolipid group. “Sophorolipids” are glycolipid biosurfactants produced by, for example, various yeasts of the Starmerella clade. SLP consist of a disaccharide sophorose linked to long chain hydroxy fatty acids. They can comprise a partially
acetylated 2-O-P-D-glucopyranosyl-D-glucopyranose unit attached P-glycosidically to 17-L- hydroxyoctadecanoic or 17-L-hydroxy-A9-octadecenoic acid. The hydroxy fatty acid can have, for example, 11 to 20 carbon atoms, and may contain one or more unsaturated bonds. Furthermore, the sophorose residue can be acetylated on the 6- and/or 6’-position(s). The fatty acid carboxyl group can be free (acidic or linear form) or internally esterified at the 4"-position (lactonic form). In most cases, fermentation of SLP results in a mixture of hydrophobic (water-insoluble) SLP, including, e.g., lactonic SLP, mono-acetylated linear SLP and di-acetylated linear SLP, and hydrophilic (water- soluble) SLP, including, e.g., non-acetylated linear SLP.
As used herein, the term “sophorolipid,” “sophorolipid molecule,” “SLP” or “SLP molecule” includes all forms, and isomers thereof, of SLP molecules, including, for example, acidic (linear) SLP and lactonic SLP. Further included are mono-acetylated SLP, di-acetylated SLP, esterified SLP, SLP with varying hydrophobic chain lengths, SLP with fatty acid-amino acid complexes attached, and other, including those that are and/or are not described within in this disclosure.
SLP can be represented by General Formula (A) and/or General Formula (B), and are obtained as a collection of multiple structural homologues:
OH where R1 and R1 independently represent saturated hydrocarbon chains or single or multiple, in particular single, unsaturated hydrocarbon chains having 8 to 20, in particular 12 to 18 carbon atoms, more preferably 14 to 18 carbon atoms, which can be linear or branched and can comprise one or more hydroxy groups, R2 and R2 independently represent a hydrogen atom or a saturated alkyl functional group or a single or multiple, in particular single, unsaturated alkyl functional group having
1 to 9 carbon atoms, more preferably 1 to 4 carbon atoms, which can be linear or branched and can comprise one or more hydroxy groups, and R3, R3 , R4and R4 independently represent a hydrogen atom or -COCH3. R5 can be, but is not limited to, —OH or -H.
Due to the structure and composition of SLP, these biosurfactants have excellent surface and interfacial tension reduction properties, as well as other beneficial biochemical properties, which can be useful in applications such as large scale industrial and agriculture uses, cosmetics, household products, health, medical and pharmaceutical fields, and oil and gas recovery.
SLP are typically produced by yeasts, such as Starmerella spp. yeasts and/or Candida spp. yeasts, e.g., Starmerella (Candida) bombicola, Candida apicola, Candida batistae, Candida floricola, Candida riodocensis, Candida stellate and/or Candida kuoi. In a specific embodiment, the microorganism is Starmerella bombicola, e.g., strain ATCC 22214.
SLP have environmental compatibility, high biodegradability, low toxicity, high selectivity and specific activity in a broad range of temperature, pH and salinity conditions. Additionally, in some embodiments, SLP can be advantageous due to their small micelle size, which can help facilitate the movement of the micelle, and compounds enclosed therein, through nanoscale pores and spaces. In certain embodiments, the micelle size of a SLP is less than 100 nm, less than 50 nm, less than 20 nm, less than 15 nm, less than 10 nm, or less than 5 nm.
As used herein, the terms “builder,” “chelating agent,” and “sequestrant” refer to a compound that forms a complex (soluble or not) with ions in a specific molar ratio. Chelating agents include, for example, sodium tripolyphosphate, EDTA, DEDTA, DTPA, NTA, citrate, and the like. Sequestrants include, for example, sodium triphosphate, zeolite A, and the like.
The transitional term “comprising,” which is synonymous with “including,” or “containing,” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. By contrast, the transitional phrase “consisting of’ excludes any element, step, or ingredient not specified in the claim. The transitional phrase “consisting essentially of’ limits the scope of a claim to the specified materials or steps “and those that do not materially affect the basic and novel characteristic(s)” of the claimed invention. Use of the term “comprising” contemplates other embodiments that “consist” or “consist essentially of’ the recited component(s).
Unless specifically stated or obvious from context, as used herein, the term "or" is understood to be inclusive. Unless specifically stated or obvious from context, as used herein, the terms “a,” “and” and “the” are understood to be singular or plural.
Unless specifically stated or obvious from context, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. About can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%,
0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from context, all numerical values provided herein are modified by the term about.
The recitation of a listing of chemical groups in any definition of a variable herein includes definitions of that variable as any single group or combination of listed groups. The recitation of an embodiment for a variable or aspect herein includes that embodiment as any single embodiment or in combination with any other embodiments or portions thereof.
All references cited herein are hereby incorporated by reference in their entirety.
Clarifying Additives
The subject invention provides advantageous clarifying additives for improving the clarity of formulations that are diluted with a liquid, as well as their use in enhancing the performance of such formulations by remediating and/or preventing the precipitation of contaminating and/or otherwise undesirable components in the liquid, such as, for example, metals, minerals, and elements.
Advantageously, the clarifying additive according to the subject invention can help improve the appearance and functioning of solutions by reducing haziness and preventing the precipitation of haze-causing salts from hardwater. This can be particularly useful in formulations that contain surfactants known to react with the ions in hardwater, e.g., SLS or sulfosuccinates.
In certain embodiments, the clarifying additive comprises a biosurfactant. The biosurfactant can be utilized in crude form, which can comprise, in addition to the biosurfactant, fermentation broth in which a biosurfactant-producing microorganism was cultivated, residual microbial cell material or live or inactive microbial cells, residual nutrients, and/or other microbial growth by-products. The product may be, for example, at least, by weight, 1%, 5%, 10%, 25%, 50%, 75%, or 100% broth. The amount of biomass in the product, by weight, may be, for example, anywhere from 0% to 100% inclusive of all percentages therebetween.
In some embodiments, the biosurfactant is utilized after being extracted and/or isolated from a fermentation broth and, optionally, purified. In some embodiments, the biosurfactant is subjected to further chemical derivatization.
In certain embodiments, the biosurfactants according to the present invention can serve as additives in environmentally-friendly formulations for use in personal care, household and industrial uses. In certain embodiments, the biosurfactants serve as enhancers for traditional components, such as surfactants and/or chelators, that are utilized in these formulations.
The biosurfactant according to the subject invention can be a glycolipid (e.g., sophorolipids, rhamnolipids, cellobiose lipids, mannosylerythritol lipids and trehalose lipids), lipopeptide (e.g., surfactin, iturin, fengycin, arthrofactin and lichenysin), flavolipid, phospholipid (e.g., cardiolipins), fatty acid ester compound, fatty acid ether compound, and/or high molecular weight polymers such
as lipoproteins, lipopolysaccharide -protein complexes, and polysaccharide -protein-fatty acid complexes.
In some embodiments, the biosurfactant can be included in the composition at, for example, 0.01 to 100,000 ppm, 0.05 to 10,000 ppm, 0.1 to 5,000 ppm, 0.5 to 2500 ppm, 1.0 to 1000 ppm, 2.0 to 750 ppm, 3.0 to 500 ppm, 4.0 to 250 ppm, 50 to 200 ppm, or 100 ppm with respect to the amount of liquid being treated or with respect to the total amount of the formulation in which the additive is utilized.
In certain specific embodiments, the biosurfactant is a sophorolipid (SLP), including linear SLP, lactonic SLP, acetylated SLP, de-acetylated SLP, salt-form SLP, esterified SLP derivatives, amino acid-SLP conjugates, and other SLP derivatives or isomers that exist in nature and/or are produced synthetically.
Mixtures of different types of SLP can also be used, for example, a mixture of linear and lactonic SLP at varying ratios. In one embodiment, the ratio of linear to lactonic SLP ranges from 99: 1 to 1:99, 95:5 to 5:95, 90: 10 to 10:90; 80:20 to 20:80; 70:30 to 30:70; to 50:50.
In certain embodiments, the SLP comprises a majority, i.e., greater than 50%, linear SLP with respect to the total SLP in the composition. In certain embodiments, the SLP comprises 20% or greater linear SLP with respect to the total SLP in the composition.
The clarifying additive can also comprise other mixtures of biosurfactants, for example, more than one glycolipid can be included, or a glycolipid and a lipopeptide. In certain embodiments, the clarifying additive comprises sophorolipids and mannosylerythritol lipids. In certain other embodiments, the clarifying additive comprises sophorolipids and rhamnolipids. Other combinations are also envisioned.
Methods of Remediating and/or Preventing Salt Precipitation
The subject invention further provides methods for remediating and/or preventing the precipitation of salts in hardwater and/or formulations diluted with a liquid containing dissolved minerals.
As used herein, the term “hardwater” refers to water containing any amount of minerals dissolved in ionic form, e.g., Ca++ and Mg++. In certain embodiments, the dissolved mineral is calcium, magnesium, iron, copper, nickel, gold, silver, molybdenum, aluminum, lead, tungsten, chromium, cadmium, zinc, or arsenic.
In some embodiments, the biosurfactants according to the subject invention function according to a surprising mechanism of action, that is, a mechanism other than chelation. Thus, the subject invention can be used for remediating and/or preventing the occurrence of haze that results when calcium and magnesium compounds precipitate as various salts such as, for example, calcium
carbonate, calcium bicarbonate, calcium chloride, calcium sulfate, magnesium carbonate, magnesium bicarbonate, magnesium chloride and magnesium sulfate — even when standard chelators, such as EDTA, do not.
In certain embodiments, the method comprises contacting a clarifying additive according to the subject invention with the liquid for a period of time to yield a mixture comprising a treated liquid. In preferred embodiments, the liquid is water, more preferably, water that is characterized as hardwater.
The treated liquid can be added to a formulation in need of dilution in an amount suitable for achieving a desired level of dilution.
The compositions can be applied to liquids or vessels that contain liquids that reside at a range of temperatures and aquatic environments, such as, for example, a stream, river, waterway, ocean, sea, lake, pond, runoff area, containment ponds, piping, fdter, press, membrane, column, screen, cone, dewaterer, classifier, scraper, hydrocyclone, agitator, drum, disk, or industrial wastewater treatment/holding tank. In certain embodiments, the clarifying additive can be added to vessels that contain liquids before the liquid is added to the vessel.
In certain embodiments, the time period in which the clarifying additive can be contacted with a liquid containing the metal, mineral, or element, or a solid with the metal, mineral, or element on the surface of said solid is about 1 second to about 1 year, about 1 minute to about 1 year, about 1 minute to about 6 months, about 1 minute to about 1 month, about 1 minute to about 1 week, about 1 minute to about 48 hours, about 30 minutes to 40 hours, or preferably about 12 hours to 24 hours.
In certain embodiments, the methods comprise pre-mixing the clarifying additive with one or more other components of the formulation, for example, a surfactant, prior to diluting the formulation with the liquid.
In certain embodiments, the clarifying additive, liquid, and other formulation components can all be mixed together simultaneously.
Other formulation components can include, but are not limited to, synthetic chelating agents, naturally-derived chelating agents, sequestrants, synthetic surfactants, essential oils, botanical extracts, cross-linking agents, fatty acids, alcohols, pH adjusting agents, reducing agents, builders, syndetics, buffers, enzymes, dyes, colorants, fragrances, preservatives, emulsifiers, foaming agents, polymers, thickeners, viscosity modifiers, and/or others as described herein. The components are dependent upon the particular formulation and use thereof.
The clarifying additive can be added at, for example, 0.01 to 100,000 ppm, 0.05 to 10,000 ppm, 0.1 to 5,000 ppm, 0.5 to 2500 ppm, 1.0 to 1000 ppm, 2.0 to 750 ppm, 3.0 to 500 ppm, 4.0 to 250 ppm, 50 to 200 ppm, or 100 ppm with respect to the amount of liquid being treated or with respect to the total amount of the formulation in which the additive is utilized.
In some embodiments, the clarifying additive can be added at, for example, about 0.1 to 15%, about 0.1 to 10%, about 0.1 to 5%, about 0. 1 to 3%, about 0. 1%, or about 1 vol % with respect to the amount of liquid being treated or with respect to the total amount of the formulation in which the additive is utilized.
In certain embodiments, the methods comprise applying the clarifying additive to the liquid, component or formulation for a period of time until the amount of precipitated metals, minerals, or elements therein have been remediated is determined to be satisfactory. Keeping dissolved ions in solution can reduce maintenance and processing costs, often resulting from the need to remove buildup or add additional surfactants, chelators or other additives, and allow for efficient industrial production.
Advantageously, the compositions and methods of the subject invention can reduce the amount of precipitation in a formulation by at least 25%, preferably by at least 50%, compared with formulations that do not contain the clarifying additive.
The methods of the subject invention can be carried out at ambient temperature, and/or at a temperature of about 15°C to about 50°C, about 20°C to about 40°C, about 20°C to about 35°C, about 20°C to about 30° C, about 25° C, about 40°C to I20°C, about 50°C to about I00°C, about 60°C to about I00°C, about 70°C to about I00°C, about 80°C to about I00°C, or about I00°C. In certain embodiments, a temperature higher than ambient temperature can be provided using a microwave, ultrasound, induction heating, plasma, electricity, or any combination thereof.
The methods of the subject invention can be carried out at ambient pressure, and/or at a pressure of about 50 bars, 75 bars, 100 bars, or greater than 100 bars.
In certain embodiments, the clarifying additive can be used in various products, including, for example, cleaners, personal care products, cosmetics, foods, beverages, and pharmaceuticals. In certain embodiments, the clarifying additive can remediate and/or prevent precipitates that can alter the taste, color, clarity, and stability of these products. Advantageously, in some embodiments, the subject invention further provides methods for reducing the amount of a traditional surfactant needed to achieve a desired function.
In certain embodiments, the clarifying additive can be used for HI&I cleaning, e.g., in laundry detergents, dishwashing detergents, dish soaps, bathroom and kitchen surface cleaners, toilet cleaners, all-purpose cleaners, floor cleaners, and glass cleaners. The clarifying additive can, for example, remove and/or prevent scale deposits, water spots, biofilms, soap scum, mold and mildew. In certain embodiments, the compositions can be used in rinse-aid formulations for reducing dullness on glass and dishes.
In certain embodiments, the clarifying additive can be used in personal care products, to prevent precipitation of metallic compounds that would otherwise interfere with the stability and appearance of the formulations. Such personal care products can include, for example, cosmetics,
hand soaps, skin care, cleansers, deodorants, hair care, oral care, and ear and eye care products. In some embodiments, the clarifying additive can be utilized in a clarifying shampoo for remediating and/or preventing the accumulation of mineral deposits on the scalp and hair.
In certain embodiments, the clarifying additive can be used in water softening processes to reduce hardwater (i.e., minerals, including dissolved calcium and magnesium) in the water, including, for example, reducing buildup on surfaces of the hardwater deposits.
In certain embodiments, the clarifying additives can be used to remove existing scale deposits particularly on surfaces of equipment used to heat materials, that include, for example, boilers, evaporators, heat exchanger, filters, and kettles.
In certain embodiments, the clarifying additives can be used to prevent and/or remove existing scale deposits in oil wells and on oil and gas industry equipment. For example, calcium carbonate (CaCOs) is one of the most common scales in oil field operations and can precipitate as a result of ions present in brines, frac water and crude oil fluids being subject to extreme pressure and heat conditions associated with oil and gas recovery.
The compositions and methods can also be utilized in a variety of industries, products, and activities, including, for example, metalworking, polymerization, pulp and paper production, descaling, textiles, mining, pharmaceuticals, agriculture, food and beverage production, and cosmetics, to name a few.
Advantageously, in certain embodiments, the clarifying additive according to the subject invention provides enhanced or increased efficiency at remediating and/or preventing the precipitation of metals, minerals, or elements from liquids or surfaces with limited negative environmental impacts. Additionally, the methods of the subject invention do not require complicated equipment or high energy consumption, and production of the clarifying additive can be performed on site, for example, at an industrial site. In certain embodiments, the subject clarifying additive can result in a decreased use of synthetic chelating agents or other potentially harmful chemicals during the sequestration and/or dissolution of metals, minerals, or elements.
Formulations
The clarifying additive can comprise, and/or be added to formulations comprising additional components, including, but not limited to, synthetic chelating agents, naturally-derived chelating agents, sequestrants, synthetic surfactants, essential oils, botanical extracts, cross-linking agents, fatty acids, alcohols, pH adjusting agents, reducing agents, builders, syndetics, buffers, enzymes, dyes, colorants, fragrances, preservatives, emulsifiers, foaming agents, polymers, thickeners, viscosity modifiers, essential oils, botanical extracts, salts, acids, lubricants, stabilizers, UV light resistant
agents, foaming agents, biocides, and water, including water characterized as hardwater. The additives are dependent upon the particular formulation and use thereof.
The additional components can be utilized at, for example, 0.001 to 99.9%, 0.01 to 90%, 0.05 to 80%, 0.1 to 70%, 1.0 to 50%, 1.5 to 25%, or 2.0 to 15% by weight, with respect to the total formulation.
In some embodiments, the clarifying additive comprises and/or is formulated with a composition comprising a surfactant. The secondary surfactant(s) can be of non-biological origin and/or they can be biosurfactants, meaning surfactants produced by a living cell and/or using naturally-derived substrates. Surfactants can be, for example, anionic, cationic, zwitterionic and/or nonionic.
Surfactants are surface active agents having two functional groups, namely a hydrophilic (water-soluble) or polar group and a hydrophobic (oil-soluble) or non-polar group. The hydrophobic group is usually a long hydrocarbon chain (C8-C18), which may or may not be branched, while the hydrophilic group is formed by moieties such as carboxylates, sulfates, sulfonates (anionic), alcohols, poly oxy ethylenated chains (nonionic) and quaternary ammonium salts (cationic).
Surfactants according to the subject compositions and methods include, but are not limited to: alkyl polyglycosides, methyl glucoside esters, polyglycol esters, alcohol ethoxylates, alkali metal alkyl sulfates, alkyl alkylaryl sulfonates, linear or branched alkyl ether sulfates, sulfonates, alcohol polypropoxylated sulfates, alcohol polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinate, alkyl ether sulfates, linear and branched ether sulfates, arginine methyl esters, alkanolamines, alkylenedilamides, propoxylated surfactants, ethoxylated surfactants, ethoxylated nonyl phenol phosphate esters, alkyl glucoside, alkyl phosphonium chloride, alkyl phosphonate surfactants, linear alcohols, nonylphenol compounds, quaternary amines, alkyoxylated fatty acids, alkylphenol alkoxylates, ethoxylated amides, methyl ester sulfonates, hydrolyzed keratin, sulfosuccinates, taurates, disodium oxybis(decylbenzenesulphonate), isopropanolamine dodecylbenzene sulfonate, disodium decyl(sulfonatophenoxy)benzenesulfonate, polyethylene glycol undecyl ether, propylene glycol, trimethyltallowammonium chloride, trimethylcocoammonium chloride, quaternary alkyl ammonium chloride, propargyl alcohol, acetylenic alcohol, phosphate esters, imidazolines, amine salts, amide salts, amine oxides, alkoxylated alcohols, lauryl alcohol ethoxylate, ethoxylated nonyl phenol, ethoxylated fatty amines, ethoxylated alkyl amines, cocoalkylamine ethoxylate, modified betaines, alkylamidobetaines, cocoamidopropyl betaine, sulfonated olefins, anionic surfactants, ammonium lauryl sulfate, sodium lauryl sulfate (also called SDS, sodium dodecyl sulfate), alkyl-ether sulfates sodium laureth sulfate (also known as sodium lauryl ether sulfate (SLES)), sodium myreth sulfate; docusates, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate (PFOS), perfluorobutane sulfonate, linear alkylbenzene sulfonates (LABs),
alkyl-aryl ether phosphates, alkyl ether phosphate; carboxylates, alkyl carboxylates (soaps), sodium stearate, sodium lauroyl sarcosinate, carboxylate-based fluorosurfactants, perfluorononanoate, perfluorooctanoate; cationic surfactants, pH-dependent primary, secondary, or tertiary amines, octenidine dihydrochloride, permanently charged quaternary ammonium cations, alkyltrimethylammonium salts, cetyl trimethylammonium bromide (CTAB) (a.k.a. hexadecyl trimethyl ammonium bromide), cetyl trimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), 5-Bromo-5-nitro-l,3-dioxane, dimethyldioctadecylammonium chloride, cetrimonium bromide, dioctadecyldi-methylammonium bromide (DODAB); zwitterionic (amphoteric) surfactants, sultaines CHAPS (3-[(3- Cholamidopropyl)dimethylammonio] - 1 -propanesulfonate), cocamidopropyl hydroxysultaine, betaines, cocamidopropyl betaine, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, sphingomyelins; nonionic surfactants, ethoxylate, long chain alcohols, fatty alcohols, cetyl alcohol, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, polyoxyethylene glycol alkyl ethers (Brij): CH3-(CH2)10-16-(O-C2H4)l-25-OH (octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether), poly oxypropylene glycol alkyl ethers: CH3-(CH2)10-16- (O-C3H6)l-25-OH, glucoside alkyl ethers: CH3-(CH2)10-16-(O-Glucoside)l-3-OH (decyl glucoside, lauryl glucoside, octyl glucoside), polyoxyethylene glycol octylphenol ethers: C8H17- (C6H4)-(O-C2H4) 1-25-OH (Triton X-100), polyoxyethylene glycol alkylphenol ethers: C9H19- (C6H4)-(O-C2H4)l-25-OH (nonoxynol-9), glycerol alkyl esters (glyceryl laurate), polyoxyethylene glycol sorbitan alkyl esters (polysorbate), sorbitan esters, sorbitan alkyl esters (spans), cocamide MEA, cocamide DEA, dodecyldimethylamine oxide, copolymers of polyethylene glycol and polypropylene glycol (poloxamers), and polyethoxylated tallow amine (POEA).
Anionic surfactants contain anionic functional groups at their head, such as sulfate, sulfonate, phosphate, and carboxylates. Prominent alkyl sulfates include ammonium lauryl sulfate, sodium lauryl sulfate (also called SDS, sodium dodecyl sulfate) and the related alkyl-ether sulfates sodium laureth sulfate, also known as sodium lauryl ether sulfate (SLES), and sodium myreth sulfate. Carboxylates are the most common surfactants and comprise the alkyl carboxylates (soaps), such as sodium stearate.
Surfactants with cationic head groups include: pH-dependent primary, secondary, or tertiary amines; octenidine dihydrochloride; permanently charged quaternary ammonium cations such as alkyltrimethylammonium salts: cetyl trimethylammonium bromide (CTAB) a.k.a. hexadecyl trimethyl ammonium bromide, cetyl trimethylammonium chloride (CTAC); cetylpyridinium chloride (CPC); benzalkonium chloride (BAC); benzethonium chloride (BZT); 5-Bromo-5-nitro-l,3-dioxane; dimethyldioctadecylammonium chloride; cetrimonium bromide; and dioctadecyldimethylammonium bromide (DODAB).
Zwiterionic (amphoteric) surfactants have both cationic and anionic centers attached to the same molecule. The cationic part is based on primary, secondary, or tertiary amines or quaternary ammonium cations. The anionic part can be more variable and include sulfonates. Zwiterionic surfactants commonly have a phosphate anion with an amine or ammonium, such as is found in the phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelins.
A surfactant with a non-charged hydrophilic part, e.g., ethoxylate, is non-ionic. Many long chain alcohols also exhibit some surfactant properties.
In certain embodiments, the chemical or non-biological surfactant is a detergent, weting agent, emulsifier, foaming agent, and/or dispersant. In some embodiments, the chemical surfactant can be included at, for example, 0.01 to 100,000 ppm, 0.05 to 10,000 ppm, 0.1 to 5,000 ppm, 0.5 to 2500 ppm, 1.0 to 1000 ppm, 2.0 to 750 ppm, 3.0 to 500 ppm, 4.0 to 250 ppm, 50 to 200 ppm, or 100 ppm with respect to the total amount of the formulation in which the additive is utilized.
In some embodiments, the chemical surfactant can be included at 0.01 to 99.9%, 0.1 to 90%, 0.5 to 80%, 0.75 to 70%, 1.0 to 50%, 1.5 to 25%, or 2.0 to 15% by weight, with respect to the total formulation.
In certain embodiments, the clarifying agent can comprise and/or be formulated into a composition comprising a synthetic chelating agent, including but not limited to, EDTA, nitrilotriacetic acid (NTA), a phosphonate, succimer (DMSA), diethylenetriaminepentaacetate (DTP A), A-acctylcystcinc. n-hydroxyethylethylenediaminetriacetic acid (HEDTA), organic acids with more than one coordination group (e.g., rubeanic acid), STPP (sodiumtripolyphosphate, Na5P3O10), trisodium phosphate (TSP) or any combination thereof.
In certain embodiments, naturally-derived and/or biodegradable chelating agents can be utilized, including, but not limited to, water, carbohydrates, organic acids with more than one coordination group (e.g., citric acid), lipids, steroids, amino acids or related compounds (e.g., glutathione), peptides, phosphates, nucleotides, tetrapyrrols, ferrioxamines, ionophores, orphenolics, sodium citrate, sodium gluconate, ethylenediamine disuccinic acid (EDDS), iminodisuccinic acid (IDS), L-glutamic acid diacetic Acid (GLDA), GLDA-Na4, methyl glycindiacetic acid (MGDA), polyaspartic acid (PASA), hemoglobin, chlorophyll, lipophilic -diketone, and (14,16)- hentriacontanedione, ethylenediamine-N,N'-diglutaric acid (EDDG), ethylenediamine-N,N'- dimalonic acid (EDDM), 3 -hydroxy-2, 2-iminodisuccinic acid (HIDS), 2-hydroxyethyliminodiacetic acid (HEIDA), pyridine-2,6-dicarboxylic acid (PDA), trimethyl glycine (TMG), Tiron, or any combination thereof.
In some embodiments, the synthetic and/or natural/biodegradable chelating agent can be included at, for example, 0.01 to 100,000 ppm, 0.05 to 10,000 ppm, 0.1 to 5,000 ppm, 0.5 to 2500
ppm, 1.0 to 1000 ppm, 2.0 to 750 ppm, 3.0 to 500 ppm, 4.0 to 250 ppm, 50 to 200 ppm, or 100 ppm with respect to the total amount of the formulation in which the additive is utilized.
In some embodiments, the chelating agent can be included at 0.01 to 99.9%, 0.1 to 90%, 0.5 to 80%, 0.75 to 70%, 1.0 to 50%, 1.5 to 25%, or 2.0 to 15% by weight, with respect to the total formulation.
Cleaning Formulations
In certain embodiments, the biosurfactants according to the present invention can serve as clarifying additives in environmentally-friendly cleaning compositions, such as, for example, dishwasher (auto-dish) detergents, laundry detergents, and bathroom and kitchen surface cleaners. Advantageously, the clarifying additives comprising the biosurfactant(s) can help with, for example, preventing and/or removing water spots and soap scum, lifting stains, dissolving food particles, and disrupting biofilms, among other uses. In certain embodiments, the biosurfactants serve as enhancers or builders for traditional surfactants.
In some embodiments, the clarifying additives can be formulated into a cleaning composition, wherein the cleaning composition can comprise additional surfactants, for example, alkyl polyglucoside surfactants. Examples of alkyl polyglucosides for use herein include alkylpolyglucosides having a hydrophobic group containing from about 6 to about 30 carbon atoms, or from about 10 to about 16 carbon atoms, and polysaccharide units.
Commercially available preferred alkylglycosides include, but are not limited to, Glucopon 425® (a Cs-Cie alkyl polyglycoside available from Cognis Corporation), Glucopon 625® (a C12- Cie alkyl polyglycoside available from Cognis Corporation), Dow Triton® CG-110 (a Cs-Cio alkyl polyglycoside available from Dow Chemical Company), AG6202® (a Cs alkyl polyglycoside available from Akzo Nobel) and Alkadet 35® (a Cs-Cio alkyl polyglycoside available from Huntsman Corporation). A C8 to CIO alkylpolyglucoside (e.g., caprylyl/capryl glucosides) includes alkylpolyglucosides wherein the alkyl group is substantially C8 alkyl, substantially CIO alkyl, or a mixture of substantially C8 and CIO alkyl. A C6 to C8 alkylpolyglucoside includes alkylpolyglucosides wherein the alkyl group is substantially C6 alkyl, substantially C8 alkyl, or a mixture of substantially C6 and C8 alkyl. In another embodiment, a C6 alkylpolyglucoside can be used in the present invention. An exemplary embodiment of a C6 alkylpolyglucoside is AG 6206® (a Ce alkyl polyglycoside available from Akzo Nobel).
In one embodiment, the composition comprises one or more of: caprylyl/capryl glucoside, lauryl glucoside, decyl glucoside and/or myristyl glucoside.
In certain embodiments, the cleaning composition can contain a fatty alcohol sulfate as an additional surfactant. The fatty alcohol sulfate is one in which the higher alcohol or alkyl group is
normally in the range of 10 to 18 carbon atoms. The cation can include sodium, triethanolamine, potassium, ammonium, magnesium and/or calcium.
Preferred fatty alcohol sulfates are those wherein the fatty alcohol is essentially saturated and has a carbon content of 10 to 18 carbon atoms, preferably 10 or 12 to 14 or 16 carbon atoms, such as 12 to 16, or that is derived from coconut oil (coco), palm oil, or palm kernel oil. Lauryl sulfates, and particularly, sodium lauryl sulfate, are preferred primary detergents but such designation also may apply to such detergents wherein the carbon chain length of the alcohol is not limited to 12 carbon atoms, but is primarily (over 50% and normally over 70 or 75%) of 12 to 14 carbon atoms. Such materials may be obtained from natural sources, such as coconut oil and palm kernel oil.
In one embodiment, the fatty alcohol sulfate is a C12-C18 fatty alcohol sulfate. In another embodiment, the fatty alcohol sulfate is a C12-C16 fatty alcohol sulfate. In another embodiment, the fatty alcohol sulfate is a C12-C14 fatty alcohol sulfate. In another embodiment, the fatty alcohol is a C12 fatty alcohol sulfate. In another embodiment, the fatty alcohol sulfate is sodium lauryl sulfate.
In certain embodiments, the cleaning composition comprises an amine oxide-based surfactant, such as, for example, layrtldimethylamine oxide (LDAO), dodecyldimethylamine oxide (DDA)), lauramine oxide and/or myristamine oxide.
In certain embodiments, if enhanced detergency and/or foaming is desired and/or required, hydrophilic and/or hydrophobic syndetics can be beneficial in delivering formulations that can decrease the interfacial tension between an aqueous solution and oily substances commonly encountered as “soils” on materials and/or surfaces.
In one embodiment, the cleaning composition can comprise a hydrophilic syndetic, which can rapidly adsorb at the interface between a water-immiscible oil and water, together with the surfactant(s), resulting in very low interfacial tension values. The short-chain hydrophilic syndetic can be a Ce alkyl polyglucoside, a Ceto Cs alkyl polyglucoside, or a Cs alkyl polyglucoside. Alternative suitable hydrophilic syndetics are Ce alkyl sulfate or Ceto Cs alkyl sulfate. Another alternative suitable hydrophilic syndetic is a CL to Cs alkyl polypentoside, an example of which is Radia®Easysurf 6505. The alkyl polypentosides are materials of desirably high RCI in which the hydrophilic groups are derived from raw material sources such as wheat bran and straw. Such biomass-based sources, when refined, yield syrups that are enriched in pentoses, or 5 carbon sugars, such as arabinose and xylose. Glycosylation of pentoses with alcohols is readily accomplished, adding the hydrophobic alkyl groups, which provide the resulting materials with interfacial activity.
Preferably, the alkyl chains are derived from fatty alcohols which are derived from a natural source, such as coconut or palm oil, or sugar beets, or distilled cuts of fatty alcohols from such plantbased raw materials. Condensation reactions between the hydrophilic pentoses may occur during synthesis of the interfacially active materials, thus producing practical final materials that can be
described as alkyl polypentosides. Herein, glycosylated pentoses and their mixtures are referred to as alkyl pentosides, alkyl xylosides or alkyl polypentosides. In order for these materials to function as hydrophilic syndetics, the alkyl chains should be relatively short, that is the average length of the chain should be from about 4 to 8 carbon atoms.
In certain embodiments, the cleaning composition comprises a hydrophobic syndetic, which can interact with the other components, including oils and surfactants. The incorporation of both hydrophilic and hydrophobic syndetics in formulations can help achieve rapid reduction of interfacial tension. As is well known in the art, the removal of oily substances from surfaces by cleaning formulations proceeds via either the so-called “roll-up” of oil, or “snap-off’ of oil, or true “solubilization” of oil. The efficiency of all of these processes is improved by the reduction of interfacial tension.
In certain embodiments, the cleaning compositions can include one or more solvents, including but not limited to water, alcohols, plant derived alcohols, glycols, mineral spirits, alkylaromatics, terpenoids, terpenoid derivatives, terpenes, and terpenes derivatives and/or vegetable oils. Water insoluble solvents can be mixed with a water-soluble solvent when employed.
In certain embodiments, the cleaning compositions can comprise one or more solvents such as, for example, ethanol, methanol, n-propanol, isopropyl alcohol, 2-methyl-2-propanol, hexanol, isopropanol, sorbitol, 1,3-propanediol, glycerine, octoxyglycerin, glycerol, propylene glycol, diglycerol, dipropylene glycol, phenoxyethanol, benzyl alcohol or its derivatives (e.g., hydroxylbenzyl alcohol, nitro benzyl alcohol, or other derivatives), l-phenoxy-2-propanol, phenethyl alcohol, isopropyl myristate, denatured alcohol (SDA 40B and SDA 3C), pinene, limonene, d- limonene, and/or mixtures thereof.
In certain embodiments, the solvents are used at amounts ranging from about 0.001% to about 25% by weight with respect to the total cleaning composition, about 0.01% to about 30%, about 0.05% to about 35%, about 0.1% to about 40%, about 0.5% to about 45%, about 0.75% to about 50%, about 1.0% to about 55%, about 1.5% to about 60%, about 2.0% to about 65%, about 3.0% to about 70%, about 4.0% to about 75%, about 5.0% to about 80%, about 6.0% to about 85%, about 7.0% to about 90%, or about 10% to about 99%.
When the composition is an aqueous composition, water can be, along with the solvent, a predominant ingredient. The water should be present at a level of less than 99.9%, more preferably less than about 99%, and most preferably, less than about 98%. Deionized water is preferred. Where the cleaning composition is concentrated, the water may be present in the composition at a concentration of less than about 85% by weight.
In some embodiments, the cleaning composition comprises a builder, which can help increase the effectiveness of surfactants. Builders can include, for example, a softener, a sequestering agent, a chelator, a buffering agent, an emulsifier, and/or a pH adjusting agent.
A variety of builders can be used, including, but not limited to, phosphate-silicate compounds, zeolites, alkali metal, ammonium and substituted ammonium polyacetates, trialkali salts of nitrilotriacetic acid, carboxylates, polycarboxylates, carbonates, bicarbonates, polyphosphates, aminopolycarboxylates, polyhydroxy-sulfonates, and starch derivatives. Builders, when used, include, but are not limited to, organic acids, mineral acids, alkali metal and alkaline earth salts of silicate, metasilicate, polysilicate, borate, hydroxide, carbonate, carbamate, phosphate, polyphosphate, pyrophosphates, triphosphates, tetraphosphates, ammonia, hydroxide, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, and 2- amino-2 -methylpropanol. Preferred buffering agents for compositions of this invention are nitrogencontaining materials. Some examples are amino acids such as lysine or lower alcohol amines like mono-, di-, and tri -ethanolamine. Other preferred nitrogen-containing buffering agents are tri(hydroxymethyl)amino methane (TRIS), 2-amino-2 -ethyl- 1,3 -propanediol, 2-amino-2-methyl- propanol, 2-amino-2-methyl-l,3-propanol, disodium glutamate, N-methyl diethanolamide, 2- dimethylamino-2-methylpropanol (DMAMP), l,3-bis(methylamine)-cyclohexane, 1,3-diamino- propanol N,N'-tetra-methyl-l, 3 -diamino-2 -propanol, N,N-bis(2-hydroxyethyl)glycine (bicine) andN- tris(hydroxymethyl)methyl glycine (tricine). Mixtures of any of the above are also acceptable.
Other useful inorganic buffers/alkalinity sources that can serve as builders include ammonia, alkali metal carbonate, alkali metal bicarbonate, alkali metal phosphates, alkali metal hydroxide, alkali metal silicate and combinations thereof. These builders are often obtained from natural sources. The term silicate is meant to encompass silicate, metasilicate, polysilicate, aluminosilicate and similar compounds.
In one embodiment, the buffer/builder is sodium silicate, sodium carbonate, sodium polyphosphate, or potassium carbonate. In certain embodiments, the composition contains essentially no phosphates.
In some embodiments, the builder can be a sequestrant, which can hold, or sequester, metal ions in solution. Sequestrants can be useful in the presence of hard water, which contains calcium and magnesium ions that bind to anionic surfactants and reduce the efficacy of a detergent.
A variety of sequestrant builders can be used, including, but not limited to, ammonium and substituted ammonium polyacetates, trialkali salts of nitrilotriacetic acid, carboxylates, polycarboxylates, polyphosphates, aminopolycarboxylates, polyhydroxy-sulfonates, and starch derivatives. Specific examples include, but are not limited to, carbamate, phosphate, polyphosphate,
pyrophosphates, triphosphates, tetraphosphates, ammonia, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, and 2-amino-2 -methylpropanol.
Some further sequestrants are nitrogen-containing materials, such as, for example, amino acids such as lysine or lower alcohol amines like mono-, di-, and tri-ethanolamine. Other preferred nitrogen-containing buffering agents are tri(hydroxymethyl)amino methane (TRIS), 2-amino-2-ethyl- 1,3 -propanediol, 2-amino-2 -methyl -propanol, 2-amino-2 -methyl- 1,3 -propanol, disodium glutamate, N-methyl diethanolamide, 2-dimethylamino-2-methylpropanol (DMAMP), l,3-bis(methylamine)- cyclohexane, 1,3 -diamino-propanol N,N'-tetra-methyl-l, 3 -diamino-2 -propanol, N,N-bis(2- hydroxyethyl)glycine (bicine) and N-tris(hydroxymethyl)methyl glycine (tricine). Mixtures of any of the above are also acceptable.
In one embodiment, a rhamnolipid biosurfactant can, in addition to and/or as an alternative to being used as a detersive surfactant, serve as a water softener and/or sequestrant by binding metals, such as calcium and magnesium, which are present in hard water.
In certain embodiments, the builder is a pH adjuster. In some embodiments, the pH is adjusted to about 0.5 to 5.0 for use in, for example, toilet bowl and/or drain cleaners, where the removal of deposits such as limescale, rust or other mineral deposits is needed. In some embodiments, the pH is adjusted to about 5.0 to about 8.0 for use in, for example, hand soaps, dish liquids, and all-purpose surface cleaners, where more neutral pH is needed to avoid corrosion of surfaces and/or skin irritation. In some embodiments, the pH is adjusted to about 8.0 to about 12.0, for use in, for example, oven cleaners, polish strippers, bathtub and tile cleaners, and some laundry and/or dishwashing detergents, wherein dirt, grease, oils and other organic and/or hydrophobic soils are present.
In an exemplary embodiment, the composition comprises sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, as a pH adjuster. In another exemplary embodiment, the composition comprises citric acid, lactic acid, or another organic acid as a pH adjusting agent.
In some embodiments, the builder is present in the cleaning composition in an amount less than 30%, less than 25%, less than 20%, less than 15%, less than 10% and less than 5% by weight. In certain embodiments, the builder is present in the composition at about 0.001% to about 20%, about 0.01% to about 25%, about 0.1% to about 30%, about 0.5% to about 30%, about 1.0% to about 30%, or about 5.0% to about 30%, about 0.001% to about 1.0% by weight, or about 0.01% to less than about 0.5%, or about 0.05% to about 0.25%, or about 0.1%.
In certain embodiments, the cleaning composition can comprise one or more organic acids. In some embodiments, organic acids can serve as builders (e.g., sequestrants, softeners and/or pH adjusters), solvents, and even disinfectants.
Organic acids include but are not limited to sulfonic acids, acetic acid, formic acid, oxalic acid, fruit acid, citric acid, glycolic acid, lactic acid, malic acid, tartaric acid, benzoic acid and its derivatives (e.g., salt forms, for example, a benzyl benzoate, paramino benzoic acid, nitro benzoic acid, hydroxyl benzoic acid, fluorobenzoic acid, and benzyl salicylate), salicylic acid and 2- hydroxy carboxylic acids. 2-hydroxycarboxylic acids include, but are not limited to, tartaric acid, citric acid, malic acid, mandelic acid, acetic acid, oxalic acid, glycolic acid and lactic acid.
In some embodiments, the amount of organic acid ranges from about 0% to about 2.5% by weight, about 0.001% to about 3.0%, about 0.01% to about 3.5%, about 0.05% to about 4.0%, about 0.1% to about 4.5%, about 0.5% to about 5.0%, about 0.75% to about 5.5%, about 1.0% to about 10%, or about 1.5% to about 25%.
In some embodiments, the composition comprises an oxidant. Oxidants include, but are not limited to, peracids, hydrogen peroxide, and/or sources of hydrogen peroxide. According to the present invention, the oxidizing agent may be an oxygen bleach, including a peroxygen, peroxyhydrate or active oxygen generating compound. Suitable peroxygen bleaches for use herein include hydrogen peroxide or sources thereof.
Hydrogen peroxide sources include any compound that generates active oxygen when in contact with water. Suitable water-soluble sources of hydrogen peroxide include, for example, percarbonates, perborates, preformed percarboxylic acids, persilicates, persulphates, organic and inorganic peroxides and/or hydroperoxides. In one embodiment, the hydrogen peroxide source is sodium percarbonate. In another embodiment, the hydrogen peroxide source is sodium perborate.
In addition, other classes of peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof. Suitable classes include dialkylperoxides, diacylperoxide, performed percarboxylic acids, organic and inorganic peroxides and/or hydroperoxides. Suitable organic peroxides/hydroperoxides include diacyl and dialkyl peroxides/hydro-peroxides such as dibenzoyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, dicumyl peroxide, and mixtures thereof. Suitable preformed peroxyacids for use in the compositions according to the present invention include diperoxydodecandioic acid DPDA, magnesium perphthalic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
Preferably, the oxidant is present in the cleaning composition in an amount ranging from about 0.01% to about 15% by weight, or about 0.1% to about 25% by weight, or about 0.5% to about 35%, or about 0.75% to about 45%, or about 1.0% to about 55%, or about 2.0% to about 65%, or about 3.0% to about 75%, or about 4.0% to about 85%, or about 5.0% to about 95%.
In some embodiments, the cleaning composition comprises an antioxidant. Suitable antioxidants include, for example, compounds having phenolic hydroxy functions, such as ascorbic
acid and its derivatives/esters; omega-3 fatty acids (e.g., DHA, EPA); beta-carotene; catechins; curcumin; ferulic acid derivatives (e.g., ethyl ferulate, sodium ferulate); gallic acid derivatives (e.g., propyl gallate); lycopene; reductic acid; rosmarinic acid; tannic acid; tetrahydrocurcumin; tocopherol and its derivatives, including tocopheryl acetate; uric acid; or any mixtures thereof. Other suitable antioxidants are those that have one or more thiol functions (— SH), in either reduced or non-reduced form, such as glutathione, lipoic acid, thioglycolic acid, and other sulfhydryl compounds. The antioxidant may be inorganic, such as bisulfites, metabisulfites, sulfites, or other inorganic salts and acids containing sulfur.
In certain embodiments, the cleaning composition can comprise one or more alkane diols. Alkane diols can serve as, for example, solvents, viscosity reducers, fragrances, skin conditioning agents, and humectants. Suitable alkane diols include, but are not limited to, propanediol, butanediol, dodecanediol, decanediol, nonanediol, octanediol, heptanediol, hexanediol, and/or pentanediol.
In particular non-limiting embodiments, the alkane diols include, for example, 1,2- alkanediol, a 1,3 -alkanediol, a 2,3-alkanediol, or a 2,4-alkanediol 1,9 nonanediol, 1,2-decanediol, 1,10-decanediol, 1,11 -undecanediol, 1,2-dodecanediol, 1,12 dodecanediol, cyclododecanediol, 1,13- tridecanediol, 1,2-tetradecanediol, 1,14-tetradecanediol, 1,15 -pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, 1,20-eicosanediol, 1,21- heneicosanediol, 1,22-docosanediol, 1,23-tricosanediol, 1,24-tetracosanediol, 1,25 -pentacosanediol.
In certain embodiments an alkane diol is obtained from a natural product. In certain embodiments an alkane diol is chemically synthesized.
In certain embodiments, a natural thickener and/or viscosifier is added to the cleaning composition to enhance foaming activity. This counteracts the decrease in viscosity that occurs if temperature increase occurs during cleaning. Thickeners and/or viscosifiers can include, for example, cellulose-based polymers, such as xanthan gum, as well as others listed below.
In some embodiments, the cleaning compositions can comprise an auxiliary nonionic or anionic polymeric thickening component, especially cellulose thickening polymers, especially a water-soluble or water dispersible polymeric materials, having a molecular weight greater than about 20,000. By “water-soluble or water dispersible polymer” is meant that the material will form a substantially clear solution in water at a 0.5%to 1% by weight concentration at 25° C. and the material will increase the viscosity of the water either in the presence or absence of surfactant.
Examples of water-soluble polymers that can be used as an additional thickening component, include, but are not limited to, hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, dextrans, for example Dextran purified crude Grade 2P, available from D&O Chemicals, carboxymethyl cellulose, plant exudates such as acacia, ghatti, and tragacanth, seaweed extracts such as sodium alginate, and sodium carrageenan.
Additional thickeners can include, for example, natural polysaccharide or cellulose materials. Examples of such materials are guar gum, locust bean gum, and xanthan gum. Also suitable herein preferred is hydroxyethyl cellulose having a molecular weight of about 700,000.
In certain embodiments, the cleaning composition comprises a thickener at an amount of about 0.05% to 2.0% by weight, or 0.1% to about 2.5% by weight.
In certain embodiments, the cleaning compositions can comprise a fragrance and/or essential oil, and/or one or more individual constituents derived from essential oils. In some embodiments, the essential oil has additional beneficial properties other than providing a fragrance to the cleaning composition. For example, some essential oils can have disinfecting properties.
“Essential oils,” as used herein, are volatile oils obtained from plant or animal sources, or their synthetic equivalents, and are composed of complex mixtures of several constituents such as monoterpenes and sesquiterpene hydrocarbons, monoterpene and sesquiterpene alcohols, esters, ethers, aldehydes, ketones, oxides and the like.
Essential oils include, but are not limited to, those obtained from thyme, lemongrass, citrus, lemons, oranges, anise, clove, aniseed, pine, cinnamon, geranium, roses, mint, lavender, citronella, eucalyptus, peppermint, camphor, sandalwood, rosmarin, vervain, fleagrass, lemongrass, ratanhiae, cedar and mixtures thereof.
Examples of essential oils include, but are not limited to, cinnamon oil (e.g., cinnamon leaf oil or cinnamon bark oil), basil oil, bergamot oil, clary sage oil, ylang-ylang oil, neroli oil, sandalwood oil, frankincense oil, ginger oil, peppermint oil, lavender oil, jasmine absolute, geranium oil bourbon, spearmint oil, clove oil, patchouli oil, rosemary oil, rosewood oil, sandalwood oil, tea tree oil, mint oil, vanilla oil, lemongrass oil, oregano oil, thymol, galangal oil, cedar wood oil, balsam oils, tangerine oil, Hinoki oil, Hiba oil, ginko oil, eucalyptus oil, lemon oil, orange oil, sweet orange oil, pomegranate seed oil, pomegranate oil, manuka oil, citronella oil, curry leaf oil, and Calendula oil.
Other essential oils include Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, Camphor powder synthetic technical, Canaga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Guijun balsam, Heliotropin, Isobomyl acetate, Isolongifolene, Juniper berry oil, L-methyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol crystals, Methyl cedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil,
Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), and Wintergreen. Each of these botanical oils is commercially available.
Individual constituents of essential oils may be isolated from the oil and used in the cleaning composition, and/or they may be entirely or partially chemically synthetic, and include, but are not limited to, thymol, oregano, curcumin, citronellol, 1-citronellol, citronellal, hydroxycitronellal, a- amylcinnamaldehyde, lyral, geraniol, famesol, isoeugenol, eugenol, methyl isoueugenol, camphor, eucalyptol, linalool, citral, limonene, d-limonene, menthol, alpha-pinene, cinnamaldehyde, cinnamylacetic ester, cinnamic acid, ethyl cinnamate, methyl chavicol, linalool, beta-caryophyllene, geranyl acetate, nerol, elemol, P-selinene, a-pinene, sabinene, myrcene, verbenone, pinocarvone, cedrol, anethol, carvacrol, hinokitiol, berberine, ferulic acid, methyl salicylic acid, methyl salycilate, terpineol and mixtures thereof.
Further examples of individual consitutents include sesquiterpenoid compounds, which may be the active compounds in the essential oils. Sesquiterpenoid compounds, containing 15 carbons, are formed biosynthetically from three 5-carbon isoprene units. Sesquiterpenoid compounds include, but are not limited to, famesol, nerolidol, bisabolol, apritone, chamazulene, santalol, zingiberol, carotol, and caryophyllen.
In an exemplary embodiment, the cleaning composition contains essential oils or fragrances including lemon oil and/or d-limonene. Lemon oil and d-limonene compositions include mixtures of terpene hydrocarbons obtained from the essence of oranges, e.g., cold-pressed orange terpenes and orange terpene oil phase ex fmit juice, and the mixture of terpene hydrocarbons expressed from lemons and grapefruit.
The essential oils may contain minor, non-essential amounts of hydrocarbon carriers. In preferred embodiments, an essential oil or individual constituent thereof can be present in the cleaning composition in an amount ranging from about 0.001% to about 0.10% by weight, or about 0.01% to about 0.20%, or about 0.10% to about 0.30%, or about 0.15% to about 0.35%, or about 0.20% to about 0.40%, or about 0.25% to about 0.45%, or about 0.30% to about 0.50%, or about 0.40% to about 1.0%, or about 0.50% to about 2.0%.
In certain embodiments, the cleaning compositions can contain dyes, colorants and/or enzymes. These dyes and colorants can be natural (occurring in nature or slightly processed from natural materials) or synthetic. Dyes and colorants include synthetic dyes such as Liquitint® Yellow or Blue or natural plant dyes, colored speckles or pigments, such as a natural yellow, orange, red, and/or brown pigment, such as carotenoids, including, for example, beta-carotene and lycopene. In one embodiment, the composition comprises a polyoxyalkylene substituted chromophore colorant.
Colored speckles can be synthetic or natural and can include green metso beads, britasel dyed with Milliken dyes, Blue Metso or UMB.
Enzymes used in the cleaning composition include, but are not limited to, proteases, amylases, lipases, mannanases and mixtures thereof.
In a preferred embodiment, the colorants, dyes and/or enzymes comprise no more than 3.0%, no more than 2.0%, no more than 1.0%, or no more than 0.5% in the cleaning composition. In another embodiment, the colorants, dyes, enzymes and mixtures thereof can be between 0.1 to 3.0%, 0.1 to 2.0%, 0.1 to 1.0%, 0.5 to 3.0%, 0.5 to 2.0%, 0.5 to 1.0%, 1.0 to 3.0% and 1.0 to 2.0%.
In some embodiments, the cleaning compositions do not contain brighteners and/or preservatives. In alternative embodiments, the cleaning compositions may contain one or more brighteners and/or preservatives.
Brighteners include, but are not limited to optical brighteners, which for example include stillbene-triazinic derivatives.
Preservatives, when used, can include, for example, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, benzyl alcohol, potassium sorbate, bisabalol, sodium benzoate, 2-phenoxyethanol, mildewstat or bacteriostat, methyl, ethyl and propyl parabens, short chain organic acids (e.g., acetic, lactic and/or glycolic acids), bisguanidine compounds (e.g., Dantagard® and/or Glydant®) and/or short chain alcohols (e.g., ethanol and/or IPA). The mildewstat or bacteriostat includes, but is not limited to, mildewstats (including non-isothiazolone compounds) including Kathon GC/ICP®, a 5-chloro-2-methyl-4-isothiazolin-3-one, KATHON ICP, a 2 -methyl - 4-isothiazolin-3-one, and a blend thereof, and KATHON 886, a 5-chloro-2-methyl-4-isothiazolin-3- one, all available from Rohm and Haas Company; BRONOPOL®, a 2-bromo-2-nitropropane 1,3 diol, from Boots Company Ltd., PROXEL CRL, a propyl-p-hydroxybenzoate, from ICI PLC; NIPASOL M, an o-phenyl-phenol, Na+ salt, from Nipa Laboratories Ltd., DOWICIDE A, a 1,2- Benzoisothiazolin-3-one, from Dow Chemical Co., and IRGASAN DP 200, a 2,4,4'-trichloro-2- hydroxydiphenylether, from Ciba-Geigy A.G.
In some embodiments, the cleaning composition may comprise disinfectants and/or sanitizers. In one embodiment, the biosurfactant can also serve as a green disinfectant and/or sanitizer. In one embodiment, the essential oil thymol can be used as a green disinfectant and/or sanitizer. In one embodiment, an organic acid, such as citric acid or lactic acid can be used as a green disinfectant. In one embodiment, an amine oxide can be used as a disinfectant, such as LDAO, DDA, lauramine oxide or myristamine oxide.
Although the compositions may contain minor amounts of traditional antimicrobials as preservatives or other uses, in preferred embodiments, the composition comprises no non-natural disinfectants or sanitizers, such as quaternary ammonium antimicrobials, biguanides or phenolics.
Non-limiting examples of these quaternary compounds include benzalkonium chlorides and/or substituted benzalkonium chlorides, di(C6-C14)alkyl di short chain (Cl -4 alkyl and/or hydroxyalkl) quatemaryammonium salts, N-(3-chloroallyl)hexaminium chlorides, benzethonium chloride, methylbenzethonium chloride, and cetylpyridinium chloride. Other quaternary compounds include the group consisting of dialkyldimethyl ammonium chlorides, alkyl dimethylbenzylammonium chlorides, dialkylmethyl-enzyhnmonium chlorides, and mixtures thereof.
Biguanide antimicrobial actives including, but not limited to polyhexamethylene biguanide hydrochloride, p-chloro-henyl biguanide; 4-chlorobenzhydryl biguanide, halogenated hexidine such as, but not limited to, chlorhexidine( 1 , 1 '-hexamethylene-bis-5-(4-chlorophenyl biguanide) (CHG) and its salts are also in this class.
Although the compositions contain surfactants, which lower the surface energy during cleaning, the compositions generally contain no surface modifying agents, which provide a lasting modification to the cleaned surface. Surface modifying agents are generally polymers other than the cellulosic thickening polymers and the others mentioned above, and provide spreading of the water on the surface or beading of water on the surface. This effect is seen when the surface is rewetted and even when subsequently dried after the rewetting.
Examples of surface modifying agents include polymers and co-polymers of N,N-dimethyl acrylamide, acrylamide, and certain monomers containing quaternary ammonium groups or amphoteric groups, along with co-monomers that favor adsorption of water, such as, for example, acrylic acid and other acrylate salts, sulfonates, betaines, and ethylene oxides. Other examples include organosilanes and organosilicone polymers, hydrophobic amphoteric polymers, nanoparticles and hydrophobic organic polymers, such as waxes derived from petrochemicals.
The cleaning composition can be used independently from or in conjunction with an absorbent and/or adsorbent material. The cleaning composition can be pre-loaded onto an absorbent and/or adsorbent material, post-absorbed and/or post adsorbed by a material during use, and/or be used separately from an absorbent and/or adsorbent material.
A wide variety of materials can be used as the cleaning substrate. For instance, the cleaning composition can be formulated to be used in conjunction with a cleaning wipe, sponge (cellulose, synthetic, etc.), paper towel, napkin, cloth, towel, rag, mop head, squeegee, toilet wand and/or other cleaning device that includes an absorbent and/or adsorbent material. The substrate should have sufficient wet strength, abrasivity, loft and porosity. The terms “nonwoven” or “nonwoven web” means a web having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted web. Nonwoven webs have been formed from many processes, such as, for example, meltblowing processes, spunbonding processes, and bonded carded web processes.
In an exemplary embodiment, a cleaning wipe, upon which the improved cleaning composition can be loaded thereon, can be made of an absorbent/adsorbent material. Typically, the cleaning wipe has at least one layer of nonwoven material. Non-limiting examples of commercially available cleaning wipes that can be used include DuPont 8838, Dexter ZA, Dexter 10180, Dexter M10201, Dexter 8589, Ft. James 836, and Concert STD60LN. All of these cleaning wipes include a blend of polyester and wood pulp. Dexter M10201 also includes rayon, a wood pulp derivative. The loading ratio of the cleaning composition onto the cleaning wipe can be about 2-5 : 1 , or about 3-4: 1. The cleaning composition is loaded onto the cleaning wipe in any number of manufacturing methods. Typically, the cleaning wipe is soaked in the cleaning composition for a period of time until the desired amount of loading is achieved. The cleaning wipe loaded with the improved cleaning composition provides excellent cleaning with little or no streaking/fdming.
In certain embodiments, the cleaning composition can be loaded into a water-soluble capsule or pod, for example, in the case of auto-dish detergents and laundry detergents. The capsule or pod can be formulated out of, for example, a polyvinyl alcohol membrane, or other water-soluble materials.
In one specific embodiment, the cleaning composition of the subject invention is a dish cleaning composition for use in hand-washing dish formulations and/or in auto-dish formulations. In certain embodiments, which are particularly useful in hand-washing dish formulations, the dish formulation is suitable for sensitive skin and eyes. The composition can be formulated with antioxidants, which, in combination with SLP and/or other biosurfactants, reduce inflammatory responses to detergents and other additives in the formulation.
In one specific embodiment, the cleaning composition of the subject invention is a laundry formulation for use in laundry washing machines. In certain embodiments, which are particularly useful for cleaning baby clothes and bedding, the laundry formulation is suitable for sensitive skin and eyes. Advantageously, SLP and/or other biosurfactants can be useful for reducing the amounts of chemical surfactants used in laundry formulations, while reducing, or even treating, skin and/or eye irritation caused by these surfactants.
EXAMPLES
A greater understanding of the present invention and of its many advantages may be had from the following examples, given by way of illustration. The following examples are illustrative of some of the methods, applications, embodiments and variants of the present invention. They are not to be considered as limiting the invention. Numerous changes and modifications can be made with respect to the invention.
EXAMPLE 1 - HARD WATER PRECIPITATION TEST
FIG. 1 shows surface tension of sodium lauryl sulfate (SDS) before and after 10pm filtration when mixed with increasing concentrations of hardwater. The addition of 1,000 ppm SDS solution in 250 ppm hardwater results in a decline in surface tension reduction after the hardwater is filtered, compared to before filtration. This correlates with the removal of insoluble surfactant salts.
When 1000 ppm of SLP is added to the above solution (1000 ppm SLS in 250 ppm hardwater), the haze is remediated, indicating that all components are in solution. FIG. 2.
EXAMPLE 2 - PREVENTION OF CALCITE SCALE PRECIPITATION Two SLP treatments were applied to brine containing the following ion profile:
As shown in FIG. 3 and Table 2 below, both treatments were effective at preventing calcite precipitation in water at 100 ppm.
Treatment A = blend of lactonic and linear SLP at 80% lactonic / 20% linear (with respect to total SLP); Treatment B = 100% linear SLP; Temperature: 180°F; Pressure: 500 psi.
EXAMPLE 3 - CLEANERS
In one embodiment, the clarifying additive can be formulated into an all-purpose cleaner that can be used on a variety of surfaces, such as, for example, counters, drains, sinks, tubs, toys, dishes, windows, faucets, stone and plastic. Preferably the pH is within a range of about 5.0 to about 8.0 so that the composition may be used on a variety of surfaces and/or materials without damaging or corroding the surface and/or material.
In one embodiment, the clarifying additive can be formulated into a liquid bathroom (glass, tub, tile, toilet) cleaner. The pH can range from about 0.5 to about 12.5, depending upon the type of soil to be treated (more alkaline for oils and greases, more acidic for dissolving stains and mineral deposits).
The formulations can be used as a liquid spray, concentrate and/or loaded onto a substrate, such as a wipe.
EXAMPLE 4 - DISHWASHING LIQUID AND DISHWASHER DETERGENT
In one embodiment, the clarifying additive can be formulated into a dishwashing (handwashing) liquid. Preferably the pH is within a range of about 5.0 to about 8.0 so that the composition is not irritating to skin or eyes. When formulated as a dishwashing (auto-dish) detergent, the pH is preferably within a range of about 8.0 to about 12.5, which is suitable for cleaning fats, oils and greases from dishes.
EXAMPLE 5- LAUNDRY DETERGENT
In one embodiment, the clarifying additive can be formulated into a laundry detergent. Preferably the pH is within a range of about 8.0 to about 12.5, more preferably about 8.0 to about 11.0, which is suitable for cleaning stains and other soils from fabrics.
EXAMPLE 6— CLARIFYING SHAMPOO
Claims
1. A method for remediating and/or preventing the precipitation of salts in a liquid, the method comprising contacting a clarifying additive comprising a biosurfactant with the liquid for a period of time that is sufficient to yield a treated liquid comprising no precipitated salts.
2. The method of claim 1, wherein the liquid is water comprising dissolved calcium and magnesium ions and/or precipitated calcium and/or magnesium salts, said salts being selected from the group consisting of calcium carbonate, calcium bicarbonate, calcium chloride, calcium sulfate, magnesium carbonate, magnesium bicarbonate, magnesium chloride and magnesium sulfate.
3. The method of claim 1, further comprising adding the treated liquid to one or more additional components to yield a formulation.
4. The method of claim 3, wherein the one more additional components are selected from the group consisting of synthetic chelating agents, naturally-derived chelating agents, chemical surfactants, essential oils, botanical extracts, cross-linking agents, fatty acids, alcohols, pH adjusting agents, reducing agents, builders, syndetics, buffers, enzymes, dyes, colorants, fragrances, preservatives, emulsifiers, foaming agents, polymers, thickeners and viscosity modifiers.
5. The method of claim 3, wherein the one or more additional components is an anionic surfactant.
6. The method of claim 5, wherein the formulation comprises 50-1200 ppm of the clarifying additive, 50-1200 ppm of the anionic surfactant and 50-250 ppm of the treated liquid.
7. The method of claim 1, comprising mixing the clarifying additive with an anionic surfactant prior to contacting the clarifying additive with the liquid.
8. The method of claim 1, wherein the liquid further comprises an anionic surfactant, and wherein the clarifying additive is contacted with the liquid and anionic surfactant simultaneously.
9. The method of claim 1, wherein the biosurfactant is a sophorolipid.
10. The method of claim 9, wherein the sophorolipids comprise a mixture of linear and lactonic sophorolipids having 20% or greater linear sophorolipids with respect to the total amount of the sophorolipids.
11. The method of claim 1, wherein the total concentration of sophorolipids with respect to the treated liquid is about 50 to 1200 ppm.
12. A clarifying additive comprising a biosurfactant and a surfactant, wherein the biosurfactant is a glycolipid and the surfactant is an anionic surfactant.
13. The clarifying additive of claim 12, wherein the anionic surfactant is SLS or SLES.
14. The clarifying additive of claim 12, wherein the glycolipid is a sophorolipid, a rhamnolipid, a trehalose lipid or a mannosylerythritol lipid, or a mixture thereof.
15. The clarifying additive of claim 14, wherein the glycolipid is a sophorolipid, and wherein the sophorolipids comprise a mixture of linear and lactonic sophorolipids having 20% or greater linear sophorolipids with respect to the total amount of the sophorolipids.
16. The clarifying additive of claim 12, comprising the biosurfactant and the anionic surfactant at a ratio of 1 : 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202363581321P | 2023-09-08 | 2023-09-08 | |
| US63/581,321 | 2023-09-08 |
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| WO2025053993A1 true WO2025053993A1 (en) | 2025-03-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2024/042990 Pending WO2025053993A1 (en) | 2023-09-08 | 2024-08-20 | Additives for improving the clarity of hard water |
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| WO (1) | WO2025053993A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014118095A2 (en) * | 2013-01-30 | 2014-08-07 | Unilever Plc | Compositions with improved aesthetic and sensorial properties |
| US20170260072A1 (en) * | 2014-06-03 | 2017-09-14 | Drei Lilien Pvg Gmbh & Co. Kg | Method and devices for de-emulsifying and complexing organic compounds in emulsions |
| CN112119147A (en) * | 2018-05-17 | 2020-12-22 | 荷兰联合利华有限公司 | Cleaning composition |
| US20210130704A1 (en) * | 2017-06-12 | 2021-05-06 | Locus Oil Ip Company, Llc | Remediation of Rag Layer and Other Disposable Layers in Oil Tanks and Storage Equipment |
| CN115895795A (en) * | 2022-12-26 | 2023-04-04 | 媞颂日化用品(广州)有限公司 | Cleaning composition containing biosurfactant and preparation method and application thereof |
-
2024
- 2024-08-20 WO PCT/US2024/042990 patent/WO2025053993A1/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014118095A2 (en) * | 2013-01-30 | 2014-08-07 | Unilever Plc | Compositions with improved aesthetic and sensorial properties |
| US20170260072A1 (en) * | 2014-06-03 | 2017-09-14 | Drei Lilien Pvg Gmbh & Co. Kg | Method and devices for de-emulsifying and complexing organic compounds in emulsions |
| US20210130704A1 (en) * | 2017-06-12 | 2021-05-06 | Locus Oil Ip Company, Llc | Remediation of Rag Layer and Other Disposable Layers in Oil Tanks and Storage Equipment |
| CN112119147A (en) * | 2018-05-17 | 2020-12-22 | 荷兰联合利华有限公司 | Cleaning composition |
| CN115895795A (en) * | 2022-12-26 | 2023-04-04 | 媞颂日化用品(广州)有限公司 | Cleaning composition containing biosurfactant and preparation method and application thereof |
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