WO2012080886A2 - Agent de nettoyage résistant à la saleté et traitement de surface - Google Patents

Agent de nettoyage résistant à la saleté et traitement de surface Download PDF

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Publication number
WO2012080886A2
WO2012080886A2 PCT/IB2011/055350 IB2011055350W WO2012080886A2 WO 2012080886 A2 WO2012080886 A2 WO 2012080886A2 IB 2011055350 W IB2011055350 W IB 2011055350W WO 2012080886 A2 WO2012080886 A2 WO 2012080886A2
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WO
WIPO (PCT)
Prior art keywords
soil
soil resistant
composition
olefin
water
Prior art date
Application number
PCT/IB2011/055350
Other languages
English (en)
Other versions
WO2012080886A3 (fr
Inventor
Kim R. Smith
Erik C. Olson
Keith E. Olson
Steven E. Lentsch
Minyu Li
Catherine Hansen
Andrew Wold
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
Application filed by Ecolab Usa Inc. filed Critical Ecolab Usa Inc.
Publication of WO2012080886A2 publication Critical patent/WO2012080886A2/fr
Publication of WO2012080886A3 publication Critical patent/WO2012080886A3/fr

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • 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
    • C11D3/3796—Amphoteric polymers or zwitterionic polymers
    • 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
    • C11D3/43—Solvents
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents

Definitions

  • the invention relates to soil resistant surface treatments.
  • soil resistant laminate compositions are formed using soil resistant treatment compositions according to the invention.
  • the soil resistant treatment compositions comprise polymers and/or copolymers and may include various carriers, including water or other organic solvents and/or detergent carriers. Kits and methods of cleaning and/or treating surfaces using the soil resistant treatment compositions and laminate compositions are provided for use on a variety of surfaces.
  • compositions have been developed for cleaning or coating hard non- porous surfaces.
  • Cleaning compositions often incorporate soil release agents, such as non-surfactant additives applied to a soiled surface as part of a detergent in order to improve soil removal capability of a detergent.
  • Soil release agents are effective by decreasing lubricity of a soiled surface in order to enhance soil removal through mechanical action.
  • Soil release agents are intended for application to soiled surfaces, as application to clean surfaces counterproductively results in attracting soil, causing the surface to become soiled again at a faster rate.
  • These prior art uses of soil release agents depend upon the change in soiled surfaces and requiring continued use for each new soil on a surface. Often they employ detergents for additional cleaning efficacy, rather than forming an evenly distributed laminate surface for soil resistance as accomplished by the present invention.
  • the soil resistant surface impairs the binding of soil through an intermediary polymer layer which makes it difficult for oily materials to wet the surface and enhances the wetting of water.
  • a further object of the invention is a novel polymeric treatment composition, including soil resistant agents that are polymers and/or copolymers, having a water or organic solvent carrier and methods of using the same to impart soil resistance to a treated surface, such as a clean surface.
  • a further object of the invention is a novel polymeric treatment composition, including soil resistant agents that are polymers and/or copolymers, preferably with a detergent composition carrier for even distribution across a treated surface, and methods of using the same to impart soil resistance to a surface, such as a soil or clean surface.
  • a further object of the invention is to provide a method of treating clean surfaces to prevent soils and limit or eliminate adherence to the surfaces.
  • a soil resistant laminate composition in one embodiment, includes a multilayer composition of a clean surface and a dried layer, wherein an aqueous solution is applied to a surface to form the dried layer and said aqueous solution is from about 0.005 wt% to about 20 wt% of at least one soil resistant agent having a molecular weight less than about 20,000 g/mol, preferably from about 1,000 to 10,000 g/mol, and more preferably from about 2,000 to 5,000 g/mol, and still more preferably about approximately 3,000 g/mol.
  • the at least one soil resistant agent is selected from copolymers from the group consisting of a maleic/olefin, an olefin/acrylate, and combinations thereof.
  • the soil resistant agent is substantially free of fluorinated, silicone, alkali soluble resin and/or plasticizer substituents and/or is modified such that no viscosity-building or threshold activity is exhibited.
  • the soil resistant laminate composition may be a floor coating that excludes floor finishes.
  • a soil resistant laminate composition includes a multilayer composition having an oil/water contact angle ratio of the laminate surface formed from the soil resistant agent and clean substrate of at least 2.
  • the composition includes a clean surface as a bottom layer and a dried layer of at least one soil resistant agent as a top layer, wherein said dried layer is formed from an aqueous solution of from about 0.1% to 5% soil resistant agent, and wherein said soil resistant agent has a molecular weight from about 1 ,000 to 20,000 g/mol.
  • a soil resistant laminate composition includes a soil release agent.
  • the soil release agent is from between about 0.1% and about 20% by weight and comprises an olefin/acrylate copolymer.
  • a soil resistant use (i.e. treatment) composition in a further embodiment, includes a soil resistant agent selected from copolymers from the group consisting of a maleic/olefin, an olefin/acrylate-and combinations thereof having a molecular weight from about 1,000 to 20,000 g/mol; at least one amphoteric acrylic copolymer, such as an olefin/acrylate; and a water or organic solvent carrier and/or a detergent carrier.
  • the soil resistant agent is a copolymer of maleic/olefin having a ratio of maleic to olefin moieties from about 0.02: 1 to 5: 1.
  • the ratio of the acrylic to the maleic moieties is from about 0.05:1 to 1 :1.
  • the composition is substantially free of fluorinated or silicone substituents and said soil release agent is modified such that no viscosity- building or threshold activity is exhibited.
  • kits in a further embodiment of the present invention a kit is provided.
  • the kit includes a soil resistant treatment use composition, an applicator, and instructions for use.
  • a method for treating a clean surface includes applying to a clean surface an aqueous solution of about 0.005% to 5% of a soil resistant agent selected from polymers and copolymers from the group consisting of a maleic/olefin, an olefin/acrylate and combinations thereof, wherein said soil resistant agent has a molecular weight from about 1 ,000 to 20,000 g/mol, forming a laminate film of the copolymer soil resistant composition over the clean surface, wherein the laminate film or layer of said soil resistant composition on the clean surface has an oil/water contact angle ratio of at least 2, and removing soils from the laminate film.
  • the method for treating a clean surface may further include diluting the soil resistant agent or composition before application to the clean surface, allowing the laminate film layer to dry and form an invisible film and/or applying a water source and/or mechanical force to remove soils.
  • FIG.1 shows a table measuring the surface contact angle for both corn oil and water of the treated surface and a control surface.
  • FIG. 2 shows cleaning efficiency results measured according to median color values according to embodiments of the invention.
  • inventions of this invention include soil resistant laminate compositions, kits and methods of use of the same, which can vary as understood by skilled artisans. It is further to be understood that all terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting in any manner or scope. For example, as used in this specification and the appended claims, the singular forms "a,” “an” and “the” can include plural referents unless the content clearly indicates otherwise. Further, all units, prefixes, and symbols may be denoted in its SI accepted form. Numeric ranges recited within the specification are inclusive of the numbers defining the range and include each integer within the defined range.
  • the term "about,” as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods; and the like.
  • the term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about”, the claims include equivalents to the quantities refers to variation in the numerical quantity that can occur.
  • hard surface includes, but is not limited to showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, floors, and the like.
  • laminate refers to a substrate and at least one continuous or non-continuous coating or layer adhered to a substrate surface by a physical or chemical bond including, for example, by ionic or covalent bonding.
  • a detergent carrier ensures even wetting of the surface, as opposed to conventional soil removal characteristics, resulting in the laminate formed on a treated surface.
  • molecular weight refers to the calculated average molecular weight value of the polymer or copolymer, which one skilled in the art will appreciate to encompass a reasonable percent error as a result of the statistical method applied for such calculation and the variations in the polymer molecules.
  • soil resistant agent refers to a chemical agent that reduces the severity of a stain (e.g. , repels staining) on a substrate surface caused by soil contact, and/or promotes easier stain removal (e.g., releases stains) from a substrate surface by decreasing the adhesion of soil on the surface through substrate surface modification or other physical or chemical mechanisms.
  • a soil resistant agent changes the soil adherence and/or release properties of a treated surface while a soil release agent changes the properties of the soil itself.
  • the properties of soil resistant agents according to the invention are distinct from soil release agents that act on a soil rather than on the surface. This difference is most clearly illustrated by the need to apply a soil release agent with each and every cleaning of the surface, as opposed to the less frequent application of the soil resistant agents according to the invention forming a laminate surface which imparts soil resistance (i.e. repels staining).
  • 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.
  • a novel polymeric treatment laminate composition, soil resistant treatment use composition and methods of use of the same are provided.
  • the soil resistant laminate composition provides the unexpected advantage of providing sufficient soil resistant activity that facilitates the removal of soil by simple mechanical means, such as a water spray or air flow (e.g. compressed air) alone.
  • treatment of a clean surface with the polymeric soil resistant treatment composition requires only the mechanical force of air or water flow for soil removal for a period of time.
  • treatment of a treated surface, which may be clean or soiled prior to application, with the polymeric soil resistant treatment composition requires only the mechanical force of air or water flow for soil removal for a period of time.
  • the removal of soil does not require any water source and is particularly suitable for use in climates having low water availability.
  • a detergent carrier is provided for the laminate compositions and soil resistant treatment compositions according to the invention.
  • the inclusion of a detergent carrier with the soil resistant agents according to the invention allows the treatment of either a clean and/or soiled surface with the polymers of the invention, leaving behind on the clean surface a polymer laminate coating.
  • the formulation according to the present invention incorporating a detergent carrier ensures even wetting of the surface rather than imparting soil removal power as was conventionally achieved through the combination with a soil release agent. Following such treatment with soil resistant agent in the presence of a detergent carrier, soil does not adhere to the laminate, enabling the detergent-free subsequent cleaning of the treated surface through the use of minimal mechanical force, such as air or water flow, providing complete soil removal for an extended period of time.
  • compositions can exclude a detergent, such that no detergent is required to clean the laminate composition according to the invention.
  • water or other organic solvents may be employed as a carrier in place of a detergent composition carrier.
  • the compositions and methods of the of the invention allow the easy removal of soils that come into contact with the treated surface through the use of minimal mechanical force, such as air or water flow, providing complete soil removal for an extended period of time.
  • soil resistant agent according to the invention soil does not adhere to the laminate, enabling detergent-free subsequent cleaning of the treated surface through the use of minimal mechanical force, such as air or water flow, providing complete soil removal for an extended period of time.
  • the soil resistant polymeric compositions (including both the soil resistant laminate compositions and soil resistant treatment compositions) of the invention have a wide variety of uses. They can be applied to a wide variety of hard surfaces. According to the invention, the soil resistant agents (which are referred to herein synonymously as the polymers and/or copolymers of the invention) can be applied to a wide variety of hard, non-porous and/or porous surfaces, including for example: architectural surfaces, such as showers, walls, windows, countertops, appliances, tabletops, etc.; vehicle surfaces, such as cars, trucks, boats, railroad cars and planes, especially for problem areas such as windshields, rubberized trim, hulls, aluminum rails, wheels, etc.
  • architectural surfaces such as showers, walls, windows, countertops, appliances, tabletops, etc.
  • vehicle surfaces such as cars, trucks, boats, railroad cars and planes, especially for problem areas such as windshields, rubberized trim, hulls, aluminum rails, wheels, etc.
  • hard surfaces may include certain porous surfaces, including for example: textiles or fabrics, floors and the like.
  • Exemplary surfaces intended for use according to the invention include, for example, glass, concrete, porcelain, ceramic, fiberglass, plastic, rubber, metals, hard flooring surfaces, including ceramic tile, concrete and/or stone, paint, a cured polymeric coating, and/or combinations thereof.
  • the soil resistant laminate compositions and soil resistant treatment compositions of the invention provides suitable compositions and methods for uses including, without limitation, glass cleaner, shower cleaner, hard surface treatment, glass treatment, transport vehicle tire and rim treatment, ware treatment and food processing area treatment.
  • the laminate compositions of the present invention can replace the need for use of detergents and other cleaning agents to remove soils from treated surfaces.
  • the soil resistant laminate compositions and soil resistant treatment compositions, along with the methods of use exclude the use of any detergent composition.
  • creation of laminate soil resistant surfaces reduces the intensity and frequency of required cleaning activities making the treated surface easier to clean.
  • the present invention allows for water-free cleaning and/or low or reduced labor required for cleaning treated surfaces.
  • the laminate compositions of the present invention may be used in combination with detergents or other cleaning agents to provide enhanced cleaning abilities and particularly imparting a soil resistant surface after initial treatment and cleaning.
  • Such uses according to the invention can effectively replace the need for routine use of detergents and other cleaning agents to continually clean and remove soils from treated surfaces.
  • the soil resistant laminate compositions and soil resistant treatment compositions exclude the need for use of a detergent in cleaning the laminate surface after exposure to soils.
  • creation of laminate soil resistant surfaces reduces the intensity and frequency of required cleaning activities making the treated surface easier to clean and minimizing the ongoing use of detergent compositions.
  • the present invention allows for water-free cleaning and/or low or reduced labor required for cleaning treated surfaces.
  • the soil resistant treatment composition comprises, consists essentially of or consists of at least one soil resistant agent.
  • the soil resistant treatment compositions change the soil repellency properties of treated surfaces to which they are applied.
  • a soil resistant agent refers to a chemical agent that reduces the severity of a stain (e.g. , repels staining) on a substrate surface caused by soil contact, and/or promotes easier stain removal (e.g., releases stains) from a substrate surface by decreasing the adhesion of soil on the surface through substrate surface modification or other physical or chemical mechanisms.
  • An embodiment of the invention includes a soil resistant agent that may be a single component or a multi-component system.
  • the compositions include at least one soil resistant agent, which are understood to refer to any combination of the various soil resistant agents disclosed herein according to the invention.
  • the soil resistant agent is a maleic/olefin copolymer.
  • the soil resistant agent is an olefin copolymer.
  • the olefin is hydrophobically modified and as a result the copolymer is oleophobic to lack affinity for oils and is hydrophilic to attract water.
  • the olefin is not hydrophobically modified.
  • the soil resistant agent is an olefin/acrylate copolymer and/or maleic/olefin copolymer.
  • the aery late is selected from at least one of an acrylate and/or methacrylate polymer, and/or a copolymer of acrylic acid and/or methacrylic acid. It is understood that the polymers and copolymers according to the invention may be modified by the addition of substituents without departing from the intent and scope of the invention. For example, in some embodiments, the polymers or copolymer do not exhibit viscosity-building or any threshold activity.
  • Copolymers of maleic and olefin moieties may be employed as a soil resistant agent according to the invention.
  • Particularly suitable maleic/olefin copolymers include those having a maleic/hydrophobicly-modified olefin moieties.
  • the olefin segment may include a variety of linear, branched and cyclic alkenes. Suitable alkenes may include or be derived from propylene, ethylene, isobutylene or butylene. Particularly suitable alkenes may include or be derived from butylene, for example, isobutylene and diisobutylene.
  • Exemplary maleic/olefin copolymers are commercially available from BASF and include ES8804 and Sokalan CP9.
  • the polycarboxylate copolymer soil resistant agent comprises, consists essentially of or consists of a maleic/hydrophobicly-modified olefin copolymer.
  • the olefin is selected from at least one of an aery late or a methacrylate.
  • the copolymer is oleophobic to lack affinity for oils and hydrophilic to attract water.
  • the maleic/hydrophobicly- modified olefin copolymer does not exhibit viscosity-building or any threshold activity.
  • the copolymer is substantially free of fluorinated or silicone substituents.
  • the copolymer and the compositions according to the invention exclude alkali soluble resins and/or plasticizers, providing suitable compositions for floor and other surfaces coatings that exclude floor finishes.
  • the copolymer is substantially free or free of volatile organic compounds and therefore does not contribute to air pollution.
  • the maleic/olefin copolymer of the soil resistant laminate composition has a low molecular weight, preferably less than about 20,000 g/mol, preferably less than 10,000 g/mol, more preferably less than about 7,000 and still more preferably less than about 3,000.
  • the copolymer has a molecular weight from about 2,000 to 10,000 g/mol or from about 2,000 to 5,000 g/mol.
  • Exemplary maleic/olefin copolymers include Sokalan CP9 and ES8804.
  • the maleic/olefin copolymer has a maleic/olefin molar ratio from about 1 :4 to 4: 1, preferably from about 1 :2 to 2: 1, more preferably about 1 :1.
  • the olefin contains an alkyl group having more than 3 carbons, preferably more than 4 carbons.
  • the glass transition temperature of the maleic/olefin copolymer is above the use temperature of the copolymer, preferably above 10°C.
  • the maleic/olefin copolymer of the soil resistant laminate composition has a molecular weight from about 2,000 to 10,000 g/mol and a maleic/olefin ratio from about 1 :4 to 4: 1. More preferably, the copolymer molecular weight is from about 2,000 to 5,000 g/mol and the maleic/olefin ratio is from about 1 :2 to 2: 1.
  • the soil release treatment composition may preferably comprise an aqueous solution of from about 0.1% to 5% maleic/olefin copolymer, and wherein said polymer or copolymer has a molecular weight from about 1 ,000 to 20,000 g/mol.
  • the copolymer is substantially free of fluorinated or silicone substituents.
  • the copolymer and the compositions according to the invention exclude alkali soluble resins and/or plasticizers, providing suitable compositions for floor and other surfaces coatings that exclude floor finishes.
  • the maleic/olefin copolymer is modified such that no viscosity-building or threshold activity is exhibited.
  • the copolymer is substantially free or free of volatile organic compounds.
  • the olefin is hydrophobically modified. However, in alternative embodiments, the olefin is not hydrophobically modified.
  • Acrylate copolymers may further be employed as a soil resistant agent according to the invention.
  • the acrylate copolymer is an acrylate/olefin copolymer.
  • the acrylate is selected from at least one of a polymer or copolymer of acrylic acid or methacrylic acid.
  • the acrylate may further be a methacrylate.
  • the copolymer does not exhibit viscosity-building or any threshold activity.
  • the acrylate/olefin er- copolymer of the soil resistant treatment compositions may comprise, consist essentially of or consist of an acrylate selected from at least one of acrylate or methacrylate.
  • the acrylate/olefin copolymer is oleophobic to lack affinity for oils and hydrophilic to attract water. According to a further embodiment of the invention, the acrylate/olefin copolymer does not exhibit viscosity-building or any threshold activity. According to a preferred embodiment, the acrylate/olefin copolymer is substantially free of fluorinated or silicone substituents. According to a further preferred embodiment the copolymer is substantially free or free of volatile organic compounds and therefore does not contribute to air pollution.
  • the acrylate/olefin copolymer of the soil resistant treatment composition has a low molecular weight, preferably less than approximately 20,000 g/mol, preferably less than 10,000 g/mol, more preferably less than about 7,000 and still more preferably less than about 3,000.
  • the copolymer has a molecular weight from approximately 2,000 to 10,000 g/mol or from approximately 2,000 to 5,000 g/mol, and more preferably about approximately 3,000 g/mol.
  • the glass transition temperature of the copolymer is above the use temperature of the copolymer, preferably above 10°C.
  • the soil release treatment composition may preferably comprise an aqueous solution of from about 0.1% to 5% acrylate/olefin copolymer, and wherein said polymer or copolymer has a molecular weight from about 1,000 to 20,000 g/mol.
  • Soil resistant agents according to the invention may be further combined and used with either additional soil resistant agents and/or in combination with soil release agents to provide improved and/or synergistic soil resistance.
  • suitable soil resistant agents are described further in Example 9. These may also include soil resistant agents, including fluorochemical materials (e.g., Capstone ST100 and ST300 from Dupont), and polycarboxylate copolymers (e.g., Acusol 460 from Dow).
  • fluorochemical materials e.g., Capstone ST100 and ST300 from Dupont
  • polycarboxylate copolymers e.g., Acusol 460 from Dow.
  • Acusol 460 is not desirable for use in a cured film on a solid substrate as it is a threshold agent.
  • Suitable soil release agents according to the invention include silicone materials such as polydimethysiloxane materials (e.g., Wacker HC303 from Wacker Silicones), and acrylic polymers (Rhoplex EZ Clean 200 from Dow, Polyquart ® Pro and Polyquart ® Ampho 149 from Cognis Corporation).
  • silicone materials such as polydimethysiloxane materials (e.g., Wacker HC303 from Wacker Silicones), and acrylic polymers (Rhoplex EZ Clean 200 from Dow, Polyquart ® Pro and Polyquart ® Ampho 149 from Cognis Corporation).
  • both the soil resistant agent and soil release agents are substantially free of fluorinated or silicone substituents.
  • the compositions, including both the soil resistant agent and soil release agents are substantially free or free of volatile organic compounds.
  • the soil resistant agents and soil release agents are not combined with nor do they contain any alkali soluble resins and/or plasticizers, providing suitable compositions for floor and other surfaces coatings that exclude floor finishes.
  • the soil release agents Polyquart ® Pro, Polyquart Ecoclean and/or Polyquart ® Ampho 149 which are available from Cognis Corporation, are particularly suitable for use in combination with the soil resistant agents disclosed herein and provide soil resistant capability that is better than the stain resistance achieved when either agent is used alone.
  • the use of a soil release agent imparts a sticky surface for easily wiping/removing soils attracted to the surface.
  • the combined use with the soil resistant agents of the present invention impart a synergistic effect of soil resistance of the treated surface for an extended period of time.
  • the soil resistance and/or repellency of the treated surface may have a beneficial impact on gloss as well.
  • Polyquart ® Pro, Polyquart Ecoclean and Polyquart ® Ampho 149 are amphoteric acrylic copolymers having molecular weights of at least 5,000 g/mol, more particularly, at least 10,000 g/mol.
  • the weight ratio of a Polyquart composition to a maleic/olefin copolymer may be, for example, from 0.02: 1 to 5: 1 (where all the materials are 100% active), particularly, from about 0.05:1 to 3: 1, more particularly, from about 0.05: 1 to 2: 1.
  • compositions of the present invention are formulated as aqueous use solutions.
  • Carriers can be included in such liquid formulations. Any carrier suitable for use in the soil resistant treatment compositions can be used in the present invention.
  • the compositions include water as a carrier.
  • the compositions include water or other organic solvents as a carrier.
  • the resulting composition can be homogeneous or non- homogeneous.
  • the carrier for the soil resistant treatment composition is not a detergent.
  • the soil resistant treatment composition excludes the use of any additional cleaning agent for use as a detergent.
  • the carrier may be an organic solvent such as an alcohol or polyol.
  • organic solvent such as an alcohol or polyol.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • dipropyleneglycolmonobutyl ether dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl ether,
  • diethyleneglycolmonohexyl ether diethyleneglycolmonopropyl ether-, diethyleneglycolmonobutyl ether, and mixtures thereof.
  • the soil resistant treatment compositions may be formulated as a concentrate and will contain no more than about 99 wt% water or organic solvent and typically no more than about 90 wt% water or organic solvent. In other embodiments, soil resistant treatment compositions will contain at least 50 wt% water or organic solvent, at least 60 wt% water or organic solvent, at least 70 wt% water or organic solvent, or at least 80 wt% water or organic solvent as a carrier. These amounts include all amounts of water or organic solvent in between the ranges as one of skill in the art shall ascertain.
  • the soil resistant treatment compositions are used as a use solution and will contain from about 0.01-10 wt% water or organic solvent carrier and typically no more than about 5 wt% water or organic solvent carrier. In other embodiments, soil resistant treatment use solutions compositions will contain at least 0.1-2 wt% water or organic solvent carrier.
  • a use solution according to the invention will contain from about 0.01-20 wt% soil resistant polymer or at a level equal to or greater than the water or organic solvent carrier concentration. These amounts include all amounts of detergent carrier in between the ranges as one of skill in the art shall ascertain.
  • compositions of the invention can include for example, solids, liquids including emulsions or dispersions, gels, and pastes.
  • Such embodiments can be a single part or multi part package.
  • the compositions include a detergent carrier.
  • the resulting composition can be homogeneous or non-homogeneous.
  • the carrier for the soil resistant treatment is a detergent, surfactant and/or rinse aid (referred to herein as a "detergent") suitable for evenly wetting a treated surface to evenly distribute the compositions to form a laminate over treated surfaces.
  • the detergent used as a carrier is not employed and/or relied upon for cleaning efficacy.
  • the detergent carrier for the compositions according to the invention may having varying amounts of detersive activity which are not required for the modification of the soil repellency of the laminate surface.
  • Use of a surfactant detergent may promote the covering of the treated surface evenly with the laminate composition, regardless of whether the soil resistant treatment composition is applied to a soiled or cleaned surface.
  • the soil resistant treatment compositions may be formulated as a concentrate and will contain no more than about 99 wt% detergent carrier and typically no more than about 90 wt% detergent carrier. In other embodiments, soil resistant treatment compositions will contain at least 50 wt% detergent carrier, at least 60 wt% detergent carrier, at least 70 wt% detergent carrier, or at least 80 wt% detergent carrier. These amounts include all amounts of detergent carrier in between the ranges as one of skill in the art shall ascertain.
  • the soil resistant treatment compositions are used as a use solution and will contain from about 0.01-10 wt% detergent carrier and typically no more than about 5 wt% detergent carrier. In other embodiments, soil resistant treatment use solutions compositions will contain at least 0.1-2 wt% detergent carrier. A use solution according to the invention will contain from about 0.01-20 wt% soil resistant polymer or at a level equal to or greater than the detergent carrier concentration. These amounts include all amounts of detergent carrier in between the ranges as one of skill in the art shall ascertain.
  • compositions of the invention can include for example, solids, liquids including emulsions or dispersions, gels, and pastes.
  • Such embodiments can be a single part or multi part package.
  • Use of a detergent or cleaning agent carrier is not intended to provide added stain resistant capability to the laminate composition.
  • Use of a detergent or cleaning agent as a carrier for the compositions of the invention allows for application to a clean and/or soiled surface.
  • the soil resistant agent is applied to a surface in a use composition with a detergent carrier to ensure even application of the polymers to a surface.
  • excess detergent which would be expected to impart cleaning efficacy from the detergent is not desirable.
  • Excess use of detergent as a carrier will result in the detergent remaining on the surface and is unexpectedly problematic for soil resistance performance according to the invention.
  • the carrier can be composed of any components used to form a detergent.
  • the cleaning agent carrier may be formed of amines, fatty acid, caustics, alkaline sources, salts, solvents or surfactants.
  • the cleaning agent is a fatty acid salt or a combination of a fatty acid and an alkalinity source.
  • the cleaning agent may be formed of a fatty acid amine salt.
  • the cleaning agent may be a mixture of oleic acid and monoethanolamine (MEA).
  • fatty acid includes any of a group of carboxylic acids that can be derived from or contained in an animal or vegetable fat or oil. Fatty acids are composed of a chain of alkyl groups and characterized by a terminal carboxyl group. The alkyl groups can be linear or branched. The fatty acid can be saturated or unsaturated. In some embodiments, the chain of alkyl groups contain from 4 to 24 carbon atoms, particularly from 6 to 24 carbon atoms, and more particularly from 12 to 18 carbon atoms.
  • the detergent composition can include combinations or mixtures of different fatty acids. An example of a suitable fatty acid is oleic acid, but as set forth above, a broad variety of other fatty acids or combinations or mixtures thereof are contemplated for use.
  • the fatty acid component can include up to about 50% by weight of the detergent composition concentrate, with the remainder comprising water.
  • the detergent composition can include, in the range of 2% to about 50% by weight fatty acid component, in some embodiments in the range of about 5% to about 35% by weight fatty acid component, and in some embodiments in the range of about 5% to about 20% by weight fatty acid component.
  • Some examples of dilute or use detergent compositions can include, in the range of 0.005 to about 10% by weight fatty acid component, in some embodiments in the range of about 0.008% to about 2.5% by weight fatty acid component, and in some embodiments in the range of about 0.015% to about 1% by weight fatty acid component.
  • suitable fatty acid-containing detergent compositions include StoneMedic DCC, NeoMat Forte and NeoMat S, which are aqueous soap based cleaners all available from Ecolab, Inc.
  • Amines are organic derivatives of ammonia in which one or more of the ammonia hydrogens are replaced by alkyl or aromatic groups.
  • organic amines may be employed in the compositions and methods of the present invention.
  • Representative organic amines are alkyl amines, which may be primary, secondary, or tertiary, such as isopropylamine, ethylmethylamine and trimethylamine, or substituted organoamines (e.g., alkanolamines) such as monoethanolamine, diethanolamine and triethanolamine, 1,2-diaminoethane, 1 ,2-diaminopropane, N- benzylethanolamine, 2-aminomethylpropanol, furfurylamine,
  • alkyl amines which may be primary, secondary, or tertiary, such as isopropylamine, ethylmethylamine and trimethylamine, or substituted organoamines (e.g., alkanolamines) such as monoethanolamine,
  • amines such as morpholine, or ethoxylate amines such as ethoxylated tallow amine, ethoxylated coconut amine, ethoxylated alkyl propylene amines, and the like, and mixtures thereof.
  • the amine may be an organoamine which may be accompanied by other amines or by salts of the amines.
  • the organic amine may represent, for example, between about up to about 50%, between about 5% and about 35% or about 5% and about 20% of the total concentrate weight.
  • the amount of amine in the detergent composition may also be expressed in terms of the molar equivalent ratio of acid to amine. For example, acid:amine molar equivalent ratios of between about 0.5: 1 and about 2:1 may be employed. However, the amount of amine may be adjusted to obtain a desired pH in the final concentrate or use-solution.
  • the detergent composition can include an effective amount of one or more caustic sources to enhance cleaning of a substrate and improve soil removal performance of the detergent composition.
  • the composition may include the caustic source in an amount of at least about 0.1 % by weight, at least about 5 % by weight, or at least about 10% by weight.
  • suitable caustic sources of the detergent composition include, but are not limited to an alkali metal carbonate and an alkali metal hydroxide.
  • exemplary alkali metal carbonates that can be used include, but are not limited to: sodium or potassium carbonate, bicarbonate, sesquicarbonate, and mixtures thereof.
  • Exemplary alkali metal hydroxides that can be used include, but are not limited to sodium, or potassium hydroxide.
  • the alkali metal hydroxide may be added to the composition in any form known in the art, including as solid beads, dissolved in an aqueous solution, or a combination thereof. Alkali metal hydroxides are commercially available as a solid in the form of prilled solids or beads having a mix of particle sizes ranging from about 12-100 U.S.
  • the alkali metal hydroxide is added in the form of an aqueous solution, particularly a 50% by weight hydroxide solution, to reduce the amount of heat generated in the composition due to hydration of the solid alkali material.
  • the detergent composition may comprise a secondary caustic source.
  • useful secondary caustic sources include, but are not limited to: metal silicates such as sodium or potassium silicate or metasilicate; metal carbonates such as sodium or potassium carbonate, bicarbonate, sesquicarbonate; metal borates such as sodium or potassium borate; and
  • caustic agents are commonly available in either aqueous or powdered form, either of which is useful in formulating the present solid detergent compositions.
  • the cleaning agent for use as detergent carrier according to the invention is present in an amount effective to provide detersive properties on the treated soiled or cleaned surface.
  • An effective amount should be considered as an amount that provides a use composition having a pH of between about 7 and about 11, particularly between about 7 and 10, and more particularly between about 7 and about 9.5.
  • Additional pH adjusting agents may be used to provide the use composition with the desired pH.
  • Suitable pH adjusting agents for such alkaline- based compositions include organic and inorganic acids, such as acetic acid, hydrochloric acid, sulfuric acid and citric acid.
  • formulations including a detergent composition may be formulated in various formulations, including for example concentrates or ready-to- use formulations.
  • formulations may be adjusted to obtain desired pH, concentration, and other conditions that may vary according to the desired use of the soil resistant composition according to the invention.
  • compositions may also include additional functional materials.
  • the soil resistant treatment composition and methods of use exclude the use of any additional cleaning agent and/or surfactant for use as a detergent.
  • additional functional ingredients may be incorporated dependent upon the particular surface in need of treatment.
  • suitable functional agents may include, for example, solvents, fragrances, anti-slip agents, gloss agents, including gloss enhancing additives, etc.
  • a gloss agent such as a gloss enhancing additive is included in the composition formulations of the invention.
  • one or more additives suitable for use in a floor finish application are excluded.
  • an alkali soluble resin, polyethylene, polypropylene and/or surfactant additive are excluded.
  • the compositions according to the invention remain clear at all times (as opposed to floor finishes which are opaque milky emulsions).
  • the terms “functional materials” and “functional agents” include materials 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.
  • a use and/or concentrate solution such as an aqueous solution
  • Some particular examples of functional materials are discussed in more detail below, although the particular materials discussed are given by way of example only, and a broad variety of other functional materials may be used.
  • many of the functional materials discussed below relate to materials used in cleaning applications. However, other embodiments may include functional materials for use in other applications.
  • solvents are suitable for use according to the invention. Solvents may be included as a carrier and/or for even spreading of the compositions across a surface.
  • Exemplary organic solvents that can be used include hydrocarbon or halogenated hydrocarbon moieties of the alkyl or cycloalkyl type, and have a boiling point well above room temperature, i.e., above about 30°C.
  • Considerations for selecting organic solvents include beneficial properties and aesthetic considerations. For example, in some applications where malodors would not be tolerated, the formulator would be more likely to select solvents which have a relatively pleasant odor, or odors which can be reasonably modified by perfuming.
  • the C6-C9 alkyl aromatic solvents especially the C6-C9 alkyl benzenes, preferably octyl benzene, exhibit excellent grease removal properties and have a low, pleasant odor.
  • glycol ethers can be used.
  • Exemplary glycol ethers include monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether,
  • Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of CI -4 alcohols, butoxy propanol, Butyl Carbitol® and l(2-n-butoxy-l- methylethoxy)propane-2-ol (also called butoxy propoxy propanol or dipropylene glycol monobutyl ether), hexyl diglycol (Hexyl Carbitol®), butyl triglycol, isopropyl alcohol, diols such as 2,2,4-trimethyl-l,3-pentanediol, and mixtures thereof, can also be used.
  • solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of CI -4 alcohols, butoxy propanol, Butyl Carbitol® and l(2-n-butoxy-l- methyleth
  • the concentrate can include the organic solvent component in an amount to provide the desired cleaning, product stability and/or evaporative properties.
  • the amount of solvent should be limited so that the use solution is in compliance with volatile organic compound (VOC) regulations for a particular class of cleaner.
  • VOC volatile organic compound
  • the organic solvent is an optional component and need not be incorporated into the concentrate or the use solution according to the invention. According to preferred embodiments the solvent does not afford cleaning properties.
  • the organic solvent is included in the concentrate, it can be provided in an amount of between about 0.1 wt% and about 75 wt%, between about 1 wt% and about 50 wt%, and between about 3 wt% and about 30 wt%.
  • the composition can include a surfactant or surfactant mixture.
  • a variety of surfactants can be used in a composition according to the invention having a detergent carrier, including, but not limited to: anionic, nonionic, cationic, and amphoteric (including zwitterionic) surfactants.
  • Surfactants are an optional component of the detergent composition and can be excluded from the concentrate.
  • Exemplary surfactants that can be used are commercially available from a number of sources. For a discussion of surfactants, see Kirk Othmer, Encyclopedia of
  • the detergent composition when provided as a concentrate, can include the surfactant in a range of about 0.05% to about 50% by weight, about 0.5% to about 40% by weight, about 1% to about 30% by weight, about 1.5% to about 20% by weight, and about 2% to about 15% by weight. Additional exemplary ranges of surfactant in a concentrate include about 0.5% to about 10% by weight, and about 1% to about 8% by weight.
  • anionic surfactants useful in the detergent composition include, but are not limited to: carboxylates such as alkylcarboxylates and
  • polyalkoxycarboxylates alcohol ethoxylate carboxylates, nonylphenol ethoxylate carboxylates; sulfonates such as alkylsulfonates, alkylbenzenesulfonates, alkylarylsulfonates, alpha olefinsulfonate, sulfonated fatty acid esters; sulfates such as sulfated alcohols including fatty alcohol sulfates, sulfated alcohol ethoxylates, sulfated alkylphenols, alkylsulfates, sulfosuccinates, and alkylether sulfates.
  • nonionic surfactants useful in the detergent composition include, but are not limited to, those having a polyalkylene oxide polymer as a portion of the surfactant molecule.
  • Such nonionic surfactants include, but are not limited to: chlorine-, benzyl-, methyl-, ethyl-, propyl-, butyl- and other like alkyl- capped polyethylene glycol ethers of fatty alcohols; polyalkylene oxide free nonionics such as alkyl polyglycosides; sorbitan and sucrose esters and their ethoxylates; alkoxylated amines such as alkoxylated ethylene diamine; alcohol alkoxylates such as alcohol ethoxylate propoxylates, alcohol propoxylates, alcohol propoxylate ethoxylate propoxylates, alcohol ethoxylate butoxylates; nonylphenol ethoxylate, polyoxyethylene glycol ether; carboxylic acid esters such as glycerol esters,
  • carboxylic amides such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides; and polyalkylene oxide block copolymers.
  • An example of a commercially available ethylene oxide/propylene oxide block copolymer includes, but is not limited to, PLURONIC®, available from BASF Corporation, Florham Park, NJ.
  • An example of a commercially available silicone surfactant includes, but is not limited to, ABIL® B8852, available from Goldschmidt Chemical Corporation, Hopewell, VA.
  • Some surfactants can also function as secondary solidifying agents if a solid detergent composition is desired.
  • anionic surfactants which have high melting points provide a solid at the temperature of application.
  • Anionic surfactants which have been found most useful include, but are not limited to: linear alkyl benzene sulfonate surfactants, alcohol sulfates, alcohol ether sulfates, and alpha olefin sulfonates. Generally, linear alkyl benzene sulfonates are preferred for reasons of cost and efficiency.
  • Amphoteric or zwitterionic surfactants are also useful in providing detergency, emulsification, wetting and conditioning properties.
  • amphoteric surfactants include, but are not limited to: N-coco-3-aminopropionic acid and acid salts, N-tallow-3-iminodiproprionate salts, N-lauryl-3- iminodiproprionate disodium salt, N-carboxymethyl-N-cocoalkyl-N- dimethylammonium hydroxide, N-carboxymethyl-N-dimethyl-N-(9- octadecenyl) ammonium hydroxide, (1-carboxyheptadecyl) trimethylammonium hydroxide, (1-carboxyundecyl) trimethylammonium hydroxide, N-cocoamidoethyl- N-hydroxyethylglycine sodium salt, N-hydroxyethyl-N-stearamidoglycine sodium salt, N-hydroxyethyl-N-lauramido-.
  • beta. -alanine sodium salt N-cocoamido-N- hydroxyethyl-.beta.-alanine sodium salt, mixed alicyclic amines and their ethoxylated and sulfated sodium salts, 2-alkyl- 1-carboxymethy 1-1 -hydroxy ethy 1-2- imidazolinium hydroxide sodium salt or free acid wherein the alkyl group may be nonyl, undecyl, and heptadecyl.
  • amphoteric surfactants include, but are not limited to: 1,1- bis(carboxymethyl)-2-undecyl-2-imidazolinium hydroxide disodium salt and oleic acid-ethylenediamine condensate, propoxylated and sulfated sodium salt, and amine oxide amphoteric surfactants.
  • amphoteric surfactants that can be used in the detergent composition include, but are not limited to: betaines such as dodecyl dimethyl sulfobetaine, imidazolines, and propionates.
  • polymer additives can be used in the detergent composition to provide desirable benefits.
  • the benefits include that some polymers can function as solidifying agents if a solid detergent composition is desired. Some polymers can function as a solution rheology modifier, some polymers can function as a chelating agent, some polymers can function as a stabilizer and some polymers can provide multi-benefits to the detergent composition.
  • Exemplary polymer rheology modifiers include Acusol 81 OA and Acusol 842, both are alkali soluble acrylic polymer emulsions available from Dow
  • polymeric stabilizers include ACUSOL 820, a hydrophobically modified alkali soluble acrylic polymer emulsion (HASE) and polyols such as ACUSOLTM 880, a hydrophobically modified, nonionic polyol. Both are available from Dow Chemical.
  • Exemplary polymeric chelating agent include acrylic polymers and their copolymers, such as ACUSOLTM 497N, a copolymer of acrylic acid and maleic anhydride available from Dow Chemical.
  • odorants including perfumes and other aesthetic enhancing agents can also be included in the composition.
  • Fragrances or perfumes that may be included in the compositions include, but are not limited to: terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, a jasmine such as CIS-jasmine or jasmal, and vanillin.
  • chelating agents such as ethylene diamine tetraacetic acid (EDTA) and its sodium salts
  • pH adjusters such as amines, acids and pH buffers
  • foam modifiers such as defoamers.
  • the soil resistant treatment compositions, along with its formulation to include a variety of other functional materials, according to the invention and the laminate formed by application of the soil resistant treatment compositions are stable over a relatively wide range of pH values, e.g., between about 3 and about 14.
  • a further embodiment of the invention includes a soil resistant laminate composition.
  • the composition comprises, consists essentially of or consists of a multilayer composition comprising a clean surface as a bottom layer and a dried layer of the soil resistant treatment composition.
  • the soil resistant laminate composition includes a clean (and/or soiled, if using a detergent carrier) surface as a bottom layer and a dried layer of a polycarboxylate copolymer of maleic/olefin soil resistant agent provided in water or other organic solvent carrier.
  • the polycarboxylate copolymer of the soil resistant laminate composition comprises, consists essentially of or consists of a maleic/olefin copolymer, which may further be a maleic/hydrophobicly-modified olefin copolymer.
  • the copolymer is oleophobic to lack affinity for oils and hydrophilic to attract water, does not exhibit viscosity-building or any threshold activity, is substantially free of fluorinated or silicone substituents, and/or is substantially free or free of volatile organic compounds.
  • a soil resistant laminate composition having a maleic/olefin copolymer as the soil resistant agent has a low molecular weight, preferably less than about 20,000 g/mol, preferably less than 10,000 g/mol, more preferably less than about 7,000 and still more preferably less than about 3,000.
  • the copolymer has a molecular weight from about 2,000 to 10,000 g/mol or from about 2,000 to 5,000 g/mol.
  • the maleic/olefin copolymer has a maleic/olefin molar ratio from about 1 :4 to 4: 1, preferably from about 1 :2 to 2: 1, more preferably about 1 :1.
  • Exemplary maleic/olefin copolymers such as Sokalan CP9 and ES8804 are produced by BASF.
  • the soil resistant laminate composition includes a clean surface (and/or soiled surface, if using a detergent carrier) as a bottom layer and a dried layer of an olefin/acrylate copolymer soil resistant agent provided in a water or other organic solvent carrier.
  • the olefin/acrylate copolymer of the soil resistant laminate composition according to the invention comprises, consists essentially of or consists of an acrylate-type moiety selected from at least one of an acrylate or a methacrylate.
  • the acrylate/olefin copolymer is oleophobic to lack affinity for oils and hydrophilic to attract water.
  • the copolymer does not exhibit viscosity-building or any threshold activity.
  • the copolymer is substantially free of fluorinated or silicone substituents.
  • the copolymer is substantially free or free of volatile organic compounds and therefore does not contribute to air pollution.
  • a soil resistant laminate composition having a olefin/acrylate copolymer as the soil resistant agent has a low molecular weight, preferably less than about 20,000 g/mol, preferably less than 10,000 g/mol, more preferably less than about 7,000 and still more preferably less than about 3,000.
  • the acrylate/olefin copolymer has a molecular weight from about 2,000 to 10,000 g/mol or from about 2,000 to 5,000 g/mol.
  • the olefin contains an alkyl group having more than 3 carbons, preferably more than 4 carbons.
  • the glass transition temperature of the acrylate/olefin copolymer is above the use temperature of the copolymer, preferably above 10°C.
  • Exemplary olefin polymers include ES8804 and are produced by BASF Corporation.
  • the soil resistant laminate composition includes a clean surface as a bottom layer (and/or soiled surface, if using a detergent carrier) and a dried layer of an acrylate polymer or copolymer soil resistant agent provided in a water or other organic solvent carrier.
  • the acrylate polymer or copolymer of the soil resistant laminate composition according to the invention comprises, consists essentially of or consists of an acrylate selected from at least one of an acrylic acid or a methacrylic acid polymer or copolymer.
  • the acrylate is oleophobic to lack affinity for oils and hydrophilic to attract water. According to a further embodiment of the invention, the acrylate does not exhibit viscosity-building or any threshold activity. According to a preferred embodiment, the acrylate polymer or copolymer is substantially free of fluorinated or silicone substituents. According to a further preferred embodiment the copolymer is substantially free or free of volatile organic compounds and therefore does not contribute to air pollution.
  • a soil resistant laminate composition having an acrylate polymer or copolymer as the soil resistant agent has a low molecular weight, preferably less than approximately 20,000 g/mol, preferably less than 10,000 g/mol, more preferably less than about 7,000 and still more preferably less than about 3,000.
  • the polymer or copolymer has a molecular weight from approximately 2,000 to 10,000 g/mol or from approximately 2,000 to 5,000 g/mol and is selected from the group consisting of acrylic acid, methacrylic acid polymers and copolymers and combinations thereof.
  • Exemplary acrylate polymers include Acusol 460 and are produced by Acusol 929.
  • the soil resistant laminate composition includes a clean surface (and/or soiled, if using a detergent carrier) as a bottom layer and a dried layer of more than one soil resistant agents selected from the group consisting of a polycarboxylate copolymer of maleic/olefin soil resistant agent, an olefin polymer or copolymer soil resistant agent, an acrylate polymer or copolymer soil resistant agent, and combinations thereof, which are provided in a water or other organic solvent carrier. Any combinations of the soil resistant agents disclosed herein may be used for the formulations of any soil resistant treatment composition and/or soil resistant laminate composition according to the invention.
  • the suitable copolymers and the compositions according to the invention may exclude alkali soluble resins and/or plasticizers, providing suitable compositions for floor and other surfaces coatings that exclude floor finishes.
  • the soil resistant laminate compositions according to the invention comprising, consisting essentially of or consisting of a multilayer composition having an oil/water contact angle ratio of the laminate surface of at least 2, comprising a clean surface as a bottom layer (and/or soiled surface, if using a detergent carrier) and a dried layer of the soil resistant treatment composition comprising at least one soil resistant agent as a top layer, wherein said dried layer is formed from an aqueous solution of from about 0.005% to about 5%, preferably from about 0.1% to about 5% soil resistant agent in an aqueous use solution of a soil resistant agent having a lower molecular weight from about 1 ,000 to about 20,000 g/mol.
  • the soil resistant agents are substantially free of fluorinated or silicone substituents, are modified such that no viscosity-building or threshold activity is exhibited, and/or are substantially free or free of volatile organic compounds.
  • the soil resistant treatment compositions modify or change the water and oil contact angles exhibited by a treated surface.
  • the soil resistant treatment compositions prevent the adhesion of soils to the treated surface while promoting displacement behavior to create a self- cleaning surface.
  • the water contact angle can be significantly reduced or the oil contact angle can be significantly increased, in order to increase the ratio of oil contact angle to water contact angle.
  • the ratio of oil contact angle to water contact angle for the laminate surface resulting from the soil resistant treatment compositions on the clean surface according to the invention is at least 2. More preferably, the ratio of oil contact angle to water contact angle of the laminate surface according to the invention is at least 4. Most preferably, the ratio of oil contact angle to water contact angle of the laminate surface according to the invention is at least 6.
  • the ratio of oil contact angle to water contact angle of the laminate surface according to the invention of at least 2, preferably at least 4 and most preferably at least 6 provides enhanced soil resistance of both inorganic and oily soils from the treated clean substrate.
  • the ratio of oil contact angle to water contact angle is sufficiently high, water tends to form a sheet on the treated surface, oil tends to form beads on the treated surface, and the water sheet tends to wedge underneath the soil and lift away the oil beads from the treated surface. This phenomenon can be observed by placing a water droplet and oil droplet side-by-side on the treated surface and observing the behavior of the droplets under magnification when they contact one another.
  • a further embodiment of the invention includes a laminate composition comprising, consisting essentially of or consisting of a porous or non-porous surface, such as a floor surface, and at least one continuous or non-continuous coating or layer adhered to the treated surface by a physical or chemical bond including, for example, by ionic or covalent bonding.
  • the dry-to-touch laminate surface formed by the soil resistant treatment compositions of the invention, in combination with the oil/water contact angle ratio of at least 2 provide enhanced soil resistance.
  • the combination of the at least two soil resistance mechanisms of action provide enhanced soil resistance.
  • the soil resistance mechanisms are distinct from those of soil release agents, as a laminate resistant surface is formed rather than a tacky film or surface, which would causes a clean surface to become soiled more quickly, as would result from commercially-available soil release agents being applied to a clean surface.
  • the laminate surface formed by the soil resistant treatment compositions of the invention can be further enhanced by the addition of a soil release agent.
  • Particularly suitable soil release agents for use in combination with the soil resistant agents according to the invention include a hydrophobically-modified amphoteric acrylic copolymer soil release agent.
  • exemplary acrylic copolymer includes Polyquart ® Pro and/or Polyquart ® Ampho 149, which are available from Cognis Corporation and may be hydrophobically modified according to embodiments of the invention.
  • An embodiment of the invention includes a method for treating a surface, preferably a clean surface or a substantially clean surface (and/or a soiled surface, if using a detergent carrier), comprising, consisting essentially of or consisting of applying to a clean surface a soil resistant treatment composition according to the invention and forming a laminate film of the soil resistant treatment composition over the clean surface.
  • An additional method step of removing soils from the top surface of the formed laminate film may further be included according to the invention.
  • the soil resistant treatment composition can be applied to a wide variety of hard, porous and/or nonporous surfaces.
  • exemplary hard surfaces include: architectural surfaces, such as showers, walls, windows, countertops, appliances, tabletops, etc.; vehicle surfaces, such as cars, trucks, boats, railroad cars and planes, especially for problem areas such as windshields, rubberized trim, hulls, aluminum rails, wheels, etc.; commercial or industrial process equipment, such as "clean in place" treatments for food, beverage and other process equipment; grill cleaners, protective treatments for water handling ⁇ e.g. , process water) systems; grill surfaces and the like.
  • hard surfaces may include certain porous surfaces, including for example: textiles or fabrics, floors and the like.
  • Floors may include uncoated floors ⁇ e.g. not coated with floor finishes), including for example, polished and unpolished marble, polished and unpolished concrete, terrazzo and ceramic tile.
  • Additional floor surfaces may include, whether porous or non-porous, marble, granite, terrazzo, concrete, dry shake, ceramic tiles, wood, linoleum, vinyl, cork, bamboo and rubber substrates.
  • Exemplary hard surfaces whether porous or nonporous, intended for use according to the invention include, for example, glass, porcelain, ceramic, wood, fiberglass, plastic, rubber, metals, hard flooring surfaces, including vinyl, vinyl composite, wood, ceramic tile, concrete and/or stone, paint a polymer or combinations thereof.
  • the method comprises, consists essentially of or consists of applying to a clean surface (and/or soiled surface, if using a detergent carrier) an aqueous solution of about 0.005% to about 5%, preferably from about 0.1 % to about 20% soil resistant agent in an aqueous use solution of a soil resistant agent having a low molecular weight from about 1 ,000 to about 20,000 g/mol. and forming a laminate film of the soil resistant treatment composition over the clean surface, and/or drying the composition to form a coating of the soil resistant treatment composition over the treated surface.
  • the treated surface can then be cleaned to remove soils from the laminate film.
  • an aqueous solution may further comprise about 0.005% to about 20%, preferably from about 0.1 % to about 5% soil release agent.
  • Methods according to the invention may further include using a separate detergent product to pre-clean a suitable surface prior to treatment with the soil resistant copolymer composition and leaving a residue, such as a laminate film of the copolymer soil resistant, on the clean surface.
  • Methods according to the invention may further include combing the copolymer with a detergent composition in order to clean a surface suitable for treatment with the soil resistant copolymer composition and leaving a residue, such as a laminate film of the copolymer soil resistant, on the clean surface.
  • the soil resistant copolymer is not used in combination with cationic surfactants.
  • the soil resistant treatment composition is not used in combination with surfactants. According to a still further preferred embodiment, the soil resistant treatment composition is not used in combination with a detergent or other cleaning agent.
  • the polymer layer of the soil resistant laminate is not discernible by visual inspection. According to a still further embodiment, the polymer layer does not constitute a floor finish.
  • subsequent cleaning of the treated surface results in easier cleaning (i.e. enhanced cleaning efficiency) due to soil being lightly adhered to the surface rather than bonded to the surface.
  • the surface may be subsequently cleaned with a gentle source of water (i.e. hose or naturally as a result of rain), or cleaned without the use of water, such as with mechanical action, compressed air, etc.
  • a treated surface such as vehicle may be cleaned with a source of compressed air (i.e. air curtain) rather than requiring a water source. This would be particularly beneficial in drought-stricken areas where water is at a premium.
  • the soil resistant treatment composition according to the invention may be applied to a clean and/or soiled surface.
  • a surface to be treated according to the invention may subsequently be cleaned using cleaning agents or solvents that will be familiar to those skilled in the art.
  • cleaning agent such as a detergent (cleaning agent) may be preferably incorporated into the soil resistant treatment composition according to the invention.
  • Application of the soil resistant treatment composition may include the step of spraying or evenly spreading the composition over the surface and wiping off (e.g. removing by mechanical force such as a sponge or other receptacle) any excess composition.
  • the method may further include allowing the laminate film layer to dry and form an invisible film after applying to said clean surface.
  • the soil resistant treatment composition is allowed to remain on the clean surface for sufficient period of time to enable formation of a dry-to-touch laminate film.
  • the soil resistant treatment composition forms a dry-to-touch laminate film within about an hour, preferably within about 30 minutes, more preferably within less than five minutes and still more preferably within less than one minute.
  • the laminate film formed over the clean surface by the soil resistant agent is an invisible film.
  • the laminate film is water resistant, more preferably the film is water resistant and not water insoluble.
  • the dry-to-touch laminate film formed by the soil resistant treatment composition is layered or coats the clean surface and exhibits soil resistant properties minimizing and/or preventing bonding of soils to the surface.
  • the step of removing soils from the laminate film may further include applying a water source and/or mechanical force to remove soils.
  • a water source and/or mechanical force can be utilized to clean the soil-resisting laminate film.
  • a source of compressed air can be used to clean the treated surface without the need for any water.
  • soil on the laminate is removed using compressed air, alone or combined with water.
  • the laminate film can be cleaned accordingly without the need to reapply the soil resistant copolymer composition, for example, for several weeks and even months.
  • additional soil resistant treatment composition may be applied to a cleaned and/or soiled surface to provide ongoing soil resistance.
  • the step of removing soils from the laminate film does not require a detergent composition for the removal of soils and/or cleaning of the treated surface to maintain soil resistance of the surface.
  • the step of removing soils from the laminate film does not require further use of a detergent composition for the removal of soils and/or cleaning of the treated surface to maintain soil resistance of the surface as a result of the formulation of the soil resistant agent in a detergent carrier.
  • soil can be removed with a cleaning agent if desired.
  • the soil resistant laminate can be cleaned with water, without causing removal of the soil resistant laminate, for extended periods of time.
  • the laminate film can be cleaned, for example with a deliberate flow of water, such as from a hose or a natural source such as rain for external surfaces, without the need to reapply the soil resistant copolymer composition, for example, for several weeks and even months.
  • additional soil resistant treatment composition may be applied to a cleaned surface to provide ongoing soil resistance.
  • the soil resistant copolymer laminate layer can be removed by those skilled in the art by a variety of techniques that can be employed to bring about such removal.
  • One convenient method is by spraying or soaking the treated surface with a removal solution.
  • the soil resistant treatment composition of the invention can be packaged and provided as kits for soil resistant surface treatments.
  • a kit may comprise, consist of and/or consist essentially of the soil resistant agent according to the invention (formulated into the soil resistant treatment composition), an applicator, and suitable instructions for use.
  • the kit may also optionally include a removal agent for removing a plurality of soils from a treated surface a removal agent for removing a plurality of soils from a treated surface.
  • the kit includes the soil resistant composition and a separate cleaning agent that may be optionally combined with the soil resistant composition prior to use.
  • An applicator for a kit according to the invention may include a variety of means of application.
  • applicator may include a mechanism to spray a liquid, including for example a misting applicator, a mop, a dispenser, and the like.
  • Soil resistant window compositions were prepared according to the invention using various dilutions of the soil resistant copolymer composition of the invention (commercially available from BASF).
  • the tested maleic/hydrophobicly modified olefin copolymer had 25% solids and a molecular weight of about 3000.
  • the copolymer was sprayed onto an exterior window and then wiped dried with paper towels to remove excess liquid.
  • the soil resistant copolymer composition was compared to a control window sprayed with a commercial glass cleaner (Glass Force®, Ecolab) which was also applied to a window and then wiped dry with paper towels to remove excess liquid.
  • Glass Force® Glass Force®
  • the windows were exposed to the elements without any cleaning for 6 months.
  • the windows were equally subjected to rain, roof run-off, blowing dust, and an in- ground irrigation system using 17 grain hardness well water.
  • the windows treated with the maleic/hydrophobicly modified olefin copolymer according to the invention (both 5% and 1%) remained significantly-free of soils after the 6 month period.
  • Results showed the control window was significantly soiled and required cleaning to remove visible soils from surface after six months.
  • the window treated with 5% soil resistant copolymer composition did not yet require cleaning.
  • the maleic/hydrophobicly modified olefin copolymer provided soil resistance to the treated windows as demonstrated by the windows being substantially cleaner at the end of the test period than the control.
  • the soil-resistant action further demonstrates unexpected longevity. Treated windows have remained with demonstrated soil resistance for up to at least three years.
  • the soil resistant agent forms a laminate layer over the treated surface and provides the soil resisting properties that effectively prevent soils from bonding to the surface.
  • a 5% solution of the maleic/hydrophobicly modified olefin copolymer was applied to half of various clean surfaces, including rubber, plastic, glass, stainless steel and aluminum, as a pretreatment.
  • the other half of the various clean surfaces was left untreated.
  • the soil resistance of those surfaces was evaluated by applying a clay dust to the entire dry surface and then rinsing the entire surface briefly with water in the absence of detergent. As the below pictures illustrate, the clay was removed by the water from all the pretreated test surfaces. The untreated portions of the surfaces remained soiled with the clay even after a water rinse.
  • a glass slide was treated with 2.5% solution of the maleic/hydrophobicly modified olefin copolymer in a detergent carrier (Glass Force®, Ecolab) to form a soil resistant laminate.
  • a second glass slide was cleaned with the unmodified formula (Glass Force®, Ecolab). Clay was used to soil the entire surface of the slides and compressed air alone was then used to blow non-adhering clay on each of the surfaces.
  • the glass slide with the soil resistant laminate provided substantial cleaning with the air flow alone, whereas the glass slide without the soil resistant laminate did not demonstrate removal of remaining soil with air flow alone.
  • the experiment demonstrates the ability to use indirect mechanical action (excluding water) to clean a surface treated with the soil resistant maleic/hydrophobicly modified olefin copolymer according to the invention.
  • One-half of the back window of a pick-up truck topper was converted to a soil resistant laminate using a maleic/hydrophobicly modified olefin copolymer in a detergent carrier (Glass Force®, Ecolab). The other half was cleaned with the unmodified glass cleaner. The vehicle was driven for about 2 hours. Results indicated that the portion of the window with the soil resistant laminate remained substantially freer of soils than the control half. Without being limited to a particular theory, the treated portion of the window comprising the soil resistant laminate remained substantially-free of soil as a result of the mechanical action of air blown on the window during the driving process.
  • Half of glass slides were treated with 300 ppm of the maleic/hydrophobicly modified olefin copolymer soil resistant, Cognis Polyquart Ecoclean soil release agent, or Cognis Polyquart Pro soil release agent.
  • Each of the glass slides were air- dried and then dusted with kaolin clay. Loose clay was removed by tapping each slide three times.
  • the Polyquart soil release agents when applied to clean glass, acted as a soil attractant and caused more clay to adhere to the treated area than the untreated area.
  • the area treated with the maleic/hydrophobicly modified olefin copolymer soil resistant agent according to the invention interfered with adhesion of the clay and left the treated area significantly cleaner than the untreated area, demonstrating the benefit of the present invention as a glass laminate for soil resistance over existing art.
  • the effects of the soil resistant agent according to the invention on wetting were analyzed and measured according to the ratio of oil contact angle to water contact angle for each surface.
  • Glass slides were treated with 300 ppm of the maleic/hydrophobicly modified olefin copolymer soil resistant and compared to untreated glass slides (control).
  • the surfaces were contacted with both corn oil and water in order to measure the oil contact angle and water contact angle of the treated surfaces.
  • the ratio of oil contact angle to water contact angle for the treated surface was then calculated (FIG. 1).
  • the ratio of oil contact angle to water contact angle for the untreated glass surface was 0.4 (oil contact angle: 8, water contact angle: 19) (control).
  • the ratio of oil contact angle to water contact angle for the soil resistant treated glass was 38 (oil contact angle: 38, water contact angle: 1).
  • Treated surfaces according to the invention demonstrate the "sheeting" of water and “beading" of oils contacting the treated surface. As a result, water sheets wedge underneath the soil and lift away the oil beads from the treated surface providing a soil resistant surface.
  • EXAMPLE 9 Half of glass slides were treated with 300 ppm of maleic/olefin copolymer soil resistant agent according to the invention. Each of the glass slides were air- dried and then dusted with kaolin clay. Loose clay was removed by tapping each slide three times. Soil release agents were compared for efficacy and formation of a soil resistant laminate with the surface. The various copolymers were examined to show that some polymers acted as a soil attractant and caused more clay to adhere to the treated area than the untreated area. Although not intending to be limited to a particular theory, the effects of attracting soil by some agents was indicative of the mechanism of action of certain soil release agents (e.g. treated surface becomes sticky which attracts soils but allows for easily wiping the surface to remove soils).
  • certain soil release agents e.g. treated surface becomes sticky which attracts soils but allows for easily wiping the surface to remove soils.
  • the area treated with the olefin copolymer soil resistant agent according to the invention interfered with adhesion of the clay and left the treated area significantly cleaner than the untreated area, demonstrating the benefit of the present invention as a glass laminate for soil resistance over existing art.
  • Acusol 929 Acusol944 Sokalan CP44 Acusol 5240
  • the above-tested commercially-available polymers and copolymers which may be further suitable for use as a soil resistant copolymer include: Acusol 929, poly aery late (trademark of Rohm & Haas, now Dow Chemical Company); Sokalan CP-9 a maleic acid/olefin copolymer sodium salt, Acusol 460, and ES8804 (aka
  • Acusol 460 is a threshold agent and therefore not desirable for use in a cured film on a solid substrate.
  • these materials are threshold agents for use in water and
  • Sokalan PM 70, Acusol 544, Acusol 445, Sokalan CP44, Alcosperse 125, Acusol 448, Acumer 2100, Versaflex 1, Dequest 2010, and Bayhibit AM did not show activity as soil resistant agents.
  • Jaypol 871, Jaypol 872, Gantrez S-95, Acusol 5240, Solalan PA30CL, and Polyquart Pro increased the extent of soiling when applied to a clean hard surface.
  • Preferred embodiments of the invention include compositions and methods employing compositions using a soil resistant agent selected from the group consisting of commercially-available soil resistant agents ES8804, Sokalan CP9, and combinations thereof.
  • a soil resistant agent selected from the group consisting of commercially-available soil resistant agents ES8804, Sokalan CP9, and combinations thereof.
  • Polyquart Pro soil release agent from Cognis Corporation
  • the soil resistant agents for improved and/or synergistic soil resistance.
  • the soil resistant agent does not include an agent selected from the group consisting of commercially-available products Jaypol 871,
  • the soil resistant agent does not include an agent selected from the group consisting of commercially- available products Sokalan PM, Acusol 544, Acusol 445, Sokalan CP44, Alcosperse 125, Acusol 448, Acumer 2100, Versaflex 1, Dequest 2010, Bayhibit AM and combinations thereof.
  • Grout coupons were treated with aqueous solutions containing the additive set forth in Table below. Sokalan CP9 was dissolved in DI H20 to form a 25.0% solids aqueous solution (Sokalan CP9 25%) prior to making the use solution for grout treatment. All of the use solutions for grout treatment were made by mixing 0.20g of the additive with tap water to a total weight of lOO.Og. The grout was treated with 1.3g per 1 ⁇ 2 coupon of the solution, and 2 applications were carried out for each condition. Coupon Coupon 1 Coupon 1 Coupon 2 Coupon 2 Coupon 2 Coupon
  • Example 1-16 The concentrate formulations set forth in the table below were used to prepare Examples 1-16 as also set forth in the table below.
  • Formulations 1-4 each include Polyquart Pro, a commercially available acrylic based cleaner from Cognis Corporation.
  • Formulation 5 did not use Polyquart Pro, and experiments using Formulation 5 are labeled as comparative examples.
  • EZ Clean 200 is an acrylic based stain resistant agent available from Dow. The various components for each concentration were combined and shaken for 15 seconds.
  • White grout coupons were prepared by mixing 19.32 wt% deionized water with 80.68 wt% PolyBlend Sanded Grout Mix, Bright White #381, which was manufactured by Custom Building products. Several "2 by 2" test coupons were formed by filling a mold with the mixture and allowing 5 to 7 days of ambient curing.
  • the coupons were soiled with two perpendicular passes of a foam brush coated with a black oily soil mixture.
  • the soiled coupons were placed in a Gardner Abraser tray and submerged in 220 g of cleaning solution.
  • Each of Experiments 1- 16 was used to treat at least one soiled coupon.
  • a yellow 33PP1 DCV sponge from Reilly Foam Corporation was loaded into the Gardner abraser carriage with no extra loaded way and the sponge was passed over the coupon for 10 cycles. The coupon was then removed and air dried for 24 hours.
  • Experiments 8-9 containing ES8804 and 14-15 containing EZ Clean 200 had high cleaning efficiency despite having a reduced concentration of Polyquart Pro.
  • Experiments 3-4 with reduced Polyquart Pro concentrations and no ES8804 or EZ Clean 200 had significantly lower cleaning efficiency.
  • the two Comparative Experiments 10 and 15 containing no Polyquart Pro, but ES8804 or EZ Clean 200 had a reduced cleaning efficiency in contrast to compositions also containing Polyquart Pro.
  • the cleaning efficiency of PolyQuart Pro is decreased when used at concentrations of less than 3.56% (conditions 3-4); however, when a second additive such as ES8804 or EZ Clean 200 is added to the system the cleaning efficiency of conditions containing less than 3.56% PolyQuart Pro is increased.
  • combinations of PolyQuart Pro and ES8804 or EZ Clean 200 shows better cleaning efficiency than conditions containing only ES8804 or only EZ Clean 200 as well as conditions that contain no PolyQuart Pro, no ES8804 and no EZ Clean 200.
  • compositions of the present invention can comprise, consist of, or consist essentially of the listed steps or ingredients.
  • a composition in accordance with embodiments of the present invention that "consists essentially of" the recited ingredients does not include any additional ingredients that alter the basic and novel properties of the composition.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Detergent Compositions (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Processing Of Solid Wastes (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Cette invention concerne une composition de stratifié résistant à la saleté et une composition à utiliser comme traitement résistant à la saleté. En particulier, une composition de stratifié comprenant une composition multicouche constituée d'une surface propre et/ou salie et d'une couche séchée d'un agent résistant à la saleté est décrite. Les agents résistant à la saleté selon l'invention comprennent des copolymères maléique/oléfine, oléfine/acrylate et leurs combinaisons et se prêtent à une application avec un véhicule comprenant, par exemple, un détergent, de l'eau ou autre véhicule de type solvant organique. Une trousse et des procédés pour traiter une surface propre à l'aide d'une composition de stratifié résistant à la saleté et une composition à utiliser comme traitement résistant à la saleté sont décrits par la présente invention.
PCT/IB2011/055350 2010-12-13 2011-11-28 Agent de nettoyage résistant à la saleté et traitement de surface WO2012080886A2 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114761522A (zh) * 2019-12-14 2022-07-15 Bl 科技公司 用于天然气处理装置的防污剂组合物和方法
CN115612565A (zh) * 2022-09-15 2023-01-17 河南海利未来科技集团有限公司 一种环保型高速动车风挡清洗剂及其制备方法

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Publication number Priority date Publication date Assignee Title
US5534184A (en) * 1993-06-23 1996-07-09 The Procter & Gamble Company Concentrated liquid hard surface detergent compositions containing maleic acid-olefin copolymers
US5707708A (en) * 1990-12-13 1998-01-13 E. I. Du Pont De Nemours And Company Maleic anhydride/olefin polymer stain-resists
US6326344B1 (en) * 2000-01-27 2001-12-04 Ecolab Inc. Carpet spot removal composition
WO2009143513A1 (fr) * 2008-05-23 2009-11-26 Colgate-Palmolive Company Compositions nettoyantes liquides et procédés
WO2010065481A1 (fr) * 2008-12-02 2010-06-10 Diversey, Inc. Nettoyage d'un dispositif ou d'un appareil de cuisson avec une composition comprenant un adjuvant de rinçage intégré

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Publication number Priority date Publication date Assignee Title
US5707708A (en) * 1990-12-13 1998-01-13 E. I. Du Pont De Nemours And Company Maleic anhydride/olefin polymer stain-resists
US5534184A (en) * 1993-06-23 1996-07-09 The Procter & Gamble Company Concentrated liquid hard surface detergent compositions containing maleic acid-olefin copolymers
US6326344B1 (en) * 2000-01-27 2001-12-04 Ecolab Inc. Carpet spot removal composition
WO2009143513A1 (fr) * 2008-05-23 2009-11-26 Colgate-Palmolive Company Compositions nettoyantes liquides et procédés
WO2010065481A1 (fr) * 2008-12-02 2010-06-10 Diversey, Inc. Nettoyage d'un dispositif ou d'un appareil de cuisson avec une composition comprenant un adjuvant de rinçage intégré

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114761522A (zh) * 2019-12-14 2022-07-15 Bl 科技公司 用于天然气处理装置的防污剂组合物和方法
CN115612565A (zh) * 2022-09-15 2023-01-17 河南海利未来科技集团有限公司 一种环保型高速动车风挡清洗剂及其制备方法

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