WO2014085271A1 - Émulsifiant sans ape utilisable pour le lavage du linge - Google Patents

Émulsifiant sans ape utilisable pour le lavage du linge Download PDF

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Publication number
WO2014085271A1
WO2014085271A1 PCT/US2013/071548 US2013071548W WO2014085271A1 WO 2014085271 A1 WO2014085271 A1 WO 2014085271A1 US 2013071548 W US2013071548 W US 2013071548W WO 2014085271 A1 WO2014085271 A1 WO 2014085271A1
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WO
WIPO (PCT)
Prior art keywords
composition
alcohol ethoxylate
compositions
guerbet
ethoxylate
Prior art date
Application number
PCT/US2013/071548
Other languages
English (en)
Inventor
Sukhwan Soontravanich
Stephan Hubig
Yang Zhang
Original Assignee
Ecolab Usa Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/689,876 external-priority patent/US8901063B2/en
Application filed by Ecolab Usa Inc. filed Critical Ecolab Usa Inc.
Priority to AU2013352450A priority Critical patent/AU2013352450B2/en
Priority to BR112015010342-1A priority patent/BR112015010342B1/pt
Publication of WO2014085271A1 publication Critical patent/WO2014085271A1/fr
Priority to AU2017201359A priority patent/AU2017201359B2/en

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Classifications

    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D1/008—Polymeric surface-active agents
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to a detergent for laundry and other hard surface cleaning system which uses an APE-free surfactant blend.
  • an emulsifier system including linear and branched fatty alcohol ethoxylates and ethoxylate propoxylate block copolymers is provided for laundry and other hard surface cleaning applications providing oily soil and greasy food removal.
  • APEs alkyl phenol ethoxylates
  • NPE nonyl phenol ethoxylates
  • NPEs are formed through the combination of ethylene oxide with nonylphenol (NP). Both NP and NPEs exhibit estrogen-like properties and may contaminate water, vegetation and marine life. NPE is also not readily
  • a further object of the invention is to provide NPE-free laundry detergents and other hard surface cleaning detergents that provide effective soil removal, including oily soils, such that organic grease, fat and oils are emulsified.
  • a further object of the invention is to provide the NPE-free compositions without using harsh solvents in place of the NPEs or other APEs, which again may cause environmental concerns such as high content of volatile organic compounds (VOCs), biodegradability, aqua toxicity, etc.
  • VOCs volatile organic compounds
  • the present invention provides laundry emulsifiers and/or hard surface cleaning compositions which include an environmentally friendly surfactant and/or surfactant blend that works at least as well as NPE.
  • the present invention is a laundry and/or cleaning composition that is a concentrated pre- treatment or pre-soak NPE-free composition.
  • the cleaning composition is substantially free of alkyl phenol ethoxylates, or preferably is free of alkyl phenol ethoxylates.
  • the present invention is a composition comprising from about 40 wt-% to about 95 wt-% of a nonionic surfactant blend, wherein the surfactant blend comprises a fatty alcohol ethoxylate, a Guerbet alcohol ethoxylate or a Guerbet ethoxylate, and an ethylene oxide - propylene oxide copolymer, and optionally from about 0.1 wt-% to about 25 wt-% stabilizers and/or water.
  • a nonionic surfactant blend comprises a fatty alcohol ethoxylate, a Guerbet alcohol ethoxylate or a Guerbet ethoxylate, and an ethylene oxide - propylene oxide copolymer, and optionally from about 0.1 wt-% to about 25 wt-% stabilizers and/or water.
  • the present invention is a concentrated pre- treatment or pre-soak NPE-free composition
  • a concentrated pre- treatment or pre-soak NPE-free composition comprising: a fatty alcohol ethoxylate; a Guerbet alcohol ethoxylate or a Guerbet ethoxylate; an ethylene oxide - propylene oxide copolymer;
  • the ratio of said fatty alcohol ethoxylate to said Guerbet alcohol ethoxylate or a Guerbet ethoxylate to said ethylene oxide - propylene oxide copolymer is from about 1: 1:1 to about 10: 1: 10.
  • the present invention is a method of removing soils from a surface.
  • the method includes removing stains from fabric or hard surfaces comprising the steps of: contacting a soiled article or surface with an aqueous composition comprising from about 40 wt-% to about 95 wt-% of a nonionic surfactant blend, wherein the surfactant blend comprises a fatty alcohol ethoxylate, a Guerbet alcohol ethoxylate or a Guerbet ethoxylate, and an ethylene oxide - propylene oxide copolymer, and optionally from about 0.1 wt-% to about 25 wt-% stabilizers and/or water, for a period of time sufficient to achieve removal of soils from said article or surface; and thereafter cleaning or laundering the treated article or surface with a conventional aqueous detergent.
  • the methods of removing soils from a surface may be employed either inside or outside a washing machine, when employing a method of removing soils from a laundry application.
  • aqueous composition when employed outside the washing machine it is used in a concentrated formulation.
  • aqueous composition when employed inside the washing machine it is used in a diluted (or a highly diluted) formulation, such as within the wash liquor of a washing machine.
  • FIG. 1 shows a graph of soil removal capacity of compositions according to embodiments of the invention against various soils on various fabrics in comparison to baseline NPE-containing and NPE-free control compositions.
  • FIG. 2 shows a graph of soil removal capacity of compositions according to embodiments of the invention as shown in FIG.1 with the addition of a source of alkalinity to demonstrate further detergency benefits in comparison to baseline NPE- containing and NPE-free control compositions.
  • FIG. 3 shows a graph combining the results of FIGS. 1-2 to demonstrate the additional efficacy of soil removal with the addition of a source of alkalinity (e.g. builder component) according to an embodiment of the methods of the invention.
  • a source of alkalinity e.g. builder component
  • FIGS. 4-6 show graphs of the effect of temperature variations on the soil removal efficacy of the compositions according to embodiments of the invention on various soils and laundry textiles.
  • FIG. 7 shows a graph of the detergent efficacy of additional NPE-free emulsifier compositions according to an additional embodiment of the invention.
  • FIG. 8 shows a graph of the detergent efficacy of additional NPE-free emulsifier compositions in combination with a source of alkalinity according to an additional embodiment of the invention.
  • FIG. 9 shows a graph combining the results of FIGS. 7-8 to demonstrate the additional efficacy of soil removal with the addition of a source of alkalinity (e.g. builder component) according to an embodiment of the methods of the invention.
  • a source of alkalinity e.g. builder component
  • FIG. 10 shows a graph of soil removal capacity of an exemplary composition according to embodiments of the invention at varying use solution concentrations (% actives), with and without the use of a builder to increase pH of the cleaning solution.
  • FIG. 11 shows a graph of the b value (removal of yellowing from soiled swatch) of the test compositions and control formulations from textiles soiled with chili oil.
  • FIGS. 12-14 show graphs of the comparison of detergency of various compositions (with and without builder components) according to embodiments of the invention at different temperatures.
  • actives or “percent actives” or “percent by weight actives” or “actives concentration” are used interchangeably herein and refers to the
  • concentration of those ingredients involved in cleaning expressed as a percentage minus inert ingredients such as water or salts.
  • alkyl or “alkyl groups” refers to saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or “alicyclic” or “carbocyclic” groups) (e.g.
  • cyclopropyl cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.
  • branched- chain alkyl groups e.g. , isopropyl, tert-butyl, sec-butyl, isobutyl, etc.
  • alkyl- substituted alkyl groups e.g. , alkyl-substituted cycloalkyl groups and cycloalkyl- substituted alkyl groups.
  • alkyl includes both "unsubstituted alkyls” and “substituted alkyls.”
  • substituted alkyls refers to alkyl groups having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone.
  • substituents may include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,
  • substituted alkyls can include a heterocyclic group.
  • heterocyclic group includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur or oxygen.
  • Heterocyclic groups may be saturated or unsaturated.
  • Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxides, oxiranes), thiirane (episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.
  • the term “cleaning” refers to a method used to facilitate or aid in soil removal, bleaching, microbial population reduction, and any combination thereof.
  • the term “microorganism” refers to any noncellular or unicellular (including colonial) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, and some algae. As used herein, the term “microbe” is synonymous with microorganism. For the purpose of this patent application, successful microbial reduction is achieved when the microbial populations are reduced by at least about 50%, or by significantly more than is achieved by a wash with water. Larger reductions in microbial population provide greater levels of protection.
  • hard surface refers to a solid, substantially non-flexible surface such as a counter top, tile, floor, wall, panel, window, plumbing fixture, kitchen and bathroom furniture, appliance, engine, circuit board, and dish. Hard surfaces may include for example, health care surfaces and food processing surfaces.
  • food processing surface refers to a surface of a tool, a machine, equipment, a structure, a building, or the like that is employed as part of a food processing, preparation, or storage activity. Examples of food processing surfaces include surfaces of food processing or preparation equipment (e.g. , slicing, canning, or transport equipment, including flumes), of food processing wares (e.g.
  • Food processing surfaces are found and employed in food anti-spoilage air circulation systems, aseptic packaging sanitizing, food refrigeration and cooler cleaners and sanitizers, ware washing sanitizing, blancher cleaning and sanitizing, food packaging materials, cutting board additives, third-sink sanitizing, beverage chillers and warmers, meat chilling or scalding waters, autodish sanitizers, sanitizing gels, cooling towers, food processing antimicrobial garment sprays, and non-to-low-aqueous food preparation lubricants, oils, and rinse additives.
  • health care surface refers to a surface of an instrument, a device, a cart, a cage, furniture, a structure, a building, or the like that is employed as part of a health care activity.
  • health care surfaces include surfaces of medical or dental instruments, of medical or dental devices, of electronic apparatus employed for monitoring patient health, and of floors, walls, or fixtures of structures in which health care occurs.
  • Health care surfaces are found in hospital, surgical, infirmity, birthing, mortuary, and clinical diagnosis rooms. These surfaces can be those typified as "hard surfaces” (such as walls, floors, bed-pans, etc.,), or fabric surfaces, e.g.
  • knit, woven, and non- woven surfaces such as surgical garments, draperies, bed linens, bandages, etc.,), or patient-care equipment (such as respirators, diagnostic equipment, shunts, body scopes, wheel chairs, beds, etc.,), or surgical and diagnostic equipment.
  • Health care surfaces include articles and surfaces employed in animal health care.
  • hydrotrope means a material used in a composition to maintain a single phase neat or aqueous composition or solubilisate (liquid solution). Such hydrotrope may also be used in aspects of embodiments and/or embodiments of the present invention. Hydrotropy is a property that relates to the ability of a material to improve the solubility or miscibility of a substance in liquid phases in which the substance tends to be insoluble. Without being limited to a particular theory of the invention, a hydrotrope modifies a formulation to increase the solubility of an insoluble substance or creates micellar or mixed micellar structures resulting in a stable suspension of the insoluble substance.
  • laundry refers to items or articles that are cleaned in a laundry washing machine.
  • laundry refers to any item or article made from or including textile materials, woven fabrics, non-woven fabrics, and knitted fabrics.
  • the textile materials can include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof including cotton and polyester blends.
  • the fibers can be treated or untreated. Exemplary treated fibers include those treated for flame retardancy.
  • linen is often used to describe certain types of laundry items including bed sheets, pillow cases, towels, table linen, table cloth, bar mops and uniforms.
  • the invention additionally provides a composition and method for treating non-laundry articles and surfaces including hard surfaces such as dishes, glasses, and other ware.
  • microemulsion refers to a thermodynamically stable liquid dispersion of one liquid phase into another that is stabilized by an interfacial film of surfactant.
  • the aqueous compositions are not microemulsions, as they lack an oily droplet and/or other component to be dispersed within another phase.
  • the aqueous compositions according to the present invention can be characterized as either solutions or dispersions of surfactants in an aqueous system, such as water.
  • an oily soil is treated according to the methods of the invention a microemulsion is formed between the aqueous composition and the oily soil.
  • alkyl phenol ethoxylate (or APE)-free or “nonyl phenol ethoxylate (or NPE)-free” refers to a composition, mixture, or ingredients that do not contain alkyl phenol ethoxylates (specifically including nonyl phenol ethoxylates) or phenol-containing compounds or to which the same has not been added.
  • alkyl phenol ethoxylates or -alkyl phenol ethoxylate containing compound be present through contamination of a composition, mixture, or ingredients, the amount of the same shall be less than 0.5 wt-%. In another embodiment, the amount of is less than 0.1 wt-% and in yet another embodiment, the amount is less than 0.01 wt-%.
  • the compositions are both APE-free and specifically NPE-free.
  • oil or “stain” refers to a non-polar oily
  • hydrophobic, water-insoluble substance which may or may not contain particulate matter such as mineral clays, sand, natural mineral matter, carbon black, graphite, kaolin, environmental dust, etc.
  • substantially similar cleaning performance refers generally to achievement by a substitute cleaning product or substitute cleaning system of generally the same degree (or at least not a significantly lesser degree) of cleanliness or with generally the same expenditure (or at least not a significantly lesser expenditure) of effort, or both.
  • cleaning performance may be measured in terms of percentage of soil removal.
  • the aqueous compositions according to the invention provide at least substantially similar cleaning performance to conventional APE-containing surfactant blends.
  • the aqueous compositions according to the invention provide superior cleaning performance to conventional APE- containing surfactant blends.
  • weight percent refers to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, “percent,” and the like are intended to be synonymous with “weight percent,” “wt- ,” etc.
  • compositions of the present invention may comprise, consist essentially of, or consist of the components and ingredients of the present invention as well as other ingredients described herein.
  • consisting essentially of means that the methods and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.
  • the combination of a linear and branched fatty alcohol ethoxylates, and an ethoxylate propoxylate block copolymer provides at least substantially similar cleaning efficacy to NPE- containing detergents.
  • the compositions are free of alkyl phenol ethoxylates (APEs), including nonyl phenol ethoxylates (NPEs), while providing effective cleaning for various soils, including oily and greasy soils, providing enhanced cleaning efficacy over commercially-available neutral, NPE-free cleaning compositions.
  • the cleaning compositions provide a green, biodegradable replacement for conventional detergent surfactants.
  • the cleaning compositions can be used in various industries, including, but not limited to: textile care or other laundering applications, and other hard- surface cleaning applications, including, for example: bathroom surfaces, dishwashing equipment, food and beverage equipment, vehicles and tabletops.
  • the compositions comprise, consist of and/or consist essentially of a combination of both linear and branched fatty alcohol ethoxylates, and an ethoxylate propoxylate block copolymer.
  • the compositions may further comprise, consist of and/or consist essentially of a linear fatty alcohol ethoxylate, a branched fatty alcohol ethoxylate, an ethoxylate propoxylate block copolymer, and water.
  • the compositions may comprise, consist of and/or consist essentially of a linear and a branched fatty alcohol ethoxylate, an ethoxylate propoxylate block copolymer, water, and additional stabilizers and/or solvents.
  • the compositions may optionally include additional functional ingredients.
  • compositions according to the invention have an approximately neutral pH.
  • the pH of the compositions is between about 6-9, preferably between about 6-8.5, more preferably between about 7-8.
  • the pH of the neutral cleaning composition is about 7.
  • the compositions may be further combined with detergency boosters, which are known to increase the pH, to provide additional cleaning efficacy.
  • compositions provide significant utility for use as both laundry emulsifiers and hard surface cleaners.
  • the liquid compositions (also referred to herein as aqueous compositions) are particularly suitable for use as a dilutable detergent or hard surface concentrate or as a ready-to-use product.
  • a concentrate refers to a composition that is intended to be further diluted with water to provide a use solution.
  • a use solution refers to an aqueous
  • a use solution can have a solids content of less than about 90 wt-%, whereas the solids content refers to the weight percent of non- water components.
  • compositions are dissolved in water to form a stable solution or surfactant dispersion. Additional stabilizing agents may be employed to improve phase stability of the compositions as disclosed herein. Beneficially the stabilized compositions of the invention avoid the -issues with phase separation during storage.
  • the compositions according to the invention may be provided in various forms for providing detersive compositions for use according to the methods of the invention. In an aspect of the invention, the compositions are provided as a liquid. The compositions may be dispensed from single or multi-use packaging in the various physical forms.
  • Non-ionic Surfactant Blends The compositions of the invention combine nonionic surfactants to provide effective detergency for use in laundry applications as emulsifiers to remove heavy soils and stains and/or in cleaning other soils as a hard surface cleaner.
  • the nonionic surfactants include the use of various nonionic surfactants.
  • the nonionic surfactants include the use of various dispersible, nonionic surfactants.
  • the surfactants include both linear and branched fatty alcohol ethoxylates (including e.g. Guerbet alcohol ethoxylates as the branched fatty alcohol ethoxylates) and polyethoxylene- polypropoxylene copolymers.
  • the surfactant blend preferably operates without substantial amounts of conventional solvents which are typical in pretreatment compositions used to soften, dissolve and/or otherwise pre-treat or pre-spot soils.
  • the presence of the surfactant blend in a pre-treated soil according to the invention renders the soils uniquely subject to cleaning and substantially complete removal in laundering methods disclosed according to the methods of the present invention.
  • the oily soils are being emulsified, which makes them dispersible in the wash liquor.
  • compositions of the invention include a linear alcohol ethoxylate nonionic surfactant.
  • the linear alcohol ethoxylate is preferably a fatty alcohol ethoxylate.
  • the alcohol ethoxylate is a branched alcohol ethoxylate.
  • the ethoxylated C 6 -C 18 fatty alcohols and C 6 -C 18 mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the present
  • Suitable ethoxylated fatty alcohols include the C 6 -C 18 ethoxylated fatty alcohols with a degree of ethoxylation from at least about 3 to 50.
  • Particularly suitable ethoxylated fatty alcohols include C 6 -C 18 , preferably C 12 -C 18 , preferably C 12 - C 16 and/or C -Qs , which may vary depending upon either the organic or synthetic source of the ethoxylated fatty alcohols.
  • Suitable ethoxylated fatty alcohols further include a degree of ethoxylation from at least about 3 or greater, preferably at least about 4 or greater.
  • the degree of ethoxylation of the ethoxylated fatty alcohols according to the invention is from between 4 to 10.
  • all ranges of the degree of ethoxylation recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • commercially available ethoxylated C 13 -C 15 fatty alcohols have a degree of ethoxylation of 7 (e.g.
  • the compositions include from about 0.1 wt-% - 80 wt-% linear alcohol ethoxylate surfactant, from about 1 wt-% - 50 wt-% linear alcohol ethoxylate surfactant, from about 10 wt-% - 50 wt-% linear alcohol ethoxylate surfactant, preferably from about 15 wt-% - 40 wt-% linear alcohol ethoxylate surfactant.
  • the linear alcohol ethoxylate surfactant is included in the compositions in an amount effective to provide detersive properties for effective cleaning.
  • An effective amount should be considered as an amount that provides a concentrate of the cleaning composition the optional detersive property.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • compositions of the invention also include a branched alcohol ethoxylate nonionic surfactant.
  • the compositions of the invention include a Guerbet alcohol ethoxylate or a Guerbet ethoxylate as the branched alcohol ethoxylate nonionic surfactant. Additional description of branched alcohol ethoxylate and alkoxylate surfactants is set forth in U.S. Patent 7,530,361 titled "Detergent
  • Preferred branched alcohol ethoxylates include Guerbet ethoxylates, which may also be referred to as Guerbet alcohol ethoxylates. Guerbet alcohol ethoxylates may also be referred to as alkyl polyethylene glycols and/or alkyl polyethylene glycol ethers Guerbet ethoxylates suitable for use according to the invention have the following formula:
  • the Guerbet ethoxylate is further defined wherein Rl is C2-C20 alkyl and R2 is H or C1-C4 alkyl.
  • the Guerbet ethoxylate is defined wherein "n” is an integer between 2 and 20 and wherein "m” is an integer between 1 and 40.
  • Guerbet alcohol ethoxylates suitable for use according to the invention have the following properties:
  • the Guerbet alcohol ethoxylate is further defined wherein Rl is a branched C2-C20 alkyl group and n is from 2 to 20.
  • the Guerbet alcohol ethoxylate is a C2-C10 Guerbet alcohol ethoxylate, preferably a C6-C10 Guerbet alcohol ethoxylate, wherein the carbon chain may be Y-shaped and have the ethoxylated end at the bottom of the Y.
  • the branched alcohol ethoxylate is a Guerbet alcohol ethoxylate that is prepared from a Guerbet alcohol by dimerization of alkenes (e.g. butane).
  • the Guerbet alcohol ethoxylate can be reacted in a self-condensation of alcohols by which alcohols having branched alkyl chains are produced. The reaction sequence is related to the
  • Aldol condensation and occurs at high temperatures under catalytic conditions.
  • the product is a branched alcohol with twice the molecular weight of the reactant minus a mole of water.
  • the reaction proceeds by a number of sequential reaction steps. At first the alcohol is oxidized to an aldehyde. Then Aldol condensation takes place after proton extraction. Thereafter the aldol product is dehydrated and the hydrogenation of the allylic aldehyde takes place.
  • These products are called Guerbet alcohols and are further reacted to the non-ionic alkoxylated Guerbet alcohols by alkoxylation with i.e. ethylene oxide or propylene oxide.
  • the ethoxylated Guerbet alcohols have a lower solubility in water compared to the linear ethoxylated alcohols with the same number of carbon atoms. Therefore the exchange of linear fatty alcohols by branched fatty alcohols makes it necessary to use good solubilizers which are able to keep the Guerbet alcohol in solution and the resulting emulsion stable even over a longer storage time. According to the invention, this is achieved through the combination with additional nonionic surfactants and optional stabilizing agents ⁇ e.g. glycols, such as alkylene glycols including propylene glycol and an alcohol, such as an isopropyl alcohol).
  • additional nonionic surfactants and optional stabilizing agents ⁇ e.g. glycols, such as alkylene glycols including propylene glycol and an alcohol, such as an isopropyl alcohol).
  • branched alcohol alkoxylates including Guerbet alcohol ethoxylates, can be prepared according to the methods disclosed for example in U.S. Pat. Nos.
  • Exemplary branched Guerbet alcohol ethoxylates include those available under the tradenames Lutensol XP-40 and Lutensol XP-50 (BASF Corporation).
  • Lutensol XP-40 can be considered to have 4 repeating ethoxy groups ⁇ i.e. 4 moles EO
  • Lutensol XP-50 can be considered to have 5 repeating ethoxy groups ⁇ i.e. 4 moles EO).
  • Branched alcohol ethoxylates or alkoxylates can be classified as relatively water insoluble or relatively water soluble.
  • a water insoluble branched alcohol ethoxylate can be considered an ethoxylate that, when provided as a composition containing 5 wt-% of the branched alcohol ethoxylate and 95 wt-% water, has a tendency to deposit on a surface and form a greasy film.
  • Lutensol XP-40 and Lutensol XP-50 from BASF Corporation are examples of water-insoluble branched alcohol ethoxylates.
  • a branched alcohol ethoxylate or alkoxylate preferably a water-insoluble Guerbet alcohol ethoxylate has from about 10 wt-% to about 90 wt-% ethylene oxide, from about 20 wt-% to about 70 wt-% ethylene oxide preferably from about 30 wt-% to about 60 wt-% ethylene oxide.
  • the alcohol ethoxylate or alkoxylate e.g. Guerbet alcohol ethoxylate
  • the compositions include from about 0.1 wt-% - 80 wt-% Guerbet alcohol ethoxylate surfactant, from about 0.1 wt-% - 75 wt-% Guerbet alcohol ethoxylate surfactant, from about 1 wt-% - 50 wt-% Guerbet alcohol ethoxylate surfactant, from about 10 wt-% - 40 wt-% Guerbet alcohol ethoxylate surfactant, preferably from about 15 wt-% - 30 wt-% Guerbet alcohol ethoxylate surfactant.
  • the branched fatty alcohol ethoxylate such as the preferred Guerbet alcohol ethoxylate surfactant, is included in the compositions in an amount effective to provide detersive properties for effective cleaning.
  • An effective amount should be considered as an amount that provides a concentrate of the cleaning composition the optional detersive property.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • compositions of the invention include an ethylene oxide - propylene oxide copolymer.
  • the compositions of the invention include water- insoluble, ethylene oxide/propylene oxide block copolymers.
  • Ethylene oxide - propylene oxide copolymers may also be referred to as ethoxylate propoxylate block copolymers, polyethoxylene-polypropoxylene copolymer, and/or EP-PO copolymers.
  • the ethylene oxide/propylene oxide block copolymers as disclosed herein also include reverse ethylene oxide/propylene oxide copolymers.
  • a combination of various traditional and/or reverse ethylene oxide/propylene oxide copolymers may also be employed in the neutral cleaning compositions of the invention.
  • the ethylene oxide/propylene oxide block copolymer is a reverse EO-PO copolymer.
  • the ethylene oxide/propylene oxide block copolymer has a molecular weight less than about 10,000. Still further, in a preferred aspect of the invention, the ethylene
  • oxide/propylene oxide block copolymer has water solubility less than about 1%.
  • ethylene oxide/propylene oxide block copolymers include but are not limited to, PLURONIC® and TETRONIC ® products (BASF Corporation) and SURFONIC® products (Huntsman Corporation). These exemplary products are polymeric compounds made from a sequential propoxylation and ethoxylation of initiator.
  • Pluronic ® compounds are difunctional (two reactive hydrogens) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule weighs from about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, controlled by length to constitute from about 10% by weight to about 80% by weight of the final molecule.
  • the compositions include from about 0.1 wt-% - 80 wt-% ethylene oxide/propylene oxide block copolymer surfactant, from about 0.1 wt-% - 50 wt-% ethylene oxide/propylene oxide block copolymer surfactant, from about 1 wt-% - 50 wt-% ethylene oxide/propylene oxide block copolymer surfactant, from about 10 wt-% - 50 wt-% ethylene oxide/propylene oxide block copolymer surfactant, preferably from about 20 wt-% - 40 wt-% ethylene oxide/propylene oxide block copolymer surfactant.
  • the ethylene oxide/propylene oxide block copolymer surfactant is included in the compositions in an amount effective to provide detersive properties for effective cleaning.
  • An effective amount should be considered as an amount that provides a concentrate of the cleaning composition the optional detersive property.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • a stabilizing agent including a carrier and/or solvent, may be included in the compositions to improve phase stability of the compositions.
  • solvents for enhanced soil removal properties are not required in the compositions, and preferably are not included. Therefore, according to an embodiment solvents and/or carriers (referred to herein as stabilizing agents) for phase stability which do not substantially contribute to soil removal may be included.
  • the cleaning compositions of the invention may include a stabilizing agent to adjust the viscosity of the final composition.
  • the intended final use of the composition may determine whether or not a stabilizing agent is included in the cleaning composition. If a stabilizing agent is included in the cleaning composition, it is usually a low cost solvent such as isopropyl alcohol and/or propylene glycol. According to the invention solvent may or may not be included to improve soil removal, handleability or ease of use of the compositions of the invention.
  • the carrier includes primarily water.
  • the carrier can include or be primarily an organic solvent, such as simple alkyl alcohols, e.g. , ethanol, isopropanol, n-propanol, benzyl alcohol, and the like.
  • Organic solvent such as simple alkyl alcohols, e.g. , ethanol, isopropanol, n-propanol, benzyl alcohol, and the like.
  • Polyols are also useful carriers, including glycerol, sorbitol, and the like.
  • Suitable stabilizing agents include, but are not limited to: glycol ethers.
  • Suitable glycol ethers include diethylene glycol n-butyl ether, diethylene glycol n- propyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol t-butyl ether, dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol tert-butyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol methyl ether acetate, propylene glycol n-butyl ether, propylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol methyl ether, tripropylene glycol methyl ether and tripropylene glycol
  • DOWANOL EPHTM commercially available as DOWANOL EPHTM from Dow Chemical Co.
  • DOWANOL PPHTM commercially available as DOWANOL PPHTM from Dow Chemical Co.
  • glycol ethers include Butoxyethyl PROPASOL , Butyl CARBITOLTM acetate, Butyl CARBITOLTM, Butyl CELLOSOLVETM acetate, Butyl CELLOSOLVETM, Butyl DIPROPASOLTM, Butyl PROPASOLTM, CARBITOLTM PM- 600, CARBITOLTM Low Gravity, CELLOSOLVETM acetate, CELLOSOLVETM, Ester EEPTM, FILMER IBTTM, Hexyl CARBITOLTM, Hexyl CELLOSOLVETM, Methyl CARBITOLTM, Methyl CELLOSOLVETM acetate, Methyl CELLOSOLVETM, Methyl DIPROPASOLTM, Methyl PROPASOLTM acetate, Methyl PROPASOLTM, Propyl CARBITOL , Propyl CELLOSOLVE
  • compositions include from about 0 wt-% - 20 wt-% stabilizing agent(s), from about 0.1 wt-% - 15 wt-% stabilizing agent(s), from about 1 wt-% - 15 wt-% stabilizing agent(s), preferably from about 5 wt-% - 10 wt-% stabilizing agent(s).
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • the compositions of the present invention include a source of water.
  • the composition may include water provided as deionized water or as softened water.
  • the water provided as part of the concentrate can be relatively free of hardness. It is expected that the water can be deionized to remove a portion of the dissolved solids. That is, the concentrate can be formulated with water that includes dissolved solids, and can be formulated with water that can be characterized as hard water.
  • the present composition of a concentrated liquid composition includes about 0.1 to about 80 wt-% water, about 1 to about 80 wt-% water, about 5 to about 50 wt-% water, or about 5 to about 20 wt-% water. It is to be understood that all values and ranges between these values and ranges are encompassed by the present invention.
  • the emulsifying compositions and/or hard surface cleaning compositions include the fatty alcohol ethoxylate, alkyl
  • polyethylene glycol and ethoxylate propoxylate block copolymer which make up a large amount, or even substantially all of the total weight of the emulsifying compositions.
  • additional functional ingredients may be included in the compositions.
  • the functional ingredients provide desired properties and functionalities to the compositions.
  • the term "functional ingredient" includes a material that when dispersed or dissolved in a use and/or concentrate solution, such as an aqueous solution, provides a beneficial property in a particular use.
  • the compositions do not include solvents contributing to soil removal. In further preferred embodiments, the compositions do not include hydro tropes, couplers, sequestrants and/or chelating agents. In preferred embodiments, the compositions used for a pre- wash or pre-soak application do not include additional surfactants, other than the blend of nonionic surfactants disclosed herein.
  • compositions may include optical brighteners, solubility modifiers, dispersants, stabilizing agents, additional surfactants, fragrances and/or dyes, rheology modifiers or thickeners/gelling agents, enzymes, enzyme stabilizing agents, carriers, buffers, solvents and the like.
  • an optical brightener component may also be present in the compositions of the present invention.
  • the optical brightener can include any brightener that is capable of eliminating graying and yellowing of fabrics. Typically, these substances attach to the fibers and bring about a brightening and simulated bleaching action by converting invisible ultraviolet radiation into visible longer- wave length light, the ultraviolet light absorbed from sunlight being irradiated as a pale bluish fluorescence and, together with the yellow shade of the grayed or yellowed laundry, producing pure white.
  • Fluorescent compounds belonging to the optical brightener family are typically aromatic or aromatic heterocyclic materials often containing condensed ring systems. An important feature of these compounds is the presence of an uninterrupted chain of conjugated double bonds associated with an aromatic ring. The number of such conjugated double bonds is dependent on substituents as well as the planarity of the fluorescent part of the molecule.
  • Most brightener compounds are derivatives of stilbene or 4,4'-diamino stilbene, biphenyl, five membered
  • heterocycles triazoles, oxazoles, imidazoles, etc.
  • six membered heterocycles cumarins, naphthalamides, triazines, etc.
  • Optical brighteners useful in the present invention are known and
  • optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles and other miscellaneous agents. Examples of these types of brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982), the disclosure of which is incorporated herein by reference.
  • Stilbene derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives of bis(triazinyl)amino-stilbene;
  • optical brighteners include stilbene derivatives.
  • Suitable optical brightener levels include from about 0.01 by weight to about 1% by weight, preferably from about 0.05% by weight to about 0.1% by weight, and more preferably from about 0.1% by weight to about 0.5% by weight.
  • Dyes may be included to alter the appearance of the composition, as for example, Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analine and Chemical), Metanil Yellow (Keystone Analine and
  • Fragrances or perfumes that may be included in the compositions include, for example, terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, a jasmine such as CIS-jasmine orjasmal, vanillin, and the like.
  • compositions can comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.
  • Enzymes can be included herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and/or for fabric restoration.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,
  • phospholipases esterases, cutinases, pectinases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases,P-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, amylases, or combinations thereof and may be of any suitable origin.
  • the choice of enzyme(s) takes into account factors such as pH-activity, stability optima, thermostability, stability versus active detergents, chelants, builders, etc.
  • detersive enzymes suitable for use herein is provided in U.S. Patent Nos. 4,261,868, 4,435,307 and 6,579,839, EP 130756, WO 91/06637, WO 94/02597, WO 95/10591, WO 96/23873, WO 99/20726 and WO 02/099091, each of which are herein incorporated by reference in its entirety.
  • compositions can comprise one or more solvents which provide cleaning performance and/or enhanced soil removal.
  • suitable solvents agents include, but are not limited to: oxygenated solvents such as lower alkanols, lower alkyl ethers, glycols, aryl glycol ethers and lower alkyl glycol ethers.
  • other solvents include, but are not limited to: methanol, ethanol, propanol, isopropanol and butanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, mixed ethylene-propylene glycol ethers, ethylene glycol phenyl ether, and propylene glycol phenyl ether.
  • Substantially water soluble glycol ether solvents include, not are not limited to: propylene glycol methyl ether, propylene glycol propyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol dimethyl ether, ethylene glycol propyl ether, diethylene glycol ethyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether and the like.
  • compositions of the present invention include additional surfactants.
  • the cleaning composition may include and/or be used in combination with additional surfactants, including co- surfactants that are either nonionic surfactants and/or anionic or other surfactant classes.
  • co- surfactants that are either nonionic surfactants and/or anionic or other surfactant classes.
  • the additional surfactants may be included in amounts from about 0.1 wt-% or more, or from about 1 wt-% or more.
  • the compositions of the present invention include about 10 ppm to about 1000 ppm of an additional surfactant. It is to be understood that all values and ranges between these values and ranges are encompassed by the present invention.
  • Useful nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety which in common practice is ethylene oxide or a polyhydration product thereof, polyethylene glycol.
  • any hydrophobic compound having a hydroxyl, carboxyl, amino, or amido group with a reactive hydrogen atom can be condensed with ethylene oxide, or its polyhydration adducts, or its mixtures with alkoxylenes such as propylene oxide to form a nonionic surface-active agent.
  • hydrophilic polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water dispersible or water soluble compound having the desired degree of balance between hydrophilic and hydrophobic properties.
  • Useful nonionic surfactants include:
  • the alcohol moiety can consist of mixtures of alcohols in the above delineated carbon range or it can consist of an alcohol having a specific number of carbon atoms within this range. Examples of like commercial surfactant are available under the trade names NeodolTM
  • the acid moiety can consist of mixtures of acids in the above defined carbon atoms range or it can consist of an acid having a specific number of carbon atoms within the range. Examples of commercial compounds of this chemistry are available on the market under the trade names NopalcolTM manufactured by Henkel Corporation and LipopegTM
  • nonionic low foaming surfactants examples include:
  • Nonionic compounds which are modified, essentially reversed, by adding ethylene oxide to ethylene glycol to provide a hydrophile of designated molecular weight; and, then adding propylene oxide to obtain hydrophobic blocks on the outside (ends) of the molecule.
  • the hydrophobic portion of the molecule weighs from about 1,000 to about 3,100 with the central hydrophile including 10% by weight to about 80% by weight of the final molecule.
  • PluronicTM R surfactants are manufactured by BASF Corporation under the trade name PluronicTM R surfactants.
  • TetronicTM R surfactants are produced by BASF Corporation by the sequential addition of ethylene oxide and propylene oxide to ethylenediamine.
  • the hydrophobic portion of the molecule weighs from about 2,100 to about 6,700 with the central hydrophile including 10% by weight to 80% by weight of the final molecule.
  • Nonionic compounds which are modified by "capping” or “end blocking” the terminal hydroxy group or groups (of multi-functional moieties) to reduce foaming by reaction with a small hydrophobic molecule such as propylene oxide, butylene oxide, benzyl chloride; and, short chain fatty acids, alcohols or alkyl halides containing from 1 to about 5 carbon atoms; and mixtures thereof. Also included are reactants such as thionyl chloride which convert terminal hydroxy groups to a chloride group. Such modifications to the terminal hydroxy group may lead to all- block, block-heteric, heteric-block or all-heteric nonionics.
  • Additional examples of effective low foaming nonionics include: The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issued Sep. 8, 1959 to Brown et al. and represented by the formula in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.
  • polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issued Aug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains where the weight of the terminal hydrophobic chains, the weight of the middle hydrophobic unit and the weight of the linking hydrophilic units each represent about one-third of the condensate.
  • defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178 issued May 7, 1968 to Lissant et al. having the general formula Z[(OR) n OH] z wherein Z is alkoxylatable material, R is a radical derived from an alkaline oxide which can be ethylene and propylene and n is an integer from, for example, 10 to 2,000 or more and z is an integer determined by the number of reactive
  • polyoxypropylene hydrophobic base is at least about 900 and m has value such that the oxyethylene content of the molecule is from about 10% to about 90% by weight.
  • Compounds falling within the scope of the definition for Y include, for example, propylene glycol, glycerine, pentaerythritol, trimethylolpropane, ethylenediamine and the like.
  • the oxypropylene chains optionally, but advantageously, contain small amounts of ethylene oxide and the oxyethylene chains also optionally, but advantageously, contain small amounts of propylene oxide.
  • Additional conjugated polyoxyalkylene surface- active agents which are advantageously used in the compositions of this invention correspond to the formula: P[(C 3 H 6 0) n (C 2 H 4 0) m H] x wherein P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms in which x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least about 44 and m has a value such that the oxypropylene content of the molecule is from about 10% to about 90% by weight.
  • the oxypropylene chains may contain optionally, but advantageously, small amounts of ethylene oxide and the oxyethylene chains may contain also optionally, but advantageously, small amounts of propylene oxide.
  • Polyhydroxy fatty acid amide surfactants suitable for use in the present compositions include those having the structural formula R 2 CON R1 Z in which: Rl is H, CrC 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy group, or a mixture thereof; R 2 is a C 5 -C 31 hydrocarbyl, which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z can be derived from a reducing sugar in a reductive amination reaction; such as a glycityl moiety.
  • alkyl ethoxylate condensation products of aliphatic alcohols with from about 0 to about 25 moles of ethylene oxide are suitable for use in the present compositions.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Suitable nonionic alkylpolysaccharide surfactants particularly for use in the present compositions include those disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include a hydrophobic group containing from about 6 to about 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the inters accharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units.
  • Fatty acid amide surfactants suitable for use the present compositions include those having the formula: R6CON(R 7 ) 2 in which R 6 is an alkyl group containing from 7 to 21 carbon atoms and each R 7 is independently hydrogen, Q- C 4 alkyl, C - C 4 hydroxyalkyl, or— ( C 2 H 4 0)xH, where x is in the range of from 1 to 3.
  • a useful class of non-ionic surfactants includes the class defined as alkoxylated amines or, most particularly, alcohol alkoxylated/aminated/alkoxylated surfactants. These non-ionic surfactants may be at least in part represented by the general formulae: R 20 -(PO) S N-(EO) t H, R 20 -(PO) S N-(EO) t H(EO) t H, and R 20 -
  • R 20 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14 carbon atoms
  • EO is oxyethylene
  • PO is oxypropylene
  • s is 1 to 20, preferably 2-5
  • t is 1-10, preferably 2-5
  • u is 1-10, preferably 2-5.
  • R 20 is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w and z are independently 1-10, preferably 2-5.
  • v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2))
  • w and z are independently 1-10, preferably 2-5.
  • These compounds are represented commercially by a line of products sold by Huntsman Chemicals as nonionic surfactants.
  • a preferred chemical of this class includes SurfonicTM PEA 25 Amine Alkoxylate.
  • Preferred nonionic surfactants for the compositions of the invention include alcohol alkoxylates, EO/PO block copolymers, alkylphenol alkoxylates, and the like.
  • the semi-polar type of nonionic surface active agents is another class of nonionic surfactant useful in compositions of the present invention.
  • semi- polar nonionics are high foamers and foam stabilizers, which can limit their application in CIP systems. However, within compositional embodiments of this invention designed for high foam cleaning methodology, semi-polar nonionics would have immediate utility.
  • the semi-polar nonionic surfactants include the amine oxides, phosphine oxides, sulfoxides and their alkoxylated derivatives.
  • Amine oxides are tertiary amine oxides corresponding to the general formula: wherein the arrow is a conventional representation of a semi-polar bond; and, R 1 , R 2 , and R may be aliphatic, aromatic, heterocyclic, alicyclic, or combinations thereof.
  • R 1 is an alkyl radical of from about 8 to about 24 carbon atoms
  • R 2 and R 3 are alkyl or hydroxyalkyl of 1-3 carbon atoms or a mixture thereof
  • R 2 and R 3 can be attached to each other, e.g. through an oxygen or nitrogen atom, to form a ring structure
  • R 4 is an alkaline or a hydroxyalkylene group containing 2 to 3 carbon atoms
  • n ranges from 0 to about 20.
  • Useful water soluble amine oxide surfactants are selected from the coconut or tallow alkyl di-(lower alkyl) amine oxides, specific examples of which are dodecyldimethylamine oxide, tridecyldimethylamine oxide, etradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide,
  • Useful semi-polar nonionic surfactants also include the water soluble phosphine oxides having the following structure: wherein the arrow is a conventional representation of a semi-polar bond; and,
  • R 1 is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 to about 24 carbon atoms in chain length; and, R 2 and R 3 are each alkyl moieties separately selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.
  • phosphine oxides examples include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphone oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide, and
  • Semi-polar nonionic surfactants useful herein also include the water soluble sulfoxide compounds which have the structure:
  • R 1 is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbon atoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxyl substituents; and R is an alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.
  • sulfoxides include dodecyl methyl sulfoxide; 3- hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methyl sulfoxide; and 3- hydroxy-4-dodecoxybutyl methyl sulfoxide.
  • Semi-polar nonionic surfactants for the compositions of the invention include dimethyl amine oxides, such as lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinations thereof, and the like.
  • Useful water soluble amine oxide surfactants are selected from the octyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(lower alkyl) amine oxides, specific examples of which are octyldimethylamine oxide, nonyldimethylamine oxide,
  • decyldimethylamine oxide undecyldimethylamine oxide, dodecyldimethylamine oxide, iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,
  • octadecyldimethylaine oxide dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide,
  • octadecyldibutylamine oxide bis(2-hydroxyethyl)dodecylamine oxide, bis(2- hydroxyethyl)-3-dodecoxy-l-hydroxypropylamine oxide, dimethyl-(2- hydroxydodecyl) amine oxide, 3,6,9-trioctadecyldimethylamine oxide and 3- dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.
  • Suitable nonionic surfactants suitable for use with the compositions of the present invention include alkoxylated surfactants.
  • Suitable alkoxylated surfactants include EO/PO copolymers, capped EO/PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixtures thereof, or the like.
  • Suitable alkoxylated surfactants for use as solvents include EO/PO block copolymers, such as the Pluronic and reverse Pluronic surfactants; alcohol alkoxylates, such as Dehypon LS-54 (R- (EO) 5 (PO) 4 ) and Dehypon LS-36 (R-(EO) 3 (PO) 6 ); and capped alcohol alkoxylates, such as Plurafac LF221 and Tegoten ECU; mixtures thereof, or the like.
  • surface active substances which are categorized as anionics because the charge on the hydrophobe is negative; or surfactants in which the hydrophobic section of the molecule carries no charge unless the pH is elevated to neutrality or above (e.g. carboxylic acids).
  • Carboxylate, sulfonate, sulfate and phosphate are the polar (hydrophilic) solubilizing groups found in anionic surfactants.
  • cations counter ions
  • sodium, lithium and potassium impart water solubility
  • ammonium and substituted ammonium ions provide both water and oil solubility
  • calcium, barium, and magnesium promote oil solubility.
  • anionics are excellent detersive surfactants and are therefore favored additions to heavy duty detergent compositions.
  • Anionic sulfate surfactants suitable for use in the present compositions include alkyl ether sulfates, alkyl sulfates, the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5 -C 17 acyl-N-(Ci -C 4 alkyl) and -N-(Ci - C 2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside, and the like.
  • alkyl sulfates alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy) sulfates such as the sulfates or condensation products of ethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylene groups per molecule).
  • Anionic sulfonate surfactants suitable for use in the present compositions also include alkyl sulfonates, the linear and branched primary and secondary alkyl sulfonates, and the aromatic sulfonates with or without substituents.
  • Anionic carboxylate surfactants suitable for use in the present compositions include carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates), ether carboxylic acids, and the like.
  • carboxylates include alkyl ethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps (e.g. alkyl carboxyls).
  • Secondary carboxylates useful in the present compositions include those which contain a carboxyl unit connected to a secondary carbon. The secondary carbon can be in a ring structure, e.g.
  • the secondary carboxylate surfactants typically contain no ether linkages, no ester linkages and no hydroxyl groups. Further, they typically lack nitrogen atoms in the head-group (amphiphilic portion). Suitable secondary soap surfactants typically contain 11- 13 total carbon atoms, although more carbons atoms (e.g. , up to 16) can be present.
  • Suitable carboxylates also include acylamino acids (and salts), such as acylgluamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyl taurates and fatty acid amides of methyl tauride), and the like.
  • Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the following formula:
  • R is a Cg to C 22 alkyl group or 5 in which R 1 is a C4-C 16 alkyl group; n is an integer of 1-20; m is an integer of 1-3; and X is a counter ion, such as hydrogen, sodium, potassium, lithium, ammonium, or an amine salt such as monoethanolamine, diethanolamine or triethanolamine.
  • n is an integer of 4 to 10 and m is 1.
  • R is a alkyl group.
  • R is a C 12 -C 14 alkyl group, n is 4, and m is 1.
  • R is and R 1 is a C 6 -C 12 alkyl group. In still yet other embodiments, R 1 is a C 9 alkyl group, n is 10 and m is 1.
  • alkyl and alkylaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are typically available as the acid forms, which can be readily converted to the anionic or salt form. Commercially available carboxylates include, Neodox 23-4, a C 12-13 alkyl polyethoxy (4) carboxylic acid (Shell
  • Emcol CNP-110 a C 9 alkylaryl polyethoxy (10) carboxylic acid (Witco Chemical).
  • Carboxylates are also available from Clariant, e.g. the product Sandopan ® DTC, a C 13 alkyl polyethoxy (7) carboxylic acid.
  • cationic surfactants may be synthesized from any combination of elements containing an "onium" structure RnX+Y— and could include compounds other than nitrogen (ammonium) such as phosphorus (phosphonium) and sulfur (sulfonium).
  • ammonium such as phosphorus (phosphonium) and sulfur (sulfonium).
  • the cationic surfactant field is dominated by nitrogen containing compounds, probably because synthetic routes to nitrogenous cationics are simple and straightforward and give high yields of product, which can make them less expensive.
  • Cationic surfactants preferably include, more preferably refer to, compounds containing at least one long carbon chain hydrophobic group and at least one positively charged nitrogen.
  • the long carbon chain group may be attached directly to the nitrogen atom by simple substitution; or more preferably indirectly by a bridging functional group or groups in so-called interrupted alkylamines and amido amines.
  • Such functional groups can make the molecule more hydrophilic and/or more water dispersible, more easily water solubilized by co-surfactant mixtures, and/or water soluble.
  • additional primary, secondary or tertiary amino groups can be introduced or the amino nitrogen can be quatemized with low molecular weight alkyl groups.
  • the nitrogen can be a part of branched or straight chain moiety of varying degrees of unsaturation or of a saturated or unsaturated heterocyclic ring.
  • cationic surfactants may contain complex linkages having more than one cationic nitrogen atom.
  • the surfactant compounds classified as amine oxides, amphoterics and zwitterions are themselves typically cationic in near neutral to acidic pH solutions and can overlap surfactant classifications.
  • Polyoxyethylated cationic surfactants generally behave like nonionic surfactants in alkaline solution and like cationic surfactants in acidic solution.
  • R represents a long alkyl chain
  • R', R" and R'" may be either long alkyl chains or smaller alkyl or aryl groups or hydrogen and X represents an anion.
  • the amine salts and quaternary ammonium compounds are preferred for practical use in this invention due to their high degree of water solubility.
  • the majority of large volume commercial cationic surfactants can be subdivided into four major classes and additional sub-groups known to those or skill in the art and described in "Surfactant Encyclopedia", Cosmetics & Toiletries, Vol. 104 (2) 86-96 (1989).
  • the first class includes alkylamines and their salts.
  • the second class includes alkyl imidazolines.
  • the third class includes ethoxylated amines.
  • the fourth class includes quaternaries, such as alkylbenzyldimethylammonium salts, alkyl benzene salts, heterocyclic ammonium salts, tetra alkylammonium salts, and the like.
  • Cationic surfactants are known to have a variety of properties that can be beneficial in the present compositions. These desirable properties can include detergency in compositions of or below neutral pH, antimicrobial efficacy, thickening or gelling in cooperation with other agents, and the like.
  • Cationic surfactants useful in the compositions of the present invention include those having the formula 1 2 rein each 1
  • R M R X Y L Z whe R is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to four of the following structures:
  • the R 1 groups can additionally contain up to 12 ethoxy groups, m is a number from 1 to 3. Preferably, no more than one R 1 group in a molecule has 16 or more carbon atoms when m is 2 or more than 12 carbon atoms when m is 3.
  • Each R is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R in a molecule being benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom positions on the Y group are filled by hydrogens.
  • Y is can be a group including, but not limited to:
  • L is 1 or 2
  • Y groups being separated by a moiety selected from R 1 and R 2 analogs (preferably alkylene or alkenylene) having from 1 to about 22 carbon atoms and two free carbon single bonds when L is 2.
  • Z is a water soluble anion, such as a halide, sulfate, methylsulfate, hydroxide, or nitrate anion, particularly preferred being chloride, bromide, iodide, sulfate or methyl sulfate anions, in a number to give electrical neutrality of the cationic component.
  • Amphoteric, or ampholytic, surfactants contain both a basic and an acidic hydrophilic group and an organic hydrophobic group. These ionic entities may be any of anionic or cationic groups described herein for other types of surfactants.
  • a basic nitrogen and an acidic carboxylate group are the typical functional groups employed as the basic and acidic hydrophilic groups.
  • surfactants sulfonate, sulfate, phosphonate or phosphate provide the negative charge.
  • Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g. , carboxy, sulfo, sulfato, phosphato, or phosphono.
  • Amphoteric surfactants are subdivided into two major classes known to those of skill in the art and described in "Surfactant Encyclopedia" Cosmetics & Toiletries, Vol. 104 (2) 69-71 (1989), which is herein incorporated by reference in its entirety.
  • the first class includes acyl/dialkyl ethylenediamine derivatives (e.g. 2-alkyl hydroxyethyl imidazoline derivatives) and their salts.
  • the second class includes N-alkylamino acids and their salts.
  • Amphoteric surfactants can be synthesized by methods known to those of skill in the art. For example, 2-alkyl hydroxyethyl imidazoline is synthesized by condensation and ring closure of a long chain carboxylic acid (or a derivative) with dialkyl ethylenediamine. Commercial amphoteric surfactants are derivatized by subsequent hydrolysis and ring-opening of the imidazoline ring by alkylation— for example with chloroacetic acid or ethyl acetate. During alkylation, one or two carboxy- alkyl groups react to form a tertiary amine and an ether linkage with differing alkylating agents yielding different tertiary amines.
  • R is an acyclic hydrophobic group containing from about 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion, generally sodium.
  • imidazoline-derived amphoterics that can be employed in the present compositions include for example: Cocoamphopropionate,
  • Cocoamphocarboxy-propionate Cocoamphoglycinate, Cocoamphocarboxy- glycinate, Cocoamphopropyl- sulfonate, and Cocoamphocarboxy-propionic acid.
  • Amphocarboxylic acids can be produced from fatty imidazolines in which the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
  • Betaines are a special class of amphoteric discussed herein below in the section entitled, Zwitterion Surfactants.
  • N-alkylamino acids are readily prepared by reaction RNH 2 , in which straight or branched chain alkyl, fatty amines with halogenated carboxylic acids. Alkylation of the primary amino groups of an amino acid leads to secondary and tertiary amines. Alkyl substituents may have additional amino groups that provide more than one reactive nitrogen center. Most commercial N-alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl) alanine.
  • N-alkylamino acid ampholytes having application in this invention include alkyl beta- amino dipropionates, RN(C 2 H 4 COOM) 2 and
  • R can be an acyclic hydrophobic group containing from about 8 to about 18 carbon atoms, and M is a cation to neutralize the charge of the anion.
  • Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acid. Additional suitable coconut derived surfactants include as part of their structure an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety, e.g. , glycine, or a combination thereof; and an aliphatic substituent of from about 8 to 18 (e.g. , 12) carbon atoms. Such a surfactant can also be considered an alkyl amphodicarboxylic acid.
  • amphoteric surfactants can include chemical structures represented as: C 12 -alkyl- C(0)-NH-CH 2 -CH 2 -N + (CH 2 -CH 2 -C0 2 Na) 2 -CH 2 -CH 2 -OH or C 12 -alkyl-C(0)-N(H)- CH 2 -CH 2 -N + (CH 2 -C0 2 Na) 2 -CH 2 -CH 2 -OH.
  • Disodium cocoampho dipropionate is one suitable amphoteric surfactant and is commercially available under the tradename MiranolTM FBS from Rhodia Inc., Cranbury, N.J.
  • Another suitable coconut derived amphoteric surfactant with the chemical name disodium cocoampho diacetate is sold under the tradename MirataineTM JCHA, also from Rhodia Inc., Cranbury, N.J.
  • Zwitterionic surfactants can be thought of as a subset of the amphoteric surfactants and can include an anionic charge.
  • Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
  • a zwitterionic surfactant includes a positive charged quaternary ammonium or, in some cases, a sulfonium or phosphonium ion; a negative charged carboxyl group; and an alkyl group.
  • Zwitterionics generally contain cationic and anionic groups which ionize to a nearly equal degree in the isoelectric region of the molecule and which can develop strong" inner-salt" attraction between positive-negative charge centers.
  • zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • a general formula for these compounds is: wherein R 1 contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8 to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R is an alkyl or monohydroxy alkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R is an alkylene or hydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
  • zwitterionic surfactants having the structures listed above include: 4- [N,N-di(2-hydroxyethyl)-N-octadecylammonio] -butane- 1 -carboxylate; 5- [S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-l-sulfate; 3-[P,P- diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-l-phosphate; 3- [N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio] -propane- 1 -phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)-propane-l-sulfonate; 3-(N,N-dimethyl-N- hexadecylammonio)-2-hydroxy-prop
  • the zwitterionic surfactant suitable for use in the present compositions includes a betaine of the general structure:
  • betaines typically do not exhibit strong cationic or anionic characters at pH extremes nor do they show reduced water solubility in their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are compatible with anionics. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C 12-14
  • acylamidodimethylbetaine C 12-16 acylamidopentanediethylbetaine; and C 12-16 acylmethylamidodimethylbetaine .
  • Sultaines useful in the present invention include those compounds having the formula (RCR 1 ⁇ N + R 2 S0 3" , in which R is a C 6 -C 18 hydrocarbyl group, each R 1 is typically independently Q-C 3 alkyl, e.g. methyl, and R is a C -C hydrocarbyl group, e.g. a Q-C 3 alkylene or hydroxyalkylene group.
  • compositions of the invention can be formed in a concentrated water-free, aqueous, or a thickened aqueous liquid concentrate for use in forming a use composition.
  • nonionic surfactant blends are in a ratio of linear alcohol ethoxylate to branched alcohol ethoxylate (e.g. Guerbet alcohol ethoxylate) to EO- PO copolymer from about 1 : 1 : 1 to about 10: 1 : 10, from about 1 : 1 : 1 to about 7.5: 1 :5 preferably from about 1 : 1 : 1 to about 2: 1 :2.
  • linear alcohol ethoxylate to branched alcohol ethoxylate e.g. Guerbet alcohol ethoxylate
  • EO- PO copolymer from about 1 : 1 : 1 to about 10: 1 : 10
  • EO- PO copolymer from about 1 : 1 : 1 to about 10: 1 : 10
  • EO- PO copolymer from about 1 : 1 : 1 to about 10: 1 : 10
  • EO- PO copolymer from about 1 : 1 : 1 to about 10: 1 : 10
  • the detergent compositions may include concentrate compositions or may be diluted to form use compositions.
  • a concentrate refers to a composition that is intended to be diluted with water to provide a use solution that contacts an object to provide the desired cleaning, rinsing, or the like.
  • the detergent composition that contacts the articles to be washed can be referred to as a concentrate or a use composition (or use solution) dependent upon the formulation employed in methods according to the invention. It should be understood that the concentration of the nonionic surfactants and other functional ingredients in the composition will vary depending on whether the detergent composition is provided as a concentrate or as a use solution.
  • a use solution may be prepared from the concentrate by diluting the concentrate with water at a dilution ratio that provides a use solution having desired detersive properties.
  • the water that is used to dilute the concentrate to form the use composition can be referred to as water of dilution or a diluent, and can vary from one location to another.
  • the typical dilution factor is between approximately 1 and approximately 10,000 but will depend on factors including the amount of soil and type of soil to be removed and the like.
  • the concentrate is diluted at a ratio of between about 1 : 10 and about 1 : 10,000 concentrate to water.
  • the concentrate is diluted at a ratio of between about 1 : 100 and about 1 :5,000 concentrate to water. More particularly, the concentrate is diluted at a ratio of between about 1 :250 and about 1 :2,000 concentrate to water.
  • a use solution of the composition provides from about 0.01 % to about 1 % actives. In further aspects of the invention a use solution of the composition provides from about 0.01 % to about 0.5 % actives.
  • the combination of the surfactants provide efficacious soil emulsification and removal at low concentrations. For example, beneficial results are achieved at concentrations as low as from about 0.01 % to about 0.25 % actives, from about 0.01 % to about 0.15 % actives, from about 0.01 % to about 0.05 % actives.
  • a use solution of the composition has between about 1 ppm to about 1000 ppm linear alcohol ethoxylate surfactant, between about 1 ppm to about 1000 ppm branched alcohol ethoxylate surfactant (e.g. Guerbet alcohol ethoxylate), and between 1 ppm to about 1000 ppm EO-PO copolymer.
  • a use solution of the composition has between about 1 ppm to about 500 ppm linear alcohol ethoxylate surfactant, between about 1 ppm to about 500ppm branched alcohol ethoxylate surfactant (e.g.
  • a use concentration of the various nonionic surfactants in the aqueous compositions of the invention is between about 100 ppm to about 5,000 ppm, from about 250 ppm to about 2,500 ppm, or more preferably from about 500 ppm to about 1,000 ppm nonionic surfactants.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • compositions are to be employed in the emulsifying of laundry soils and cleaning articles, e.g. , textiles, which have become soiled.
  • oily soils are emulsified, making them dispersible in a wash liquor.
  • the compositions of the present invention can be used to remove stains from any conventional textile, including but not limited to, cotton, poly-cotton blends, wool, and polyesters.
  • the compositions can be used on any item or article made from or including textile materials, woven fabrics, non-woven fabrics, and knitted fabrics.
  • the textile materials can include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof including cotton and polyester blends.
  • the fibers can be treated or untreated.
  • Such textiles are commonly used as table linens, kitchen rages, chef coats, massage towels, etc. and other applications wherein greasy and oily soils are expected.
  • compositions of the present invention are also textile tolerant, i.e., they will not substantially degrade the textile to which they are applied.
  • the compounds of the present invention can be used to remove a variety of stains from a variety of sources including, but not limited to, lipstick, pigment/sebum, pigment/lanolin, soot, olive or other vegetable oils, mineral oil, motor oil, other oils, blood, make-up, red wine, tea, ketchup, organic grease and fat soils, including those from meat, protein and/or carbohydrate sources, any additional soils and combinations thereof.
  • the methods of removing soils from a textile may be employed either inside or outside a washing machine, when employing a method of removing soils in a laundry application.
  • aqueous composition when employed outside the washing machine it is used in a concentrated formulation.
  • the aqueous composition when employed inside the washing machine it is used in a diluted (or a highly diluted) formulation, such as within the wash liquor of a washing machine in order to remove soils from textiles.
  • textile materials can be subjected to several treatment steps in an industrial sized laundry washing machine to provide cleaning.
  • exemplary treatment steps include a presoak or a prewash step, a wash step ⁇ e.g. soap and suds step), a rinse step for the removal of soil containing wash liquor, a bleach step (separate or in combination with the wash step), several optional rinse steps to remove the bleaching composition, an optional sour step to adjust the pH, softening step, and an extract step that often involves spinning the textiles to remove water.
  • the compositions of the invention can be employed in such exemplary conventional prewash or presoak steps, washing steps, and/or
  • compositions of the invention may be employed with a variety of laundry washing machines, including industrial, commercial and/or consumer machines (e.g. residential and/or home laundry washing machine).
  • the method for treating laundry according to the invention can be provided as part of an overall method for cleaning laundry according to the invention. That is, as part of a laundry cleaning operation, the compositions of the present invention can be used alone to treat the articles, e.g. , textiles, or can be used in conjunction with conventional detergents suitable for the articles to be treated.
  • a laundry cleaning process according to the invention can include the removal of soil, the removal of staining or the appearance of staining, and/or the reduction of a population of microbes.
  • the compositions of the invention can be used with conventional detergents in a variety of ways, for example, the compositions of the invention can be formulated with a conventional detergent.
  • Such formulation can include, for example, detergents for a pre-wash or pre-soak step and/or a soap/suds/bleach step.
  • detergents for a pre-wash or pre-soak step and/or a soap/suds/bleach step.
  • the compositions of the invention are employed to provide a detergency booster, such that the emulsifying efficacy of the compositions are combined with cleaning and/or bleaching efficacy of conventional detergents.
  • the compositions of the invention can be used to treat the article as a separate additive from a conventional detergent.
  • the compositions can be provided in the form of a concentrate that is diluted with water to provide a use solution.
  • the compositions can be provided in the form of a use solution (already diluted with water).
  • the compositions of the present invention can contact the article to be treated at any time.
  • the compounds and compositions of the invention can contact the article before, after, or substantially simultaneously as the articles are contacted with the selected detergent.
  • the use solution can be used for washing the articles and/or emulsifying soils from the articles.
  • the compositions are applied to a warm prewash step (e.g.
  • the article can then be washed thoroughly in a main or conventional sud step (i.e. wash step) using detergents, bleaching agents and/or alkaline builders.
  • the compositions contact the article before the articles are contacted with the selected detergent, e.g. a pre-soak or a pre-wash situation, wherein the articles are contacted with the composition of the invention initially to emulsify soils on the substrate fabric.
  • This step may include a contact time from a few minutes to a few hours, such as from about 2 hours to about 8 hours.
  • This step may optionally include the use of a builder or component compositions for providing a source of alkalinity, such as to increase the pH from neutral to an alkaline pH, including for example of a pH of at least 10, or at least 11 or greater.
  • the step may be conducted at a broad range of temperatures due to the unique blend of surfactants employed.
  • the pre-soak and/or pre-wash step may be at a use temperature of from about room temperature to at least about 60-70°C for a period of time effective to remove excess soils through emulsification.
  • the compositions may be combined with a bleaching and/or antimicrobial step, such that the emulsifying composition according to the invention is a detergent booster in a main wash step which increases the level of nonionic surfactants in the system.
  • This bleaching and antimicrobial step can follow or precede steps of washing the laundry with a composition of the invention and draining and/or rinsing the composition solution from the laundry.
  • it is expected that the bleaching and antimicrobial step can occur simultaneously with the washing step. It is expected that in situations where the soiling is relatively light, it may be advantageous to combine the washing step employing the emulsifying composition of the invention with the bleaching and antimicrobial step.
  • the bleaching and antimicrobial step can include a soil removal step and/or it can occur before or after a soil removal step.
  • the aqueous emulsifying composition is particularly suited for use as a pretreatment (i.e. pre-spotting) of stains on soiled articles using concentrated compositions outside of a washing machine. Such methods are preferably followed by a regular wash / laundry process, such as those disclosed herein the description of the invention.
  • the aqueous emulsifying composition is particularly suited for use as a presoak of a soiled article, such as a linen, within a container or vessel that is filled with water containing a dose of the aqueous emulsifying composition.
  • a soiled article such as a linen
  • a container or vessel that is filled with water containing a dose of the aqueous emulsifying composition.
  • Such methods are preferably followed by a regular wash / laundry process, such as those disclosed herein the description of the invention.
  • the aqueous emulsifying composition is particularly suited for use as a prewash step with or without added alkalinity (also referred to herein as a builder) in the washing machine.
  • a prewash step with or without added alkalinity (also referred to herein as a builder) in the washing machine.
  • Such methods may be include the use of laundry detergents or may preceed the steps of using laundry detergents, such as having the wash / laundry process follow with the subsequent use of other wash steps with main detergent, etc.
  • Such exemplary processes are disclosed herein the description of the invention.
  • the aqueous emulsifying composition is particularly suited for use as an additive composition within a regular wash / laundry process.
  • the aqueous emulsifying compositions can be employed as a detergency booster to a regular suds bath (regular wash / laundry process) which already contains a main detergent, alkalinity, and/or possibly bleach.
  • regular suds bath regular wash / laundry process
  • Such exemplary processes are disclosed herein the description of the invention.
  • compositions of the present invention can be used as a cleaning agent and/or bleaching agent to whiten or lighten or remove stains from a substrate, e.g. , hard surface.
  • the compositions are particularly suitable for treating non-laundry articles and surfaces including hard surfaces such as dishes, glasses, and other ware.
  • Embodiments of the present invention are further defined in the following non-limiting Examples. It should be understood that these Examples, while indicating certain embodiments of the invention, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the invention to adapt it to various usages and conditions. Thus, various modifications of the embodiments of the invention, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.
  • a tergotometer test procedure was employed to measure detergency of test compositions according to the invention.
  • a tergotometer along with 500 mL pots and water bath were employed.
  • First, unwashed swatches from the lot numbers to be used in the test are read on the Konica Minolta Spectrophotometer model CM-3600d to establish the average initial (before washing) L value.
  • a sampling of 25 of each swatch type is used.
  • the desired wash temperature is programmed into the
  • Tergotometer and its water bath is allowed to heat up to that temperature.
  • 500 mL of the desired water type is added to each Tergotometer pot and allowed to equilibrate to the desired temperature.
  • Test swatches (clean) were dipped into the solution of interest (e.g. chili oil, etc.). The soiled swatches are dried overnight before the detergency experiment. The following standard, commercially available (EMPA) soiled swatches were used for baseline testing in the Examples, as shown in Table 2.
  • EMPA commercially available
  • test detergent compositions are weighed out and added to the test detergent compositions.
  • Nonionic surfactant blend surfactant blend Liner fatty alcohol ethoxylate
  • nonionic surfactant Linear fatty alcohol ethoxylate blend Guerbet alcohol ethoxylate (5 moles)
  • the detergent systems were agitated for 30 sec to 1 minute (longer if necessary) to mix and dissolve in a hard water system (5 grains) to form a use solution of 0.03% in the hard tap water (concentration 0.03% unless indicated otherwise).
  • the agitation / mixing speed RPM was adjusted to 200.
  • the swatches are added quickly to their respective pots in a left to right sequence in order to minimize differences in exposure time to the detergent systems.
  • a wash run is completed for at least 10 minutes.
  • the swatches are removed from the pots quickly in a left to right sequence using a forceps and are transferred into 500 mis - 1 liter of cold water to rinse.
  • One container of cold rinse water is used for each pot.
  • the swatches are removed from the cold water and are further rinsed under cold tap water using a strainer or colander in a sink.
  • test compositions F43 and F64 provided improved oily soil removal (shown as % L* diff) over both control formulations, including the NPE-containing and NPE-free compositions.
  • % L* diff oily soil removal
  • the test compositions according to the invention provide superior cleaning performance (namely oily soil removal) in comparison to controls.
  • Example 1 The beneficial results obtained in Example 1 were further analyzed in the presence of a builder product to increase the pH conditions of the laundry application.
  • the methods of Example 1 were employed along with the use of an alkalinity-containing builder composition (commercially-available from Ecolab, Inc.).
  • the building provides to the cleaning system a source of sodium hydroxide and a polyacrylate (to control build-up caused by the hard water employed).
  • the pH of the cleaning systems was increased from about neutral to a pH between about 11.3 to about 11.5 with the addition of the builder component, with all other test conditions remaining constant.
  • both test compositions F43 and F64 provided improved soil removal (shown as % L* diff) over both control formulations, including the NPE-containing and NPE-free compositions.
  • the inclusion of a building to increase the pH conditions of the laundry cycle provided increased soil removal (shown as % L* diff) in comparison to the results shown in FIG. 1.
  • the test compositions according to the invention provide superior cleaning performance (soil removal) in comparison to controls.
  • FIG. 3 further demonstrates that additional detergency and soil removal achieved with the combination of the builder component with the compositions of the invention. This figure shows the side-by-side comparison of FIG. 1 and FIG. 2 data sets.
  • Example 1 Additional testing of the compositions according to the invention were conducted at additional higher temperature ranges.
  • the methods of Example 1 were further conducted using the laundry emulsifiers (F43, F64) in comparison to controls (NPE-containing, NPE-free) at temperatures of 30°C, 40°C, and 50°C.
  • FIG. 4 shows the results of the test formulations on EMPA 104 swatches at varying temperatures.
  • FIG. 5 shows the results of the test formulations on EMPA 106 swatches at varying temperatures.
  • FIG. 6 shows the results of the test formulations on EMPA 101 swatches at varying temperatures. The test compositions outperform the controls at all temperatures analyzed.
  • compositions according to the invention were analyzed to determine the impact of the degree of ethoxylation of the Guerbet alcohol ethoxylates.
  • the methods of Example 1 were conducted at a temperature of 40°C and using a 0.05 wt-% actives concentration of the use solutions (2 mL/kg linens).
  • the laundry emulsifiers (F64, F70) demonstrated improved detergency in comparison to both controls (NPE-containing, NPE-free) on all soil and linens evaluated, as shown in FIG. 7.
  • Example 2 employing a builder component with the use solutions of the compositions were further analyzed.
  • the builder was added at 6 mL/kg linens to reach a pH of 12.
  • the laundry emulsifiers (F64, F70) demonstrated additional improvements in detergency in comparison to the results of FIG. 7 and the resulted obtained by both controls (NPE-containing, NPE-free) on all soil and linens evaluated, as shown in FIG. 8.
  • FIG. 9 shows a comparison of the results from FIGS. 7-8, showing an embodiment of the invention of enhanced or boosted detergency with the emulsifier compositions according to the invention when used in combination with a builder (i.e. alkalinity source) or washing at elevated pH (above neutral).
  • a builder i.e. alkalinity source
  • a preferred NPE-free composition according to the invention was further analyzed to determine the impact of the concentration of the use solution on the soil removal in comparison to controls.
  • the methods of Example 1 were conducted using the EMPA 104 soiled swatches at concentrations of 1.2 mL/kg (0.03% actives), 2 mL/kg (0.05% actives) and 2 mL/kg with a builder (source of alkalinity at 6 mL/kg). The results are shown in FIG. 10.
  • the laundry emulsifier according to the invention F64
  • the tergotometer was employed to analyzed the b value (i.e. removal of yellowing from linen swatch) of the various test compositions and control formulations. The extent of the removal of yellow spectrum from the linen swatches were measured, wherein the lower the b value indicates detergency. As shown in
  • FIG. 11 the laundry emulsifiers (F64, F70) demonstrated at least equivalent detergency to the NPE-containing control and improved detergency in comparison to the NPE-free control.
  • the stability of the compositions according to the invention were further analyzed by adding stabilizing agents propylene glycol and isopropyl alcohol to the formulation of F70 employed in Examples 4 and 6.
  • the methods of Example 1 were employed at temperatures of 30°C and 50°C using 0.05 wt-% actives in use solution (2 mL/kg linen). Thereafter, the methods of Example 2 using a builder component to increase the pH of the use compositions (0.15 wt-% active) from neutral to pH 11.7 were analyzed. A mixing speed of 130 rpm was employed for 10 minutes for both tests at varying temperatures.
  • FIG. 12 shows additional results at 50°C with and without a builder component.
  • FIG. 14 shows a comparison at temperatures of 40°C, 50°C, 60°C , and 80°C wherein the
  • compositions (both stabilized and only active compositions) outperform the controls according to the embodiments of the invention using a builder to increase the pH of the use composition.
  • a builder to increase the pH of the use composition.
  • stabilizing agents into the compositions to provide phase stability does not impart any negative performance.

Abstract

La présente invention concerne un émulsifiant détergent utilisable pour le lavage du linge et le nettoyage de surfaces dures au moyen d'un mélange de tensioactifs ne contenant pas d'APE. Ledit système émulsifiant se révèle efficace pour ce qui est de l'élimination des salissures de nature huileuse et des taches d'aliments gras. Les compositions selon l'invention contiennent des éthoxylates d'alcools gras linéaires et ramifiés et des copolymères à blocs éthoxylate-propoxylate. L'invention concerne également des procédés d'utilisation dudit émulsifiant.
PCT/US2013/071548 2012-11-30 2013-11-23 Émulsifiant sans ape utilisable pour le lavage du linge WO2014085271A1 (fr)

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AU2013352450A AU2013352450B2 (en) 2012-11-30 2013-11-23 APE-free laundry emulsifier
BR112015010342-1A BR112015010342B1 (pt) 2012-11-30 2013-11-23 Composição concentrada isenta de ape para prétratamento ou pré-imersão e método para remover manchas de tecidos ou superfícies rígidas
AU2017201359A AU2017201359B2 (en) 2012-11-30 2017-02-28 APE-free laundry emulsifier

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US13/689,876 US8901063B2 (en) 2012-11-30 2012-11-30 APE-free laundry emulsifier
US13/689,876 2012-11-30
CN201310001447.6 2013-01-04
CN201310001447.6A CN103849476A (zh) 2012-11-30 2013-01-04 无烷基苯酚乙氧基化物的待洗衣物乳化剂

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WO2015191434A3 (fr) * 2014-06-09 2016-04-21 Stepan Company Détergents pour nettoyage à l'eau froide
US9890350B2 (en) 2015-10-28 2018-02-13 Ecolab Usa Inc. Methods of using a soil release polymer in a neutral or low alkaline prewash
US10233406B2 (en) * 2016-12-22 2019-03-19 Oxiteno S.A. Industria E Comercio Nonionic surfactant composition and surface cleaning formulation
US10947480B2 (en) 2016-05-17 2021-03-16 Conopeo, Inc. Liquid laundry detergent compositions
CN113046192A (zh) * 2019-12-27 2021-06-29 佛山市顺德区美的洗涤电器制造有限公司 适用于洗碗机的养护剂组合物

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US20110039748A1 (en) * 2007-12-10 2011-02-17 Reckitt Benckiser Inc. Hob Cleaning Composition
US20120199249A1 (en) * 2009-10-06 2012-08-09 Bwe I Malmo Ab Floor treatment
US20120066839A1 (en) * 2010-09-17 2012-03-22 Ecolab Usa Inc. Cleaning compositions employing extended chain anionic surfactants
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WO2015191434A3 (fr) * 2014-06-09 2016-04-21 Stepan Company Détergents pour nettoyage à l'eau froide
US9890350B2 (en) 2015-10-28 2018-02-13 Ecolab Usa Inc. Methods of using a soil release polymer in a neutral or low alkaline prewash
US10377979B2 (en) 2015-10-28 2019-08-13 Ecolab Usa Inc. Methods of using a soil release polymer in a prewash composition
US10947480B2 (en) 2016-05-17 2021-03-16 Conopeo, Inc. Liquid laundry detergent compositions
US11572529B2 (en) 2016-05-17 2023-02-07 Conopeo, Inc. Liquid laundry detergent compositions
US10233406B2 (en) * 2016-12-22 2019-03-19 Oxiteno S.A. Industria E Comercio Nonionic surfactant composition and surface cleaning formulation
CN113046192A (zh) * 2019-12-27 2021-06-29 佛山市顺德区美的洗涤电器制造有限公司 适用于洗碗机的养护剂组合物

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