WO2015164677A1 - Formulations de nettoyage pour des individus sensibles aux produits chimiques : compositions et procédés - Google Patents

Formulations de nettoyage pour des individus sensibles aux produits chimiques : compositions et procédés Download PDF

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Publication number
WO2015164677A1
WO2015164677A1 PCT/US2015/027403 US2015027403W WO2015164677A1 WO 2015164677 A1 WO2015164677 A1 WO 2015164677A1 US 2015027403 W US2015027403 W US 2015027403W WO 2015164677 A1 WO2015164677 A1 WO 2015164677A1
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Prior art keywords
cleaning
ingredients
ingredient
weight
individuals
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PCT/US2015/027403
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English (en)
Inventor
Gregory Van Buskirk
Anne STEINEMANN
Vinod S. NAIR
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Gregory Van Buskirk
Steinemann Anne
Nair Vinod S
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Application filed by Gregory Van Buskirk, Steinemann Anne, Nair Vinod S filed Critical Gregory Van Buskirk
Priority to EP15782790.8A priority Critical patent/EP3134499A4/fr
Priority to AU2015252006A priority patent/AU2015252006A1/en
Priority to US15/306,109 priority patent/US10767137B2/en
Priority to CA2981702A priority patent/CA2981702A1/fr
Publication of WO2015164677A1 publication Critical patent/WO2015164677A1/fr
Priority to US16/987,416 priority patent/US10968415B2/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the present disclosure relates to cleaning compositions in general, and cleaning compositions well suited for those individuals, who experience multiple chemical sensitivities (MCS), in particular. Individuals with MCS are virtually unable to use commercially available cleaners.
  • MCS chemical sensitivities
  • the instant disclosure concerns the selection of ingredients and methods for formulating and evaluating a series of cleaning products for use by any person, including individuals with MCS.
  • NTA nitrilotriacetic acid
  • VOCs volatile organic compounds
  • cleaning products available in the market today do not explicitly address all aspects of consumer safety. While the vast majority of cleaning product manufacturers ensure that their products cause minimal acute and chronic toxicity problems, exposure to cleaning product chemicals has been associated with the development and exacerbation of asthma and related disorders. However, consumers who may desire to lessen their exposure to harmful chemicals by purchasing safe cleaning products are unable to do so because product ingredients are not fully disclosed on labels. Further, the ingredient profiles of cleaning products that are claimed to be green are remarkably similar to those not labeled green, causing confusion in the minds of consumers looking for safe cleaning products. Indeed, experts on indoor air quality have shown the presence of known carcinogens and hazardous air pollutants even in cleaning products that are free of fragrances and dyes.
  • the methods taught by Long require first the function of a given raw material in a product first be identified, and then a set of predetermined criteria be applied based on the function of the raw material, to determine the raw material's designated environmental class rating, which is then given an environmental grade of from 1-3.
  • the problem with this method is that it requires an individual, burdensome analysis of each component of a composition to arrive at a final value for the composition as a whole.
  • it requires that the individual components be analyzed by their function and one or more components in a composition may have multiple functions.
  • this method requires knowledge of all the components, their percentages in the formulation and their functions in a given formulation, which makes testing products off the shelf impossible or impractical because the required information is often not readily available.
  • This method provides a standardized method for measuring the environmental impact of a given chemical formulation, it too is burdensome and requires too much information about the components and their functions to make it practical for use in testing a wide range of compositions that are available on store shelves.
  • the present disclosure concerns a new scientific protocol for the formulation of cleaning products to minimize the triggering of asthma or other immunological responses in humans.
  • products generated according to the criteria described herein, while virtually non- petroleum based, are equivalent in performance to existing cleaning products on the market.
  • Active ingredient or active material refers to entities that contribute to the cleaning of stains and soils and/or disinfecting of fabrics or surfaces.
  • a chemical mixture as procured from suppliers may be diluted with a solvent such as water, which serves no purpose in cleaning and/or disinfection; in such case, the active ingredient refers only to the portion of the chemical mixture that serves a purpose to clean and/or disinfect.
  • This term does not generally include aesthetic ingredients such as fragrance materials, colorants, viscosity modifiers, preservatives, or the like.
  • Bio-based carbon or bio-based carbon is carbon derived from plant or animal sources that have lived up until the relatively recent past. It is distinguished from carbon derived from fossil sources such as coal, subterranean natural gas, oil or petroleum-based carbon. Bio-based carbon is characterized by the presence of radioactive 14 C, unlike fossil sources of carbon in which radioactive 14 C is depleted or entirely absent.
  • Chemical allergy describes the adverse health effects that my result when exposure to a chemical elicits an immune response in an individual.
  • Chemical allergens are produce reactions similar to allergens such as pollens, weeds, and dander, but appear to be generated when lower-molecular weight chemicals function as haptens and bind to carrier macromolecules. See M.H. Karol, O.T. Macina, and A. Cunningham, "Cell and molecular biology of chemical allergy,” Ann Allergy Asthma Immunol. 87 (2001) 28-32.
  • Cleaning composition or cleaning formulation as used herein refers to a mixture of ingredients assembled together for the purpose of providing an aid to the removal of dirt, soil, grime, food waste, etc., from a surface or individual.
  • a cleaning composition may be formulated for use in cleaning laundry, hard surfaces such as dishes, kitchen surfaces, bathrooms, glass, mirrors, etc., and may be comprised of both of active ingredients and aesthetic ingredients.
  • a cleaning composition is distinguished from a product that is primarily a single cleaning active, such as a bar of soap.
  • a cleaning composition is typically the product presented for sale to consumers.
  • Greenwashing refers to the practice of making or making a false, misleading, or inflated green marketing claims. This practice was expanded upon in December 2007 by the environmental marketing firm TerraChoice. See “The Six Sins of GreenwashingTM,” A 'Green Paper' by TerraChoice Environmental Marketing Inc. (November 2007); http://www.sinsofgreenwashing.com/index6b90.pdf. This article is incorporated herein by reference in its entirety.
  • Haptens are small molecules that are not immunogenic on their own, but which can conjugate to a carrier protein.
  • the protein-hapten conjugate can induce an immune response.
  • Haptens can enter the body through numerous routes, such as skin absorption, inhalation, ingestion and the olfactory pathways. Once inside the body, the haptens can impact any organ or system. Some of these materials are known to cause both skin and respiratory sensitization. It has also been found that skin contact may play a role in respiratory sensitization. See M.H. Karol, O.T. Macina, and A. Cunningham, "Cell and molecular biology of chemical allergy," Ann Allergy Asthma Immunol. 87 (2001) 28-32.
  • Headspace or headspace technology as used herein concerns measurement and characterization of components present in the space above a particular composition or ingredient.
  • Headspace analysis involves removing volatile compounds from the headspace surrounding an object or other material of interest using either an inert gas or by establishing a vacuum. The compounds are then trapped and analyzed with techniques such as gas chromatography, mass spectrometry or Carbon- 13 NMR. ⁇ See, for example, en.wikipedia.org/wiki/Headspace_technology).
  • Modern carbon refers to carbon derived from modern life forms, either plant or animal. It is distinguished from carbon derived from fossil sources such as coal, subterranean natural gas, oil or petroleum-based carbon. It is characterized by presence of radioactive 14 C in its make-up, which is depleted in feedstocks sourced from fossil carbon.
  • Product refers to a cleaning composition or cleaning formulation offered for commercial sale.
  • the term can be understood to be synonymous with cleaning composition or cleaning formulation.
  • Renewable carbon source or renewably sourced carbon is synonymous with modern carbon, and refers to carbon sourced from non-primitive or non- ancient sources, i.e., it is not derived from fossil sources, which is coal, subterranean natural gas, oil or petroleum-based carbon.
  • Renewable carbon source or renewably sourced carbon derives from modern life forms, either plant or animal, and is labeled as renewable because it is relatively easily replenished relative to fossil carbon, which takes millennia if not eons to form. It is characterized by presence of radioactive 14 C in its make-up, which is depleted in feedstocks sourced from fossil carbon.
  • Soap as used herein refers to saponified animal fats and vegetable oils. Soap is understood to be distinguishable from synthetic surfactants, builders, pH adjusters, solvents, soil release agents, antimicrobials, enzymes and bleaching agents.
  • the instant disclosure concerns a multi-tiered approach to screening ingredients for suitability for use in cleaning products, formulating cleaning products that contain acceptable ingredients, and evaluating the resulting cleaning products thus formulated.
  • all cleaning products are combinations of raw materials, which individually may constitute mixtures, the chance of including undesirable chemicals in cleaning products is therefore high without an appropriate screening process.
  • Radiocarbon dating and analysis is a commonly used process to date carbon- based artifacts and remains within the field of archeology. More recently, radiocarbon dating has been used for testing a variety of different products including but not limited to: personal care products, wipes, lubricants, plastics, cleaning products, gardening products, etc. The subject is discussed extensively in "Determining the Modern Carbon Content of Biobased Products Using Radiocarbon Analysis", by G.A. Norton and S.L. Devlin, from Iowa State University, published by Bioresource Technology 97 (2006) 2084-2090; the article in its entirely is herein incorporated by reference.
  • the article on determining modern carbon content describes the process of radiocarbon dating for the determination of bio-based content in a formulation.
  • Several carbon isotopes are present in nature, 12 C, 13 C and 14 C.
  • the 12 C is a stable isotope and the 14 C is an unstable isotope and undergoes radioactive decay.
  • the 14 C is produced in the atmosphere where it is oxidized to C0 2 and C0 2 is then absorbed by plants until the 12 C/ 14 C ratio in all living matter is essentially the same as that in the atmosphere.
  • something dies it stops absorbing carbon and the amount of 14 C diminishes with time, as it naturally undergoes radioactive decay.
  • the rate of decay for the 14 C is measurable and can be calculated.
  • the decay rate for 14 C is slow, about 5730 years, relative to the movement of carbon through the food chain, from plants to animals to bacteria. All carbon in biomass at earth's surface contains atmospheric levels of 14 C whereas petrochemical feedstock that has been dead and in the ground for millions of years will have little to no 14 C. Therefore, material derived from a recently living plant will have an abundance of 14 C that is approximately equal to that in the atmosphere, whereas petrochemical feedstocks will not have a 14 C signature.
  • one can analyze for bio-based or modern carbon content can be carried out by standard test methodology such as radiocarbon analysis, according to ASTM method D6866-05, which relies on analyzing the sample for radioactive 14 C.
  • pMC Percent Modern Carbon
  • ASTM method D6866-05 which relies on analyzing the sample for radioactive 14 C.
  • 14 C analysis and calculations one can determine or confirm the amount of carbon in a material from fossil carbon, which is coal, oil or petroleum-based carbon. By measuring the amount of radioactive carbon in a sample, the amount of modern carbon or bio-based carbon can be determined.
  • the Percent Modern Carbon (pMC), Biorenewable Carbon Index (BCI) or Renewable Carbon Index (RCI) is a measure of the percent of modern or biobased carbon in an individual ingredient or in a composition.
  • the Percent Modern Carbon (pMC), Biorenewable Carbon Index (BCI) or Renewable Carbon Index (RCI) only refers to the element, carbon, in the molecule or compound. Therefore, it is an index of the ratio of new, modern, bio-based carbon to "old", typically petrochemical-based carbon.
  • pMC (as well as its synonymous terms BCI and RCI) does not refer to any other elements such as H, N, O, S, etc. that may be present in a compound.
  • BCI and RCI does not refer to any other elements such as H, N, O, S, etc.
  • One complication in the calculation of pMC is that inorganic carbon, such as that from the carbonates, would be included as "old” carbon, although it might originate from a "natural” mineral source.
  • laboratories do have ways to deal with this complication experimentally and can account for mineral-based carbon. Materials with 100% modern carbon or bio-based carbon have no fossil carbon or petroleum based carbon and are considered carbon from renewable resources.
  • the radioactive carbon dating analysis that serves as the bases for pMC/BMI/RCI may be performed using American Society of Testing Materials (ASTM) method D6866-05, which is herein incorporated by reference.
  • ASTM D6866-05 describes various techniques for measuring radioactive carbon using 1) accelerator mass spectrometry (AMS), 2) benzene synthesis, or 3) carbon dioxide absorption, also known as the carbon dioxide cocktail method.
  • AMS accelerator mass spectrometry
  • benzene synthesis or carbon dioxide absorption methods a liquid scintillation counter (LSC) is used to detect byproducts of the 14 C decay process.
  • LSC liquid scintillation counter
  • the sample composition maybe dehydrated, to prepare the sample for testing.
  • the degree of uncertainty may vary slightly.
  • the degree of uncertainly is approximately 1 to 2%.
  • the degree of uncertainly reaches approximately ⁇ 3%.
  • radioactive carbon count must be corrected for isotropic fractionation to obtain a corrected radiocarbon count.
  • the carbon dioxide cocktail method does not require a correction for isotropic fractionation.
  • the radioactive carbon dating process and analysis may be done for whole compositions or for individual components of compositions, and any combinations or variations thereof.
  • a method for determining the suitability of ingredients for use in the novel cleaning compositions described herein involves performing an assessment of the bio-basis of the ingredient, either through the estimation means described above or by analytical data such as that described in ASTM D6866-05. It is preferable that ingredients used herein are predominantly, if not entirely, renewably sourced, i.e., biologically-based or bio-based, as well as readily and completely biodegradable. It has been found in the course of the present work that individuals with Multiple Chemical Sensitivities or MCS may tolerate ingredients with higher content of modern carbon better than ingredients high in content of non-modern carbon, such as petrochemicals.
  • the analytes from such a headspace determination can be compared against authoritative lists of hazardous ingredients, such as can be found in the Clean Air Act— Toxic and Flammable Substances for Accidental Release Prevention list, the Clean Air Act— Hazardous Air Pollutant list, the Comprehensive Environmental Response, Compensation, and Liability Act— Hazardous Substance list, the Clean Water Act— Priority Pollutant list, the Emergency Planning & Community Right to Know Act— Toxic Release Inventory Chemical list, the Federal Insecticide, Fungicide, and Rodenticide Act— Registered Pesticide list, the Occupational Safety and Health Act— Air Contaminants list, and/or the Resource Conservation and Recovery Act— Hazardous Constituents list.
  • a method for determining the suitability of an ingredient for use in novel cleaning compositions as described herein involves determining the level of VOCs that may be contributed to a final formulation by performing a headspace analysis on the ingredient.
  • a method for determining the suitability of a cleaning composition for use with individuals that exhibit MCS involves determining the level of VOCs in the headspace of the as- formulated cleaning composition. It may be understood that physiological responses may differ for each contaminant, and most preferably none of the analytes found in the headspace is to be found on the authoritative lists. Analytes that might be found on the authoritative lists should be present at levels below about 100 ⁇ g/m 3 , more preferably below 10 ⁇ g/m 3 .
  • cleaning compositions essentially contain no active components that have a vapor pressure exceeding 0.1 mm Hg at 20°C. It is further desirable to screen out chemicals that may react with proteins to form protein-hapten conjugates. Without being bound by theory, it is believed that moieties such as surfactant residues that have a chain length of greater than 8 carbon atoms are insufficiently reactive with proteins to form protein-hapten complexes. Alternatively, it is postulated that any protein-hapten conjugate having greater than an 8-carbon atom chain length that may form, are present in concentrations that are lower than a threshold level needed to trigger an immunogenic response.
  • cleaning products that contain ingredients, especially surfactants with hydrophobic carbon chains that are essentially devoid of carbon chains of 8 or less.
  • surfactants and other moieties having greater than 8-carbon chain lengths are especially preferred.
  • a cleaning composition it is further advantageous for a cleaning composition to also be devoid of impurities that have a vapor pressure exceeding 0.1 mm Hg at 20°C. Impurity or impurities as used herein therefore refer to an ingredient that is not knowingly or intentionally desired to be incorporated into a cleaning composition of the instant disclosure by a formulator or other individual, as will be readily understood by one skilled in the relevant art.
  • a method for determining the suitability of ingredients for use in novel cleaning compositions as described herein involves selecting ingredients that contain no active component that has a vapor pressure exceeding 0.1 mm Hg at 20°C.
  • a method for determining the suitability of ingredients for use in formulating the novel cleaning compositions described herein involves selecting ingredients that contain no impurities that have a vapor pressure greater than 0.1 mm Hg at 20°C.
  • Marketing studies have confirmed that consumers associate fragrance substantivity with increased cleanliness. However, multiple scientific studies have implicated fragrances as being the culprit in exacerbating or causing deleterious health effects in susceptible individuals or entire segments of the population. It is therefore preferable to incorporate fragrances that are known to not cause deleterious effects. Without being bound by theory, the incorporation of optically active isomers of fragrance molecules in their naturally occurring form is favored as possibly having less adverse effects than their synthetic analogs.
  • candidate ingredients are identified and tested as described above, they are evaluated for use in potential cleaning formulations using a blind study protocol.
  • the blind studies used in the course of the instant work were comprised of a specially selected panel of volunteers. Volunteers diagnosed with both multiple chemical sensitivities (MCS) and asthma have been found to be able to detect the presence of problematic chemicals, even at low levels. A panel comprised of just such individuals was used for many aspects of the studies conducted herein. While animals use olfactory-mediated defense systems to detect, locate and identify predators in their surrounding environment, it has been found that human subjects are similarly able to discriminate among negative odors accurately. See E.A. Krusemark and W. Li, "Enhanced olfactory sensory perception of threat in anxiety: An event-related fMRI study," Chemosensory Perception, 5 (2012) 37-45; the article in its entirely is herein incorporated by reference.
  • step 1. evaluating the ingredient or ingredients from step 1. for acceptability by at least one individual who manifests multiple chemical sensitivities;
  • VOC volatile organic carbon
  • cleaning products using these approved chemicals may then be formulated and evaluated for efficacy.
  • evaluations of fully formulated products were then carried out via sensory evaluation and VOC analysis. This permits further evaluation of the suitability of product formulations and the ability to assess product performance as compared with existing cleaning products. This was done on a qualitative rating scale both for cleaning efficacy and for presumed safety.
  • a method for providing cleaning formulations for use by chemically-sensitized individuals in addition to the general public involves:
  • step 1 evaluating the ingredient or ingredients from step 1. for acceptability by at least one individual who manifests multiple chemical sensitivities;
  • step 4 performing a VOC headspace analysis of the cleaning product formulated in step 3, wherein a headspace analysis of less than about 100 ⁇ g/m 3 is regarded as acceptable.
  • a method for providing cleaning products for use by chemically-sensitized individuals as well as for the general public involves, in addition to steps 1. through 4. above, at least one of the steps of:
  • a method for providing cleaning products that are particularly well suited for use by chemically-sensitized individuals includes:
  • step 1 evaluating the ingredient or ingredients from step 1. for acceptability by at least one individual who manifests multiple chemical sensitivities;
  • step 4 performing a headspace analysis of the cleaning product formulated in step 3; wherein assessing step 1. includes an analysis of the feedstock of the ingredient or ingredients according to ASTM method D6866-05 or one consistent therewith.
  • a method for providing cleaning products according to the instant disclosure includes any of assessing steps 1. above, further wherein the assessing is achieved by analysis according to or consistent with ASTM D6866-05.
  • a method for providing cleaning products that are particularly well suited for use by chemically-sensitized individuals as well as the general public includes:
  • step 1 evaluating the ingredient or ingredients from step 1. for acceptability by at least one individual who manifests multiple chemical sensitivities;
  • step 1. performing a headspace analysis of the cleaning product formulated in step 3; wherein assessing step 1. includes an analysis of the feedstock of the ingredient or ingredients by analysis that may be according to ASTM method D6866-05, a method that is consistent therewith, by consulting appropriate tabulated material, or by any combination of the foregoing.
  • a method for providing cleaning products that are particularly well suited for use by chemically-sensitized individuals as well as the general public, includes, in addition to any of steps 1. through 5. above, at least one of the following criteria: a. the ingredient or ingredients of step 1. have a pMC of at least 80%, more preferably at least 85%, and most preferably at least 90%;
  • the cleaning formulation has a pMC of at least 90%, more preferably at least 95%, and most preferably at least 99%;
  • the cleaning formulation is deemed acceptable by at least one individual who manifests multiple chemical sensitivities or MCS.
  • a cleaning product according to the disclosure herein that is particularly well suited for use by chemically-sensitized individuals as well as the general public, includes: a composition comprising at least one ingredient that is a non-soap cleaning active, wherein the ingredient has a pMC of at least 80%, wherein a headspace analysis of the composition reveals the absence of phenyl compounds or their derivatives, wherein less than about 5% by weight of the ingredients have a vapor pressure that is above 0.1 mm Hg at 20°C, wherein the composition contains less than about 1% by weight of a fragrance material; wherein headspace analysis of the cleaning product reveals less than about 1000 ⁇ g/m 3 VOCs that are regulated by governmental bodies; and wherein the composition has less than 0.1%) by weight of ingredients that have been demonstrated to cause adverse reactions in chemically-sensitive individuals.
  • Cleaning formulations are generally comprised of a mixture of ingredients, each of which serves a purpose in the removal of soils and stains.
  • such formulations can include one or more of the following active ingredients: surfactants, builders, pH adjusters, solvents, soil release agents, antimicrobials, enzymes and bleaching agents.
  • Such formulations often include ingredients that are more aesthetic in their function: fragrance materials, dyes and colorants, viscosity control agents, pearlizing and opacifying agents, brighteners, preservatives, etc.
  • Cleaning compositions according to the instant disclosure can contain an anionic surfactant.
  • an anionic surfactant When an anionic surfactant is added to the compositions described herein, it can typically be added at a level from about 0.05% to about 15% by weight, preferably from about 0.05% to about 5% by weight, and more preferably from about 0.1% to about 1% by weight of the composition.
  • anionic surfactants have alkyl chain lengths greater than 10. It is further preferred that they be sourced from bio-based materials rather than petrochemicals. While this largely eliminates phenyl derivatives, it is envisioned that these materials could also be sourced from bio- based materials. It is yet further preferred that these materials be devoid of contaminants such as 1,4-dioxane.
  • Anionic surfactants suitable for use in the formulations discussed herein include C 10 -C 14 alkyl sulfates and ethoxysulfates (e.g., Stepanol WA-EXTRA from Stepan Company), C 10 -C 18 alkyl sulfonates, C 10 -C 14 linear or branched alkyl benzene sulfonates, and C 10 -C 15 alkyl ethoxycarboxylate.
  • Anionic surfactants may be paired with organic counterions or multivalent counterions in order to prevent interference with cationic species. Further examples of suitable surfactants are described in McCutcheon's Vol. 1 : Emulsifiers and Detergents, North American Ed., McCutcheon Division, MC Publishing Co., 1995, which is incorporated herein by reference.
  • anionic surfactants containing ethylene oxide either through petrochemical or bio-based sources, contained detectable levels of 1,4-dioxane as a contaminant. Such surfactants are to be scrupulously avoided, with preference given to anionic surfactants that have no detectable level of 1,4-dioxane.
  • anionic surfactants are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to air, moisture or sunlight.
  • NONIONIC SURFACTANTS are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to air, moisture or sunlight.
  • compositions can contain a nonionic surfactant.
  • a nonionic surfactant When a nonionic surfactant is added to the composition, it can typically be added at a level from about 0.05% to about 30% by weight, preferably from about 0.05%> to about 20%> by weight, and more preferably from about 0.1% to about 10% by weight of the composition.
  • Nonionic surfactants that are suitable for use herein include alkylpolysaccharides, as disclosed in U.S. Patent No. 4,565,647 to Llenado, incorporated herein by reference. Especially preferred are those nonionic surfactants that have a hydrophobic group containing from about 10 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms in addition to at least one hydrophilic saccharide group such as glucose. Most preferred are alkylpolysaccharides whose hydrophobic groups are sourced from bio-based materials such as coconut or palm oil, and whose hydrophilic groups are source from bio-based materials, an example of which is glucose sourced from corn. Certain alkylpolysaccharides that contain low levels of phenyl derivatives may also be acceptable for use with the formulations presented herein, providing the source of phenyl is bio-based.
  • nonionic surfactants include addition products of fatty alcohols, fatty acids, and fatty amines (most preferably sourced from bio-based materials such as vegetable oils), coupled with alkoxylating agents such as ethylene oxide (EO), propylene oxide (PO), isopropylene oxide (IPO), or butylene oxide (BO), or a mixture thereof. While most alkylene oxide units are derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources in the future. Moreover, it was found that a number of such ingredients had detectable levels of 1,4-dioxane as a contaminant.
  • alkoxylating agents such as ethylene oxide (EO), propylene oxide (PO), isopropylene oxide (IPO), or butylene oxide (BO), or a mixture thereof. While most alkylene oxide units are derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources in the future
  • nonionic surfactant is selected from the group consisting of primary and secondary alcohol ethoxylates as well as mixtures thereof.
  • Nonionic surfactants may also contain a mixture of alcohol ethoxylates and propoxylates and mixtures thereof. Further examples of suitable surfactants are described in McCutcheon's Vol. 1 : Emulsifiers and Detergents, North American Ed., McCutcheon Division, MC Publishing Co., 1995, which is incorporated herein by reference.
  • Highly preferred nonionic surfactants are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices or fabrics into which they are introduced or applied, either during treatment followed by drying and/or curing, or after drying and/or curing followed by normal exposure to air, moisture or sunlight exposure.
  • compositions of the present disclosure can contain amphoteric and/or zwitterionic surfactants.
  • an amphoteric or zwitterionic surfactant When an amphoteric or zwitterionic surfactant is added to a composition of the present disclosure, it can typically be added at a level from about 0.05% to about 30%, preferably from about 0.05%> to about 20%> by weight, and more preferably from about 0.1% to about 10% by weight of the composition.
  • Suitable amphoteric surfactants include amine oxides having the formula (Ri)(R 2 )(R 3 )NC ) wherein each of Ri, R 2 and R 3 is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chain containing from 1 to 30 carbon atoms.
  • Preferred amine oxide surfactants that can be used herein include amine oxides having the formula (Ri)(R 2 )(R 3 )NO wherein Ri is a hydrocarbon chain having from 1 to 30 carbon atoms, preferably from 10 to 20, more preferably from 10 to 16, further preferably from 10 to 12, and wherein R 2 and R 3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups. Ri may be a saturated substituted or unsubstituted, linear or branched hydrocarbon chain.
  • Suitable amine oxides for use herein are, for instance, naturally derived C 12 -C 16 amine oxides commercially available from Lonza Group and Stepan Company. It is especially preferred that the pendent alkyl groups R 2 and R 3 are derived from bio-based sources, such as wood alcohol.
  • Suitable zwitterionic surfactants for use with the formulations presented herein may contain both cationic and anionic hydrophilic groups on the same molecule at a relatively wide pH range.
  • a typical cationic group is a quaternary ammonium group, although other positively charged groups like phosphonium, imidazolium and sulfonium groups can be used.
  • Typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
  • Ri- N'(R 2 )(R 3 )R 4 X A generic formula for some zwitterionic surfactants that can be used herein is Ri- N'(R 2 )(R 3 )R 4 X, wherein Ri is a hydrophobic group comprising from 10 to 30 carbon atoms; R 2 and R 3 are each C 1 -C4 alkyl, hydroxyalkyl or other substituted alkyl group which can also be joined to form ring structures with the N; R 4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group which is preferably a carboxylate or sulfonate group.
  • Preferred hydrophobic groups Ri are bio-based alkyl groups containing from 10 to 24, preferably less than 18, and more preferably less than 16 carbon atoms.
  • the hydrophobic group can contain unsaturation and/or substituents and/or linking groups such as aryl groups, amido groups, ester groups and the like.
  • the simple alkyl groups are preferred for cost and stability reasons.
  • the pendent alkyl groups R 2 and R 3 could be derived from bio-based sources, such as methyl groups derived from bio-based sources such as wood alcohol.
  • amphoteric surfactants include alkylamphoglycinates, and alkyl iminopropionate.
  • Highly preferred zwitterionic surfactants include betaine and sulphobetaine surfactants, derivatives thereof or mixtures thereof.
  • the betaine or sulphobetaine surfactants are preferred herein as they are particularly suitable for the cleaning of delicate materials, including fine fabrics such as silk, wool and other naturally derived textile materials.
  • Betaine and sulphobetaine surfactants are also extremely mild to the skin and/or fabrics to be treated that come in contact with the user's skin.
  • Suitable betaine and sulphobetaine surfactants to be used herein include the betaine/sulphobetaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of pH values.
  • Some common examples of these detergents are described in U.S. Patent No. 2,082,275 to Daimler, et al., U.S. Patent No. 2,702,279 to Funderburk, et al, and U.S. Patent No. 2,255,082 to Orthner, et al., which are incorporated herein by reference.
  • Further examples of suitable surfactants are described in McCutcheon's Vol. 1 : Emulsifiers and Detergents, North American Ed., McCutcheon Division, MC Publishing Co., 1995, which is incorporated herein by reference.
  • Highly preferred materials of this class of amphoteric and zwitterionic surfactants are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • compositions of the present disclosure can contain a cationic surfactant.
  • a cationic surfactant When a cationic surfactant is added to the compositions disclosed herein, it can typically be added at a level from about 0.05% to about 30%> by weight, preferably from about 0.05%) to about 20%> by weight, and more preferably from about 0.1 % to about 10%) by weight of the composition.
  • the cationic surfactant can optionally be one or more fabric softener actives.
  • Preferred fabric softening actives according to the present disclosure include amines and quaternized amines. The following are examples of preferred softener actives: N,N-di(tallowyl-oxy-ethyl)-N.N-dimethyl ammonium chloride; N,N-di(canolyl-oxy- ethyl)-N,N-dimethyl ammonium chloride; N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2- hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2- hydroxyethyl) ammonium methyl sulfate; N,N-di(tallowylamidoethyl)-N-methyl, N-(2- hydroxyethyl
  • N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride where the tallow chains are at least partially unsaturated and N,N-di(canoloyl-oxy- ethyl)-N,N- dimethyl ammonium chloride, N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2- hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2- hydroxyethyl) ammonium methyl sulfate; and mixtures thereof.
  • Suitable cationic surfactants include ethoxylated quaternary ammonium surfactants.
  • Some preferred ethoxylated quaternary ammonium surfactants include PEG-5 cocoammonium methosulfate; PEG- 15 cocoammonium chloride; PEG- 15 oleoammonium chloride; and bis(polyethoxyethanol) tallow ammonium chloride. While these cationic surfactants are not preferred due to the ethylene oxide units usually being petrochemically-based, it is envisioned that the ethylene oxide units could also be bio-based. Further examples of suitable surfactants are described in McCutcheon's Vol. 1 : Emulsifiers and Detergents, North American Ed., McCutcheon Division, MC Publishing Co., 1995, which is incorporated herein by reference.
  • the counterion to these cationic surfactants may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like.
  • Highly preferred materials of this class of cationic surfactants and their counterions are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Builders are materials used to boost the performance of surfactants used for cleaning. Their best builder compounds react with multivalent cations, “softening” water by removing “hardness” ions (e.g., calcium and magnesium) that bind with surfactants, reducing their effectiveness. Moreover these hardness ions can react with stains, making them more difficult to remove. Some builders also modify solution pH to provide alkalinity, which aids cleaning (stain neutralization, saponification, surface modification). Further, some builders can disperse and/or suspend soils, due to their ability to modify the surface charge on the soils that come into solution.
  • hardness ions e.g., calcium and magnesium
  • Some builders also modify solution pH to provide alkalinity, which aids cleaning (stain neutralization, saponification, surface modification). Further, some builders can disperse and/or suspend soils, due to their ability to modify the surface charge on the soils that come into solution.
  • Adjustment of pH may be carried out by including a small quantity of an acid in the formulation. Because no strong pH buffers need be present, only small amounts of acid may be required.
  • the pH may be adjusted with inorganic or organic acids, for example hydrochloric acid or alternatively with monobasic or dibasic organic acids, such as acetic acid, maleic acid or in particular glycolic acid. Additional acids that can be used include, but are not limited to, methyl sulfonic, hydrochloric, sulfuric, phosphoric, citric, maleic, and succinic acids.
  • Adjustment of pH may be carried out by including a small quantity of a base in the formulation. Because no strong pH buffers need be present, only small amounts of base may be required.
  • the pH may be adjusted with inorganic bases, including, but not limited to, alkali metal or alkaline earth metal salts of hydroxides, carbonates, bicarbonates, borates, sulfonates, phosphates, phosphonates and silicates.
  • the pH may be adjusted with organic bases, including, but not limited to, salts of monocarboxylic acids, salts of dicarboxylic acids, salts of citric acid and other suitable organic acids with water soluble conjugate bases presented previously herein.
  • the pH may be adjusted with organic bases such as the alkanolamines including methanol, ethanol and propanol amines, including dimethanol-, diethanol- and dipropanolamines, and including trimethanol-, triethanol- and tripropanolamines.
  • organic bases such as the alkanolamines including methanol, ethanol and propanol amines, including dimethanol-, diethanol- and dipropanolamines, and including trimethanol-, triethanol- and tripropanolamines.
  • highly preferred materials of this class of pH adjusters are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the cleaning compositions can contain organic solvents that act as diluents, coupling agents, and to some extent aid cleaning. It is preferred that such solvents be bio-based, and while many solvents are typically obtained from petrochemical sources, it is envisioned that they could be derived from bio-based sources. Further preferred are solvents that do not appreciably contribute to VOCs.
  • organic solvents include, but are not limited to, Ci-C 6 alkanols, Ci-C 6 diols, Ci-Cio alkyl ethers of alkylene glycols, C3-C24 alkylene glycol ethers, polyalkylene glycols, short chain carboxylic acids, short chain esters, isoparaffinic hydrocarbons, mineral spirits, alkylaromatics, terpenes, terpene derivatives, terpenoids, terpenoid derivatives, formaldehyde, and pyrrolidones.
  • Alkanols include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, and hexanol, and isomers thereof.
  • Diols include, but are not limited to, methylene, ethylene, propylene and butylene glycols.
  • Alkylene glycol ethers include, but are not limited to, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, di- or tri-polypropylene glycol methyl or ethyl or propyl or butyl ether, acetate and propionate esters of glycol ethers.
  • Short chain esters include, but are not limited to, glycol acetate, and cyclic or linear volatile methylsiloxanes.
  • Water insoluble solvents such as isoparaffinic hydrocarbons, mineral spirits, alkylaromatics, terpenoids, terpenoid derivatives, terpenes, and terpenes derivatives can be mixed with a water-soluble solvent when employed.
  • the composition can include a soil release agent that is present from about 0% to about 5% by weight, preferably from about 0.05% to about 3% by weight, and more preferably from about 0.1% to about 2% by weight of the composition.
  • Polymeric soil release agents useful in the present disclosure include co-polymeric blocks of terephthalate and polyethylene oxide or polypropylene oxide, and the like.
  • a preferred soil release agent is a copolymer having blocks of terephthalate and polyethylene oxide. While most terephthalate and alkylene oxide units are derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources.
  • These polymers may be comprised of repeating units of ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units from about 25:75 to about 35:65, and the polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights from about 300 to about 2000.
  • the molecular weight of this type of polymeric soil release agent can be in the range from about 5,000 to about 55,000. Suitable soil release agents are disclosed in U.S. Patent Nos.
  • polymeric soil release agents comprising block copolymers of polyalkylene terephthalate and polyoxyethylene terephthalate, and block copolymers of polyalkylene terephthalate and polyethylene glycol.
  • the polyalkylene terephthalate blocks may preferably comprise ethylene and/or propylene groups.
  • soil release polymers are nonionic, for example, the nonionic soil release polymer described in U.S. Patent No. 4,849,257 to Borcher, Sr., et al, which is incorporated herein by reference.
  • the polymeric soil release agents useful in the present disclosure can include anionic and cationic polymeric soil release agents. Suitable anionic polymeric or oligomeric soil release agents are disclosed in U.S. Patent No. 4,018,569 to Chang, which is incorporated herein by reference. Other suitable polymers are disclosed in U.S. Patent No. 4, 808,086 to Evans, et al, which is incorporated herein by reference.
  • Highly preferred materials of this class of soil release polymers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the composition can include antistatic agents, which can be present at a level from about 0% to about 5% by weight, preferably from about 0.005% to about 5% by weight, more preferably from about 0.05% to about 2% by weight, and further preferably from about 0.2% to about 1% of the composition. While many of these compounds are derived from petrochemical sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources.
  • Preferred antistatic agents of the present disclosure include cationic surfactants, including quaternary ammonium compounds such as alkyl benzyl dimethyl ammonium chloride; dicoco quaternary ammonium chloride; coco dimethyl benzyl ammonium chloride; soya trimethyl quaternary ammonium chloride; hydrogenated tallow dimethyl benzyl ammonium chloride; and methyl dihydrogenated tallow benzyl ammonium chloride.
  • Other preferred antistatic agents of the present disclosure are alkyl imidazolinium salts.
  • preferred antistatic agents are the ion pairs of, e.g., anionic detergent surfactants and fatty amines, or quaternary ammonium derivatives thereof, e.g., those disclosed in U.S. Patent No. 4,756,850 to Nayar, which is incorporated herein by reference.
  • Other preferred antistatic agents are ethoxylated and/or propoxylated sugar derivatives; while most alkylene oxide units are derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources.
  • Preferred antistatic agents include monolauryl trimethyl ammonium chloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride (available from BASF Corporation under the trade name DEHY QUART E), and ethyl bis(polyethoxyethanol) alkyl ammonium ethyl sulfate (available from Evonik Corporation under the trade name VARIQUAT 66), polyethylene glycols, polymeric quaternary ammonium salts (such as those available from Rhodia Group under the MIRAPOL trade name), quaternized polyethyleneimines, vinylpyrrolidone/methacrylamidopropyl trimethylammonium chloride copolymer (available from Ashland Inc. under the trade name GAFQUAT HS- 100), triethonium hydro lyzed collagen ethosulfate (available from Angene Chemical under the trade name QUAT-PRO E), and mixtures thereof.
  • monolauryl trimethyl ammonium chloride available from BASF Corporation under the trade
  • Highly preferred materials of this class of antistatic agents are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • fragrance materials While not preferred due to their propensity to induce untoward symptoms in sensitized individuals, it has been discovered that truly natural, bio-based fragrance materials may be added to the composition. It appears that preferred fragrance materials are comprised of extracts of natural products, upon which no additional functionalization reactions have been carried out. Further, preferred fragrance materials should not have been isolated in such a way as to introduce petrochemical solvents, which appear to further exacerbate symptoms of sensitization. Such materials may have been isolated by methods well-known to the industry such as extraction with suitable solvents, supercritical fluid extraction, steam distillation, rectification, and expression. It is also foreseen that by adding fragrance sources such as plant materials directly to the product, and relying on the product matrix itself to extract the desired fragrance notes, one can obtain desired fragrance notes.
  • the selection of the perfume or perfumes maybe based upon the application, the desired effect on the consumer, and preferences of the formulator.
  • the perfume selected for use in the compositions and formulations of the present disclosure may contain ingredients with odor characteristics which are preferred in order to provide a fresh impression on the surface to which the composition is directed, for example, those which provide a fresh impression for fabrics.
  • Such perfume may be preferably present at a level from about 0.01 % to about 5% by weight, preferably from about 0.05% to about 3% by weight, and more preferably from about 0.1 % to about 2% by weight of the total composition.
  • the fragrance materials are mixtures comprising multiple ingredients selected from the group consisting of aromatic and aliphatic esters having molecular weights from about 130 to about 250; aliphatic and aromatic alcohols having molecular weights from about 90 to about 240; aliphatic ketones having molecular weights from about 150 to about 260; aromatic ketones having molecular weights from about 150 to about 270; aromatic and aliphatic lactones having molecular weights from about 130 to about 290; aliphatic aldehydes having molecular weights from about 140 to about 200; aromatic aldehydes having molecular weights from about 90 to about 230; aliphatic and aromatic ethers having molecular weights from about 150 to about 270; and condensation products of aldehydes and amines having molecular weights from about 180 to about 320; and mixtures thereof.
  • aromatic and aliphatic esters having molecular weights from about 130 to about 250
  • aliphatic and aromatic alcohols having molecular weight
  • Highly preferred materials of this class of fragrances and perfumes are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Antimicrobials and/or preservatives can be used with the formulations presented herein.
  • Typical concentrations for biocidal effectiveness of these compounds may range from about 0.001% to about 0.8% by weight, preferably from about 0.005% to about 0.3%) by weight, and more preferably from about 0.01% to 0.2%> by weight of the usage composition.
  • the corresponding concentrations for the concentrated compositions are from about 0.003% to about 2% by weight, preferably from about 0.006%) to about 1.2% by weight, and more preferably from about 0.1 % to about 0.8%> by weight of the concentrated compositions.
  • Preservatives are especially preferred when organic compounds that are subject to microorganisms are added to the compositions of the present disclosure, especially when they are used in aqueous compositions.
  • organic compounds that are subject to microorganisms are added to the compositions of the present disclosure, especially when they are used in aqueous compositions.
  • long term and even short-term storage stability of the compositions and formulations becomes an important issue since contamination by certain microorganisms with subsequent microbial growth often results in an unsightly and/or malodorous solution. Therefore, because microbial growth in these compositions and formulations is highly objectionable when it occurs, it is preferable to include a solubilized water-soluble, antimicrobial preservative, which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the preferably clear and often aqueous compositions and formulations of the present disclosure.
  • Typical microorganisms that can be found in laundry products include bacteria, for example, Bacillus thurigensis (cereus group) and Bacillus sphaericus, and fungi, for example, Aspergillus ustus.
  • Bacillus sphaericus is one of the most numerous members of Bacillus species in soils.
  • microorganisms such as Escherichia coli and Pseudomonas aeruginosa are found in some water sources, and can be introduced during the preparation of aqueous solutions of the present disclosure. It is preferable to use a broad spectrum preservative, for example, one that is effective on both bacteria (both Gram positive and Gram negative) and fungi.
  • a limited spectrum preservative for example, one that is only effective on a single group of microorganisms, for example, fungi, can be used in combination with a broad spectrum preservative or other limited spectrum preservatives with complimentary and/or supplementary activity.
  • a mixture of broad-spectrum preservatives can also be used.
  • Antimicrobial preservatives useful in the present disclosure can be biocidal compounds, that is, substances that kill microorganisms, or biostatic compounds, that is, substances that inhibit and/or regulate the growth of microorganisms.
  • Preferred antimicrobial preservatives include those that are water-soluble and are effective at low levels. While such compounds are commonly derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources.
  • the water-soluble preservatives that may be used include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary compounds, dehydroacetic acid, phenyl and phenoxy compounds, and mixtures thereof.
  • preservatives useful with the formulations presented herein include, but are not limited to, the short chain alkyl esters of p-hydroxybenzoic acid (commonly known as parabens); N-(4-chlorophenyl)-N-(3,4-dichlorophenyl) urea (also known as 3,4,4- trichlorocarbanilide or triclocarban); 2,4,4-trichloro-2'-hydroxydiphenyl ether, commonly known as Triclosan®); a mixture of about 77% 5-chloro-2-methyl-4- isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available from the Dow Chemical Company as a 1.5% aqueous solution under the trade name KATHON CG; 5-bromo-5-nitro-l,3-dioxane, available from BASF Corporation under the trade name BRONIDOX L; 2-bromo-2-nitropropane-l
  • GERMALL II N,N"-methylenebis-[N'-[l-(hydroxymethyl)-2,5-dioxo-4- imidazolidinyljurea] (commonly known as imidazolidinyl urea), available, for example, from 3V-Sigma under the trade name ABIOL, from Induchem USA, Inc. under the trade name UNICIDE U-13, and from Ashland Inc. under the trade name GERMALL 115; polymethoxy bicyclic oxazolidine, available from Ashland Inc.
  • the preservative can be any organic preservative material that is appropriate for applying to a fabric.
  • such preservative(s) will preferably not cause damage to a fabric appearance, for example, through discoloration, coloration, or bleaching of the fabric.
  • the antimicrobial preservative is included in the compositions and formulations of the present disclosure, it is preferably present in an effective amount, wherein an "effective amount” means a level sufficient to prevent spoilage or prevent growth of inadvertently added microorganisms for a specific period of time.
  • an "effective amount” means a level sufficient to prevent spoilage or prevent growth of inadvertently added microorganisms for a specific period of time.
  • Preferred levels of preservative are from about 0.0001% to about 0.5% by weight, more preferably from about 0.0002% to about 0.2%) by weight, further preferably from about 0.0003%) to about 0.1 %> by weight, of the composition.
  • the preservative can be used at a level that provides an antimicrobial effect on the treated fabrics.
  • the composition may suitably use an optional solubilized, water-soluble antimicrobial active, useful in providing protection against organisms that become attached to the treated material.
  • the free, uncomplexed antimicrobial, e.g., antibacterial, active provides an optimum antibacterial performance. Sanitization of fabrics can be achieved by the compositions of the present disclosure containing, antimicrobial materials, e.g., antibacterial halogenated compounds, quaternary compounds, and phenolic compounds.
  • Some of the more robust antimicrobial halogenated compounds which can function as disinfectants/sanitizers as well as finish product preservatives, and are useful in the compositions of the present disclosure include 1 , ⁇ -hexamethylene bis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, in addition to its salts, e.g., with hydrochloric, acetic and gluconic acids.
  • the digluconate salt is highly water-soluble, at about 70% by weight in water, while the diacetate salt has a solubility of about 1.8% weight in water.
  • chlorhexidine When chlorhexidine is used as a sanitizer with the formulations discussed herein, it can typically be present at a level from about 0.001% to about 1.0% by weight, preferably from about 0.002% to about 0.3%) by weight, and more preferably from about 0.01% to about 0.1 %> by weight of the usage composition. In some cases, a level from about 1%> to about 2%> by weight may be needed for virucidal activity.
  • Other useful biguanide compounds include COSMOCIL CQ, VANTOCIL IB, including poly (hexamethylene biguanide) hydrochloride.
  • Other useful cationic antimicrobial agents include the bis-biguanide alkanes.
  • Usable water soluble salts of the above are chlorides, bromides, sulfates, alkyl sulfonates such as methyl sulfonate and ethyl sulfonate, phenylsulfonates such as p- methylphenyl sulfonates, nitrates, acetates, gluconates, and the like.
  • Non- limiting examples of useful quaternary compounds include: (1) benzalkonium chlorides and/or substituted benzalkonium chlorides such as commercially available BARQUAT (available from Lonza), MAQUAT (available from Pilot Chemical), VARIQUAT (available from Evonik), and HY AMINE (available from Lonza); (2) dialkyl quaternary such as BARD AC products of Lonza, (3) N-(3- chloroallyl) hexaminium chlorides such as DOWICIDE and DOWICIL available from Dow; (4) benzethonium chloride such as HY AMINE 1622 from Lonza; (5) methylbenzethonium chloride represented by HY AMINE 10X supplied by Lonza, (6) cetylpyridinium chloride such as Cepacol chloride available from of Merrell Labs.
  • BARQUAT available from Lonza
  • MAQUAT available from Pilot Chemical
  • VARIQUAT available from Evonik
  • HY AMINE available from Lonza
  • Preferred antimicrobial compounds for use herein include quaternary ammonium compounds containing alkylor substituted alkyl groups, alkyl amide and carboxylic acid groups, ether groups, unsaturated alkyl groups, and cyclic quaternary ammonium compounds, which can be chlorides, dichlorides, bromides, methylsulphates, chlorophenates, cylcohexyl sulphamates or salts of the other acids.
  • alkylpyridinium chlorides and/or sulphates the alkyl group being preferably cetyl, dodecyl or hexadecyl group
  • -alkylisoquinolyl chlorides and/or bromides the alkyl group being preferably dodecyl group.
  • Particularly suitable quaternary ammonium compounds for use herein include alkyldimethylbenzyl ammonium chloride, octyl decyl dimethylammonium chloride, dioctyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, alkyl dimethyl ammonium saccharinate, cetylpyridinium and mixtures thereof.
  • inorganic materials based on silver, copper, or clays materials such as DragoniteTM Halloysite clay (Applied Minerals, New York, NY) may be suitable for this purpose.
  • Silver and copper materials may be embedded within the packaging matrix, so as to keep liquids contained therein preserved.
  • Highly preferred materials of this class of antimicrobials and preservatives are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Colorants can be added to the formulations disclosed herein. As many people manifest sensitivity to synthetic dyes, they are not preferred. However, certain natural colorants such as chlorophyll may be suitable for incorporation herein. Pigments, which are insoluble colorants, may also be suitable for incorporation in the formulations described herein. Typical concentrations of these compounds may range from about 0.001% to about 0.8% by weight, preferably from about 0.005% to about 0.3% by weight, and more preferably from about 0.01% to 0.2% by weight of the composition.
  • Colorants and dyes, especially bluing agents can be optionally added to the compositions of the present disclosure for visual appeal and performance impression. When colorants are used, they may be used at extremely low levels to avoid fabric staining.
  • Highly preferred materials of this class of dyes and colorants are those that do not effectively bind to or permanently dye or color fabrics treated by use of the compositions disclosed herein, nor cause any significant color change, nor impart any discoloration, such as graying, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Optionally added viscosity control agents can be organic or inorganic in nature and may either lower or raise the viscosity of the formulation. While many such compounds are commonly derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources.
  • organic viscosity modifiers to lower viscosity are aryl carboxylates and sulfonates (for example including, but not limited to benzoate, 2-hydroxybenzoate, 2- aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2- aminobenzenesulfonate), fatty acids and esters, fatty alcohols, and water-miscible solvents such as short chain alcohols.
  • inorganic viscosity control agents are water-soluble ionizable salts.
  • ionizable salts can be used.
  • suitable salts are the halides and acetates of ammonium ion and the group IA and IIA metals of the Periodic Table of the Elements, for example, calcium chloride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, ammonium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, ammonium iodide, sodium acetate, potassium acetate, or mixtures thereof.
  • the ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity.
  • the amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desire of the formulator. Typical levels of salts used to control the composition viscosity are from 0 to about 10% by weight, preferably from about 0.01% to about 6%> by weight, and more preferably from about 0.02% to about 3% by weight of the composition.
  • Viscosity modifiers or thickening agents can be added to increase the ability of the compositions to stably suspend water-insoluble articles, for example, perfume microcapsules.
  • Such materials include hydroxypropyl substituted guar gum (such as that available from Rhodia Group under the trade name JAGUAR HP200), polyethylene glycol (such as that available from Dow Chemical Corporation under the trade name CARBOWAX 20M), hydrophobically modified hydroxyethylcellulose (such as that available from the Ashland Inc.
  • viscosity raisers or thickeners can typically be used at levels from about 0.5% to about 30%) by weight, preferably from about 1% to about 5% by weight, more preferably from about 1.5% to about 3.5% by weight, and further preferably from about 2% to about 3%) by weight, of the composition.
  • Highly preferred materials of this class of thickeners and viscosity control and viscosity modifiers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Examples of pearlizing or opacifmg agents that can be added to the compositions disclosed herein include, but are not restricted to, glycol distearate, propylene glycol distearate, and glycol stearate. Some of these products are available from PMC Group under the KEMESTER trade name. While many such compounds are commonly derived from petrochemicals sources at present, and are as such not preferred, it is envisioned that they could be derived from bio-based sources at some future point.
  • Highly preferred materials of this class of pearlizing and opacifying agents are those that do bind to treated fabrics, nor cause any significant color change nor impart any discoloration, such as whitening, graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • antioxidants examples include propyl gallate, available from Eastman Chemical Products, Inc. under the trade names TENOX PG and TENOX S-l, and dibutylated hydroxytoluene, available from UOP Inc. under the trade name SUSTANE BHT. Also preferred are antioxidants for providing sun-fade protection for fabrics treated with composition of the present disclosure, such antioxidants being described in EP0773982, and incorporated herein by reference.
  • Preferred antioxidants include 2-(N-methyl-N-cocoamino)ethyl-3',5'-di-tert- butyl-4'-hydroxybenzoate; 2-(N, N-dimethyl-amino)ethyl-3',5'-di-tert-butyl-4'- hydroxybenzoate; 2-(N- methyl-N-cocoamino)ethyl-3',4',5'-trihydroxybenzoate; and mixtures thereof, more preferably 2-(N-methyl-N-cocoamino)ethyl-3',5'-di-tert-butyl-4'- hydroxy benzoate.
  • the butylated derivatives are preferred in the compositions of the present disclosure because tri-hydroxybenzoates have a tendency to discolor upon exposure to light. While many such compounds are commonly derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources in the future.
  • the antioxidant compounds of the present disclosure demonstrate light stability in the compositions of the present disclosure. Light stable as used herein means that the antioxidant compounds disclosed herein do not discolor when exposed to either sunlight or simulated sunlight for approximately 2 to 60 hours at a temperature of from about 25°C to about 45°C.
  • Antioxidant compounds and free radical scavengers can generally protect dyes from degradation by first preventing the generation of single oxygen and peroxy radicals, and thereafter terminating the degradation pathways. Not to be limited by theory, a general discussion of the mode of action for antioxidants and free radical scavengers is disclosed in Kirk-Othmer Encyclopedia of Chemical Technology, Volume 3, pages 128 - 148, Third Edition (1978) which is incorporated herein by reference.
  • the formulations that are the subject of the instant disclosure may comprise an organic sunscreen.
  • Suitable sunscreens can have UVA absorbing properties, UVB absorbing properties, or a combination of both.
  • the formulations newly presented herein may preferably comprise a UVA absorbing sunscreen actives that absorb UV radiation having a wavelength from about 320 nm to about 400 nm.
  • Suitable UVA absorbing sunscreen actives include dibenzoylmethane derivatives, anthranilate derivatives such as methylanthranilate and homomethyl-l-N-acetylanthranilate, and mixtures thereof. Examples of dibenzoylmethane sunscreen actives are described in U.S. Patent No.
  • the UVA absorbing sunscreen active is preferably present in an amount to provide broad-spectrum UVA protection either independently, or in combination with, other UV protective actives that may be present in the composition.
  • Preferred UVA sunscreen actives include dibenzoylmethane sunscreen actives and their derivatives.
  • They include, but are not limited to, those selected from 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4- isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4- dimethyldibenzoylmethane, 2, 5-dimethyldibenzoylmethane, 4,4'- diisopropylbenzoylmethane,4-( 1 , 1 -dimethylethyl)-4'- methoxydibenzoylmethane, 2- methyl-5 -isopropyl-4'-methoxy dibenzoylmethane, 2-methyl-5 -tert-butyl-4'- methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl- 4'-tert-butyl-4'-methoxydibenzoylme
  • Preferred dibenzoyl sunscreen actives include those selected from 4-(l,l-dimethylethyl)-4'- methoxydibenzoylmethane, 4-isopropyldibenzoylmethane, and mixtures thereof.
  • a more preferred sunscreen active is 4-(l,l-dimethylethyl)-4'-methoxy dibenzoylmethane, which is also known as butylethoxydibenzoylmethane or Avobenzone, is commercially available under the names of PARSOL 1789 from DSM Nutritional Products, LLC and EUSOLEX 9020 from EMD Chemicals Inc./Rona.
  • the sunscreen 4- isopropyldibenzoylmethane which is also known as isopropyldibenzoylmethane, is commercially available from EMD Chemicals Inc./Rona under the name of EUSOLEX 8020.
  • the formulations of the instant disclosure may preferably further comprise a UVB sunscreen active that absorbs UV radiation having a wavelength of from about 290 nm to about 320 nm.
  • the compositions may preferably comprise an amount of the UVB sunscreen active that is safe and effective to provide UVB protection either independently, or in combination with, other UV protective actives that may be present in the compositions.
  • compositions preferably comprise from about 0.1% to about 16%, more preferably from about 0.1% to about 12%, and further preferably from about 0.5%) to about 8%) by weight, of UVB absorbing organic sunscreen.
  • UVB sunscreen actives are suitable for use herein. Non-limiting examples of such organic sunscreen actives are described in U.S. Patent No 5,087,372 to Toyomot and U.S. Patent Nos. 5,073,371 and 5,073,372 both to Turner, et al., which are incorporated herein by reference.
  • Preferred UVB sunscreen actives are selected from 2- ethylhexyl-2-cyano-3,3-diphenylacrylate (referred to as octocrylene), 2-phenyl- benzimidazole-5-sulphonic acid (PBS A), cinnamates and their derivatives such as 2- ethylhexyl-p-methoxycinnamate and octyl-p-methoxycinnamate, TEA salicylate, octyldimethyl PABA, camphor derivatives and their derivatives, and mixtures thereof.
  • octocrylene 2- ethylhexyl-2-cyano-3,3-diphenylacrylate
  • PBS A 2-phenyl- benzimidazole-5-sulphonic acid
  • cinnamates and their derivatives such as 2- ethylhexyl-p-methoxycinnamate and octyl-p-methoxyc
  • Preferred organic sunscreen actives include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (commonly named octocrylene), 2-phenyl-benzimidazole-5-sulphonic acid (PBSA), octyl-p-methoxycinnamate, and mixtures thereof. Salt and acid neutralized forms of the acidic sunscreens are also useful.
  • An agent may also be added to any of the formulations described in the present disclosure to stabilize the UVA sunscreen and to prevent it from photo- degrading on exposure to ultraviolet radiation and thereby maintaining its UVA protection efficacy.
  • Wide ranges of compounds have been cited as providing these stabilizing properties and should be chosen to compliment both the UVA sunscreen and the composition as a whole.
  • Suitable stabilizing agents include, but are not limited to, those described in U.S. Pat. No. 5,972,316 to Robinson; U.S. Pat. No. 5,968,485 to Robinson; U.S. Pat. No. 5,935,556 to Tanner, et al.; and U.S. Pat. 5,827,508 Tanner, et al., which are incorporated herein by reference.
  • Preferred examples of stabilizing agents for use in the present formulations disclosure herein include 2-ethylhexyl-2- cyano-3,3-diphenylacrylate (referred to as octocrylene), ethyl-2-cyano-3,3-diphenyl- acrylate-2-ethylhexyl-3,3-diphenylacrylate, ethyl-3,3-bis (4-methoxyphenyl)acrylate, and mixtures thereof.
  • octocrylene 2-ethylhexyl-2- cyano-3,3-diphenylacrylate
  • ethyl-2-cyano-3,3-diphenyl- acrylate-2-ethylhexyl-3,3-diphenylacrylate ethyl-3,3-bis (4-methoxyphenyl)acrylate, and mixtures thereof.
  • Highly preferred materials of this class of antioxidants and sunscreen actives are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the formulations of the present disclosure may preferably deposit from about 0.1 mg/g fabric to about 5 mg/g fabric of the sun- fade actives to reduce the sun fading of the fabric. Repeated treatment of fabric with formulations presented herein, may result in higher deposition levels, which contributes even further to the sun-fading protection benefit.
  • the formulations disclosed herein can comprise from about 0.001% to about 20%) by weight, preferably from about 0.5%> preferably to about 10%> by weight, and more preferably from about 1 % to about 5% by weight of one or more dye transfer inhibitors or dye fixing agents.
  • compositions and formulations of the present disclosure can contain ethoxylated amines, amphoterics, betaines, polymers such as polyvinylpyrrolidone, and other ingredients that inhibit dye transfer. While many such compounds are commonly derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources.
  • Optional dye fixing agents can be cationic, and based on quaternized nitrogen compounds or on nitrogen compounds having a strong cationic charge that is formed in situ under the conditions of usage. Cationic fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1981, Code No.
  • SANDOFIX TPS ex Sandoz
  • Additional non- limiting examples include SANDOFIX SWE (a cationic resinous compound) from Sandoz, REWIN SRF, REWIN SRF-0 and REWIN DWR Crochet-Beitlich GMBH; Tinofix ECO, Tinofix FRD and Solvent from Ciba-Geigy.
  • Dye fixing agents suitable for use in the formulations of the instant disclosure include ammonium compounds such as fatty acid-diamine condensates, inter alia, the hydrochloride, acetate, methosulphate and benzyl hydrochloride salts of diamine esters.
  • ammonium compounds such as fatty acid-diamine condensates, inter alia, the hydrochloride, acetate, methosulphate and benzyl hydrochloride salts of diamine esters.
  • Non- limiting examples include oleyldiethyl aminoethylamide, oleylmethyl diethylenediamine methosulphate, and monostearylethylene diaminotrimethylammonium methosulphate.
  • N-oxides of tertiary amines are suitable for use as dye fixatives in the compositions of the presented herein.
  • Highly preferred materials of this class of dye transfer inhibitors and dye fixatives are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • compositions of the present disclosure may optionally comprise from about 0.01%, preferably from about 0.02%, more preferably from about 0.25% to about 15%, further preferably to about 10%, and yet more preferably to about 5% of a chlorine scavenger.
  • a chlorine scavenger In cases wherein the cation portion and the anion portion of the non-polymeric scavenger each react with chlorine, the amount of scavenger can be adjusted to fit the needs of the formulator. While many such compounds are commonly derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources.
  • Suitable chlorine scavengers include ammonium salts having the formula: [(R)3R'N]X wherein each R is independently hydrogen, C1-C4 alkyl, C1-C4 substituted alkyl, and mixtures thereof; preferably R is hydrogen or methyl, more preferably hydrogen; R is hydrogen C1-C10 alkyl, C1-C10 substituted alkyl, and mixtures thereof.
  • R is hydrogen and X is a compatible anion.
  • Non-limiting examples include chloride, bromide, citrate, and sulfate; preferably X is chloride.
  • Non- limiting examples of preferred chlorine scavengers include ammonium chloride, ammonium sulfate, and mixtures thereof, preferably ammonium chloride.
  • Other chlorine scavengers include reducing agents such as thiosulfate.
  • Highly preferred materials of this class of chlorine scavengers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the formulations and compositions disclosed herein may contain as an optional ingredient from about 0.005% to about 3.0% by weight, and more preferably from about 0.03%> to 1.0% by weight of a wetting agent.
  • a wetting agent may be selected from polyhydroxy compounds. While many such compounds are commonly derived from petrochemicals sources, and are as such not preferred, it is envisioned that they could be derived from bio-based sources.
  • water soluble polyhydroxy compounds that can be used as wetting agents in the compositions disclosed herein include glycerol, polyglycerols having a weight-average molecular weight from about 150 to about 800, and polyoxyethylene glycols and polyoxypropylene glycols having a weight-average molecular weight from about 200 to about 4000, preferably from about 200 to about 1000, and more preferably from about 200 to about 600.
  • Polyoxyethylene glycols having a weight-average molecular weight from about 200 to about 600 are especially preferred.
  • Mixtures of the above-described polyhydroxy compounds may also be used.
  • a particularly preferred polyhydroxy compound is polyoxyethylene glycol having a weight-average molecular weight of about 400, available from Dow Chemical Corporation under the trade name PEG-400.
  • Highly preferred materials of this class of wetting agents are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Suitable inorganic salts for use as an optional electrolyte in the present compositions include Mgl 2 , MgBr 2 , MgCl 2 , Mg(N03) 2 , Mg 3 (P0 4 ) 2 , Mg 2 P 2 0 7 , MgS0 4 , magnesium silicate, Nal, NaBr, NaCl, NaF, Na 3 P0 4 , Na 2 S0 3 , Na 2 S0 4 , NaN0 3 , Na 4 P 2 0 5 , sodium silicate, sodium metasilicate, sodium tetrachloroaluminate, sodium tripolyphosphate (STPP), Na2S307, sodium zirconate, CaF 2 , CaCl 2 , CaBr 2 , Cal 2 , CaS0 4 , Ca(N0 3 ) 2 , KI, KBr, KC1, KF, KN0 3 , KI0 3 , K 2 S0 4 , K 2 S
  • potassium aluminum A1K(S0 4 ) 2 and salts with mixed anions e.g. potassium tetrachloroaluminate and sodium tetrafluoroaluminate.
  • Salts incorporating cations from groups Ilia, IVa, Va, Via, Vila, VIII, lb, and lib on the periodic chart with atomic numbers greater than are also useful in reducing dilution viscosity but less preferred due to their tendency to change oxidation states and thus they can adversely affect the odor or color of the formulation or lower weight efficiency.
  • Salts with cations from group la or Ila with atomic numbers greater than 20 as well as salts with cations from the lanthanide or actinide series are useful in reducing dilution viscosity, but less preferred due to lower weight efficiency or toxicity. Mixtures of above salts are also useful.
  • quaternary ammonium salts quaternary alkyl ammonium salts, quaternary dialkyl ammonium salts, quaternary trialkyl ammonium salts and quaternary tetraalkyl ammonium salts wherein the alkyl substituent comprises a methyl, ethyl, propyl, butyl or higher C 5 -Ci 2 linear alkane radical, or combinations thereof.
  • Organic salts useful with the compositions presented herein include magnesium, sodium, lithium, potassium, zinc, and aluminum salts of carboxylic acids, including formates, acetates, proprionates, pelargonates, citrates, gluconates, lactates, and aromatic acids such as benzoates, phenolates, and substituted benzoates or phenolates, such as phenolates, salicylates, polyaromatic acids, terephthalates, and polyacids e.g. oxylates, adipates, succinates, benzenedicarboxylates and benzenetricarboxylates.
  • carboxylic acids including formates, acetates, proprionates, pelargonates, citrates, gluconates, lactates, and aromatic acids such as benzoates, phenolates, and substituted benzoates or phenolates, such as phenolates, salicylates, polyaromatic acids, terephthalates, and polyacids e.g. oxylate
  • organic salts include carbonates and/or hydrogen carbonate (HCO 3 "1 ) when the pH is targeted to be alkaline, alkyl and aromatic sulfates and sulfonates, e.g., sodium methyl sulfate, benzene sulfonates and derivatives such as xylene sulfonate, and amino acids.
  • HCO 3 "1 hydrogen carbonate
  • Electrolytes can comprise mixed salts of the above single salts, salts neutralized with mixed cations such as potassium/sodium tartrate, partially neutralized salts such as sodium hydrogen tartrate or potassium hydrogen phthalate, and salts comprising one cation with mixed anions.
  • Highly preferred mixed salt materials comprising inorganic and organic electrolytes are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after a drying and/or curing step that may be followed by normal exposure to air, moisture or sunlight.
  • inorganic electrolytes are preferred over organic electrolytes for better weight efficiency and lower costs.
  • Mixtures of inorganic and organic salts can be used.
  • Typical levels of electrolyte in the present compositions can be less than about 10% by weight, preferably from about 0.5%> to about 5% by weight, more preferably from about 0.75% to about 2.5% by weight, and further preferably from about 1 % to about 2% by weight of the inventive composition.
  • Additional desirable adjuncts may be enzymes (although it may be preferred to also include an enzyme stabilizer), including, but not limited to hydrolases, hydroxylases, cellulases, peroxidases, laccases, mannases, amylases, lipases and proteases.
  • Proteases are one especially preferred class of enzymes. Typical examples of proteases include Maxatase and Maxacal from Genencor International, Alcalase, Savinase, and Esperase, all available from Novozymes North America, Inc. See also U.S. Pat. No. 4,511,490 to Stanislowski, et al, incorporated herein by reference.
  • amylases which are carbohydrate-hydro lyzing enzymes. It may also be preferred to include mixtures of amylases and proteases. Suitable amylases include Termamyl from Novozymes, North America Inc, and Maxamyl from Genencor International Co. Still other suitable enzymes are cellulases, such as those described in U.S. Pat. No. 4,479,881 to Tai; U.S. Pat. No. 4,443,355 to Murata, et al; U.S. Pat. No. 4,435,307 to Barbesgaard, et al; and U.S. Pat. No. 3,983,082 to Ohya, et al, incorporated herein by reference.
  • hydrolytic enzyme may be present in an amount of about 0.01-5%, more preferably about 0.01- 3%, and further preferably about 0.1-2% by weight of the detergent. Mixtures of any of the foregoing hydrolases are desirable, especially protease/amylase blends.
  • Highly preferred materials of this class of enzymes are those that do not cause any significant residual odor or color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • compositions disclosed herein may optionally comprise from about 0.01 %, preferably from about 0.02% by weight, more preferably from about 0.25% to about 15%) by weight, further preferably to about 10%> by weight, and yet more preferably to about 5%> by weight of a bleaching agent.
  • Suitable bleaching agents include peroxygen and peroxide -releasing compounds.
  • Peroxygen compounds include alkali metal salts of percarbonate, perborate and peroxymonosulfate.
  • Peroxide compounds including hydrogen peroxide and compounds generating hydrogen peroxide in solution, peroxyacids and precursors to peroxyacids and peroxyimidic acids, and metal based oxidants are also suitable.
  • Suitable bleaching agents include preformed peracids and organic peroxides, including alkonyl and acyl peroxides such as tertiary butyl peroxide and benzoyl peroxide, and related alkonyl and acyl peroxide and superoxide derivatives of alkyls and arenes. Additionally, an appropriate bleach activator for the active oxygen source or peroxide may be present, such those found in Arbogast, et al, U.S. Pat. Nos. 5,739,327 and 5,741,437; Alvarez, et al; U.S. Pat. No. 5,814,242, Deline, et al; U.S. Pat. No. 5,877,315; and U.S. Pat. No.
  • Highly preferred materials of this class of bleaching agents are those that do not cause any significant fabric damage or color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • BEIGHTENERS are those that do not cause any significant fabric damage or color change, nor impart any discoloration, such as graying or yellowing, to the matrices into which they are introduced, or to fabrics to which they may be applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • Optical brighteners also referred to as fluorescent whitening agents or FWAs
  • FWAs fluorescent whitening agents
  • These fluorescent materials act by absorbing ultraviolet wavelength, of light and emitting visible light, generally in the color blue wavelength ranges.
  • the FWAs settle out or deposit onto fabrics dining the wash cycle.
  • These include the stilbene, stymie, and. naphthalene derivatives, which upon being impinged by ultraviolet light, emit or fluoresce light in the visible wavelength. While many such compounds are commonly derived from petrochemicals sources, and are as such not preferred, it is envisioned thai they could be derived from bio-based sources. It is also envisioned that, by being dyes, there are individuals with MCS that may not be able tolerate their presence, and as such natural ingredients such as pigments that possess the ability to fluoresce may be preferable.
  • FWAs or brighteners are useful for improving the appearance of fabrics, which have become dingy through repeated soilings and washings. Due to the cationic nature of the composition, it is preferred that the FWAs not be explicitly anionic but rather either nomoeic: cationic: amphoteric; or neutralized, ion-paired moieties of anionic FWAs as described in Petrin, ei i, U.S. Pat. No. 5,057,236. Preferred anionic FWAs for ion-pairing according to Petrin, el at, '236 are Blankophor BBH, RKH and BHC, from Blankophor GmbH & Co.
  • Examples of such DASC fluorescent whiteners include those sold by BASF Corporation under the trade name "Tinopal", which are substituted stilbene 2,2'- disulfonic acid products, e.g., disodium 4,4'-bis-((4-anilino-6-morpholino-l,3,5-triazin- 2-yl)amino)stilbene-2,2'-disulfonate (sold as Tinopal AMS); disodium 4,4'-bis-((4- anilino-6-(N-2-hydroxyethyl-N -methyl amino)- 1,3, 5-triazin-2-yl)amino)stilbene-2,2'- disulfonate (sold as Tinopal 5BM); disodium 4,4'-bis-((4-anilino-6-(bis-(2- hydroxyethyl)amino)-l,3,5-triazin-2-yl)amino)stilbene-2,2'-disulfon
  • Bayer Corporation is disodium 4,4'-bis-((4-anilino- 6-methylamino)-l,3,5-triazin-2-yl)amino)stilbene-2,2'-disulfonate (sold as Phorwite HRS).
  • cationic, nonionic, and amphoteric FWAs such as those cited in U.S. Pat. Nos. 4,433,975, 4,432,886, 4,384,121, all to Meyer and U.S. Pat. No. 4,263,431 to Weber, et al, and incorporated herein by reference.
  • suitable FWAs are described in McCutcheon's Vol. 2: Functional Materials, North American Ed., McCutcheon Division, MC Publishing Co., 1995, and Encyclopedia of Chemical Technology, 11th volume, John Wiley & Sons, 1994, both of which are incorporated herein by reference.
  • Highly preferred materials of this class of brighteners are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the fabrics to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • surfactants possess a significant portion, that is 25% or more by weight, of petrochemical contribution. In other words, despite being positioned as “natural” surfactants, their Biorenewable Carbon Index (and thus their biorenewable carbon content) is less than 80% by weight. As such, it has been found that surfactants that are preferred for use with the compositions described herein are those having a Biorenewable Carbon Index of at least 80%, that is, with a BCI of > 80%.
  • Chemicals that have a carbon chain length greater than eight carbon atoms may be insufficiently reactive with proteins to form protein-hapten complexes.
  • any protein-hapten conjugates having greater than eight-carbon atom chain lengths that may form are present in concentrations that are lower than a threshold level needed to trigger an immunogenic response.
  • a number of raw materials were evaluated by a number of chemically sensitive individuals for acceptability using the same scale as above. The results are presented in TABLE 3 below.
  • HAPs hazardous air pollutants
  • the inventors believe that minimizing or eliminating sources of VOC can significantly reduce contaminants that may introduce hazardous air pollutants into consumer cleaning compositions.
  • the vapor pressure of ethanol at room temperature is about 45 mm Hg at 20°C, while that of 1,3- propanediol is 0.08 mm Hg, and that of glycerine is about 0.00018 mm Hg.
  • Substitution of ethanol with other low-volatility solvents can therefore not only lower the overall vapor pressure of a product, and but may reduce the likelihood of untoward effects on persons that suffer from MCS.
  • a laundry detergent was formulated in accordance with the guidelines presented above. Accordingly, 15.0 parts of alkyl polyglucoside (Triton CG-600, 50% active from Dow Chemical Company) were added to 63.1 parts deionized water with mixing, followed by 13.0 parts of sodium coco sulfate (Stepanol WA-Extra, 29% active from Stepan Company), 2.0 parts glycerine (Pricerene 9091 from Croda), 2.0 parts boric acid, 2.0 parts oleic acid (Acme-Hardesty Co), 1.0 part sodium gluconate, 1 part sodium hydroxide, 0.1 part protease (Novozymes), 0.1 part calcium chloride, 0.1 part sodium chloride, 0.05 parts amylase (Novozymes), and 0.05 parts preservative (Neolone M10, 10% active).
  • alkyl polyglucoside Triton CG-600, 50% active from Dow Chemical Company
  • Sample F in TABLE 4 A portion of the resulting formulations, designated Sample F in TABLE 4 below, was then submitted for evaluation and analysis versus a commercially available, safety-positioned, unfragranced liquid detergent product, labeled Sample E in TABLE 4 below.
  • the samples were analyzed via two different methods: U.S. EPA Compendium Method TO- 15, "Determination Of Volatile Organic Compounds (VOCs) In Air Collected In Specially-Prepared Canisters And Analyzed By Gas Chromatography/Mass Spectrometry (GC/MS)," EPA, 1999, and U.S.
  • Sample F Laundry detergent formulated according to the instant disclosure, described in EXAMPLE 1, above.
  • CAA-TFS a Clean Air Act— Toxic and Flammable Substances for Accidental
  • CAA-HAP b Clean Air Act— Hazardous Air Pollutant
  • FIFRA Federal Insecticide, Fungicide, and Rodenticide Act— Registered Pesticide
  • Samples E and F were then analyzed via U.S. EPA Method TO- 11 A, which is specific for aldehydes such as formaldehyde and acetaldehyde.
  • Sample F a composition prepared in accordance with the methods described in the instant specification, had significantly less acetaldehyde than commercial product Sample B, and is absent of formaldehyde down to the detection limit. Results are summarized below in TABLE 6.
  • Sample F Laundry detergent formulated according to the instant disclosure, described in EXAMPLE 1, above.
  • Alkyl polyglucoside 50% 15.0% 9.0% 3.0% 5.0% active
  • Cocoamine oxide 12.0% — —
  • Citric acid 0.25% — 4.0%
  • a liquid laundry detergent that may be prepared according to the information presented herein and be well suited for use by chemically-sensitive individuals, contains: 1) 30% sodium coco sulfate, 29% active; 2) 15% alkyl polyglucoside, 50% active; 3) 2.5% glycerine; 4) 2.0% boric acid; 5) 2.0% oleic acid; 6) 1.0% sodium gluconate; 7) 1.0% sodium hydroxide; 8) 0.1% protease; 9) 0.1% calcium chloride; 10) 0.1% sodium chloride; 11) 0.05% amylase; 12) 0.05% preservative, 10% active; and the balance water, where all percents are understood to refer to weight percent. Furthermore, a liquid laundry detergent that may be prepared according to the methods presented herein and consistent with the above composition may be found to have a percent modern carbon (pMC) of approximately 99.97%.
  • pMC percent modern carbon
  • a dishwashing detergent that may be prepared according to the information presented herein and be well suited for use especially by chemically- sensitized individuals, contains: 1) 45.0% sodium coco sulfate, 29% active; 2) 9.0%> alkyl polyglucoside, 50% active; 3) 12% cocamine oxide, 30%; 4) 3.5% glycerine; 5) 0.25%) citric acid; 6) 0.05% preservative, 10% active; and the balance water, where all percents are understood to refer to weight percent.
  • a dishwashing detergent that may be prepared according to the methods presented herein and consistent with the above composition may be found to have a percent modern carbon (pMC) of approximately 97.96%
  • an all-purpose cleaner that may be prepared according to the information presented herein and be found to be well suited for use especially by chemically-sensitized individuals, contains: 1) 3.0%> alkyl polyglucoside, 50% active; 2) 1.5% glycerine; 3) 0.5% potassium citrate, 4) 0.05% preservative, 10% active; and the balance water, where all percents are understood to refer to weight percent. Furthermore, an all-purpose cleaner that may be prepared according to the methods presented herein and consistent with the above composition may be found to have a percent modern carbon (pMC) of approximately 99.86%.
  • pMC percent modern carbon
  • a general bathroom cleaner that may be prepared according to the information presented herein and be found to be well suited for use especially by chemically-sensitized individuals, contains: 1) 5.0% alkyl polyglucoside, 50%) active; 2) 4% citric acid; 3) 0.05%> preservative, 10%> active; and the balance water, where all percents are understood to refer to weight percent. Furthermore, a general bathroom cleaner that may be prepared according to the methods presented herein and consistent with the above composition may be found to have a percent modern carbon (pMC) of approximately 99.92%.
  • pMC percent modern carbon

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Abstract

La présente invention se rapporte à des compositions de nettoyage en général et en particulier à des compositions de nettoyage qui conviennent bien pour être utilisées par des individus qui subissent des effets néfastes sur la santé qui peuvent se produire lors de l'exposition à certains produits chimiques. Cette affection, appelée polysensibilité chimique (PC), rend pratiquement impossible pour certains individus l'utilisation de produits de nettoyage disponibles dans le commerce sans induire des réponses immunologiques. La présente invention présente et décrit des protocoles pour la formulation et l'évaluation de divers produits de nettoyage à l'aide d'une combinaison de dosage de 14C, d'analyse de phase gazeuse et de criblage d'ingrédients et de produits par des individus fortement sensibilisés. Les nouveaux procédés et les nouvelles compositions selon la présente invention permettent d'éviter de provoquer des réponses néfastes sur la santé chez des individus et conviennent pour être utilisés par toute personne, en particulier des individus qui souffrent de PC.
PCT/US2015/027403 2014-04-23 2015-04-23 Formulations de nettoyage pour des individus sensibles aux produits chimiques : compositions et procédés WO2015164677A1 (fr)

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AU2015252006A AU2015252006A1 (en) 2014-04-23 2015-04-23 Cleaning formulations for chemically sensitive individuals: compositions and methods
US15/306,109 US10767137B2 (en) 2014-04-23 2015-04-23 Cleaning formulations for chemically sensitive individuals: compositions and methods
CA2981702A CA2981702A1 (fr) 2014-04-23 2015-04-23 Formulations de nettoyage pour des individus sensibles aux produits chimiques : compositions et procedes
US16/987,416 US10968415B2 (en) 2014-04-23 2020-08-07 Cleaning formulations for chemically sensitive individuals: compositions and methods

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US10849929B2 (en) 2016-08-30 2020-12-01 Chuch & Dwight Co., Inc. Composition and method for allergen deactivation
GB2595918A (en) * 2020-06-11 2021-12-15 Reckitt & Colman Overseas Hygiene Home Ltd Novel composition
WO2023211956A1 (fr) * 2022-04-29 2023-11-02 Stepan Company Compositions d'esterquat de glycine betaïne-alcools de guerbet et leurs procédés de préparation

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