WO2013116486A1 - Liquid and soil repellent compositions for fibers - Google Patents

Liquid and soil repellent compositions for fibers Download PDF

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Publication number
WO2013116486A1
WO2013116486A1 PCT/US2013/024092 US2013024092W WO2013116486A1 WO 2013116486 A1 WO2013116486 A1 WO 2013116486A1 US 2013024092 W US2013024092 W US 2013024092W WO 2013116486 A1 WO2013116486 A1 WO 2013116486A1
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WO
WIPO (PCT)
Prior art keywords
composition
wax
surfactant
soil
repellent composition
Prior art date
Application number
PCT/US2013/024092
Other languages
English (en)
French (fr)
Inventor
Isaac K. Iverson
James E. COPENHAFER
Kelcey N. CHARLES
Michelle A. IVY
Original Assignee
Invista Technologies S.À.R.L.
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 Invista Technologies S.À.R.L. filed Critical Invista Technologies S.À.R.L.
Priority to EP13743033.6A priority Critical patent/EP2809840A4/en
Priority to IN1670MUN2014 priority patent/IN2014MN01670A/en
Priority to US14/375,867 priority patent/US9657436B2/en
Priority to CN201380017429.5A priority patent/CN104169490A/zh
Priority to CA2863525A priority patent/CA2863525C/en
Priority to AU2013215097A priority patent/AU2013215097B2/en
Publication of WO2013116486A1 publication Critical patent/WO2013116486A1/en

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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188Monocarboxylic acids; Anhydrides, halides or salts thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53Polyethers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08Processes in which the treating agent is applied in powder or granular form
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01Stain or soil resistance
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10Repellency against liquids
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/23907Pile or nap type surface or component
    • Y10T428/23921With particles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2279Coating or impregnation improves soil repellency, soil release, or anti- soil redeposition qualities of fabric

Definitions

  • liquid and soil repellent compositions for application on fiber and methods of applying these compositions.
  • the liquid repellent composition includes a wax and the soil repellent composition includes at least one clay nanoparticle.
  • Textiles that include fiber such as carpet can be exposed to a variety of different substances that can stain and ultimately diminish the appearance of carpet.
  • the substances can be hydrophilic and/or hydrophobic in nature.
  • Stain and soil repellent chemicals are often applied during the production of textiles including carpets and textile products used for upholstery, bedding, and other textiles.
  • Anti-soil treatments of such textiles have primarily been based on variations of highly fluorinated polymers which, among other effects, tend to reduce the surface energy of the fibers resulting in a decrease in the soiling of the textiles.
  • a considerable disadvantage of such fluorinated polymers is their high cost, owing in part to the somewhat limited raw material supplies required for their production.
  • Non-fluorinated polymers or materials have also been developed to treat textiles, especially carpets, to reduce soiling. Examples include silicones, silicates, and certain silsesquioxanes.
  • these non-fluorinated compositions generally do not provide the same soil and water-repellent effects on textiles compared to the fluorinated polymers. They are, however, much more readily sourced from raw materials, thus further improvements using silicon-based materials is advantageous.
  • a satisfactory hand, including smooth interactions between carpet fibers, is especially important for textiles such as carpets and textile products used for upholstery, bedding, and other interior applications. Increased value-in-use is associated with a luxurious tactile sensation that is preferred and desirable for these textiles.
  • non-fluorochemical topically-applied agents have been problematic because such agents tend to cause increased soiling and they generally wear or wash off quickly, rapidly losing their tactile effectiveness.
  • this composition would include a soil resistant/repellent
  • composition in an aqueous dispersion including a combination of a soil repellent composition and a liquid repellent composition
  • the soil repellent composition including at least one clay nanoparticle component and optionally a first surfactant
  • liquid repellent composition including a wax and a second surfactant.
  • this composition excludes the addition of fluorochemical. In other words, no fluorochemical is added to either the soil repellent composition or the liquid repellent composition.
  • Another aspect provides a method of providing soil and liquid repellency to an article including applying a composition to the article where the composition, in an aqueous dispersion, includes a combination of a soil repellent composition and a liquid repellent composition;
  • said soil repellent composition including at least one clay nanoparticle
  • said liquid repellent composition including a wax and a second surfactant.
  • a still further aspect provides an article including fiber and a composition in an aqueous dispersion, where the aqueous dispersion combines a soil repellent composition and a liquid repellent composition;
  • the soil repellent composition including at least one clay nanoparticle component and a first surfactant
  • liquid repellent composition including a wax and a second surfactant.
  • Nanoparticle A multidimensional particle in which one of its dimensions is less than 100 nm in length.
  • OWF On weight of fiber
  • WPU Weight Pick-up
  • Liquid repellencv The ability of an article to avoid penetration of a liquid into the article.
  • the liquid can include water, solvents, or hydrophobic (i.e., oil-based) materials.
  • Soil repellencv and dry soil resistance Terms used herein interchangeably to describe the ability to prevent dry soils from sticking to a fiber.
  • the dry soil may be dirt tracked in by foot traffic.
  • Alkyl Straight or branched hydrocarbon radicals, such as methyl, ethyl, propyl, butyl, octyl, isopropyl, tert-butyl, sec-pentyl, and the like.
  • Alkyl groups can either be unsubstituted or substituted with one or more substituents, e.g., halogen, alkoxy, aryl, arylalkyi, aralkoxy and the like.
  • Alkyl groups include, for example, 1 to 25 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 to carbon atoms.
  • first and second are only used only for convenience to differentiate between different components of the composition and imply nothing regarding the order of addition, or require that the component be included.
  • compositions of some aspects provide soil and liquid repellency to fibers, such as those in carpeting.
  • This composition is prepared by either separately preparing a liquid repellent composition and a soil repellent composition, which are then combined or, as an alternative, the components of each of the liquid repellent composition and the soil repellent composition are combined in a single step.
  • the soil repellent includes at least one clay nanoparticle component and optionally a first surfactant.
  • the liquid repellent composition includes a wax and a second surfactant. Regardless of whether the liquid repellent composition and the soil repellent composition are prepared together or separately, the second surfactant, and the first surfactant (when included) are independently selected and may be the same or different. Examples of suitable components are described in greater detail hereinbelow.
  • the combination of the soil repellent composition and liquid repellent composition provides these desired properties to fiber.
  • the composition may be combined by any suitable method known in the art.
  • this composition can be prepared and is effective in the absence of added fluorochemicals.
  • the composition may exclude fluorochemicals and is prepared in the absence of fluorochemicals.
  • the aqueous composition includes the soil repellent composition in an amount of about 1.0% to about 20.0% by weight of the composition, such as about 5% to about 10% by weight of the composition and includes the liquid repellent composition in an amount of 0.1% to about 10.0% by weight of the composition, such as about 1% to about 3% by weight of the
  • Additives may also be included such as a preservative and/or antimicrobial agent.
  • the article of one aspect includes fiber and a composition in an aqueous dispersion including a combination of a soil repellent composition and a liquid repellent composition.
  • the soil repellent composition includes at least one clay nanoparticle component and optionally a first surfactant; and the liquid repellent composition includes a wax and a second surfactant.
  • the article may be a textile selected from the group consisting of a rug, carpet, yarn, bedding, clothing, window treatments, upholstery, and table coverings.
  • Another aspect provides a method for providing soil and liquid repellency to an article including applying a composition to the article wherein said composition, in an aqueous dispersion, includes a combination of a soil repellent composition and a liquid repellent composition.
  • the soil repellent composition includes at least one clay nanoparticle component and optionally a first surfactant.
  • the liquid repellent composition includes a wax and a second surfactant. The method may also include where the composition is applied to the surface of the article.
  • the soil repellent composition is a mixture of:
  • the soil repellent composition includes at least one clay nanoparticle component.
  • Suitable clay nanoparticles are disclosed in U.S. Patent Application Publication No.
  • Clay nanoparticles can be selected from the group consisting of smectites, kaolins, illites, chlorites, attapulgites, and combinations thereof. More specific examples include montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite,
  • volkonskoitevolkonskoite vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, muscovite, paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, palygorskyte, and combinations thereof.
  • the clay nanoparticle component may be natural or synthetic.
  • the nanoparticle component includes synthetic hectorite. Regardless of whether the clay nanoparticle is natural or synthetic, the clay nanoparticle component may be present in an amount from about 0.01% to about 25% by weight of the combined composition. Typically, the clay nanoparticle is present in an amount of about 4% to about 38% by weight of the soil repellent composition.
  • suitable clay nanoparticles are commercially available from Rockwood Additives Ltd under the brand name Laponite®. These include Laponite RD®, Laponite RDS®, Laponite JS®, and
  • the soil repellent composition can include a fluorochemical.
  • a suitable fluorochemical may be derived from any of the classes specific to fluorinated matter including fluoropolymers, perfluoropolyethers (PFPEs), and side- chain-fluorinated polymers.
  • fluoropolymers examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and polymers and copolymers of tetrafluoroethylene (TFE), hexafluoropropylene (HFP), vinylidene fluoride, and ethylene.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PVF polyvinyl fluoride
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • vinylidene fluoride examples include polyethylene.
  • PFPEs include polymers and copolymers of TFE and HFP polymerized in the presence of 0 2 ; another example is the homopolymer of hexafluoropropylene oxide (HFPO).
  • suitable oligomeric or polymeric fluorochemicals that may be used with the compositions of some embodiments include fluorinated allophanates, fluorinated polyacrylates, fluorinated urethanes, fluorinated oxetanes, fluorinated carbodiimides, fluorinated guanidines, perfluoropolyethers, fluorochemicals incorporating C 2 to C 8 chemistries, and combinations thereof.
  • a fluorochemical may be charge neutral or have an associated cationic or anionic charge.
  • the fluorochemicals can include any liquid containing at least one dispersed or emulsified fluorine containing polymer or oligomer.
  • the liquid can also contain other nonfluorine containing compounds.
  • fluorochemical compositions used in the disclosed composition include anionic, cationic, or nonionic fluorochemicals such as the fluorochemical allophanates disclosed in U.S. Pat. No. 4,606,737; fluorochemical polyacrylates disclosed in U.S. Pat. Nos. 3,574,791 and 4,147,851 ; fluorochemical urethanes disclosed in U.S. Pat. No. 3,398,182; fluorochemical carbodiimides disclosed in U.S. Pat. No. 4,024,178; and
  • fluorochemical guanidines disclosed in U.S. Pat. No. 4,540,497. The above listed patents are hereby incorporated by reference in their entirety.
  • a short chain fluorochemical with less than or equal to six fluorinated carbons per fluorinated side-chain bound to the active ingredient polymer or surfactant can also be used.
  • the short chain fluorochemicals can be made using fluorotelomer raw materials or by electrochemical fluorination.
  • Another fluorochemical that can be used in the disclosed composition is a fluorochemical emulsion sold as Capstone RCP® from DuPont.
  • the disclosed soil repellency aqueous dispersion can be made using various
  • One technique comprises contacting at least one clay nanoparticle component with water to form an aqueous clay nanoparticle solution.
  • Aqueous solvent mixtures containing low molecular weight alcohols such as methanol, ethanol, isopropanol, and the like
  • the clay nanoparticle component can be present in an amount from about 0.01% to about 25% weight in solution, including about 1% to about 20%, about 0.05% to about 15%, about 0.01% to about 5%, about 0.05% to about 5%, about 0.5% to about 5%, and about 5% to about 15%.
  • the concentration is from about 0.05% to about 25% weight in solution, including from about 0.05% to 1% w/w and from about 5% to about 15% w/w.
  • the aqueous clay nanoparticle solution is then optionally contacted with a fluorochemical to form the soil repellency aqueous dispersion.
  • the % elemental fluorine in the combined dispersion can be present in an amount from about 0.0001% to about 5% by weight fluorine atoms present in the dispersion, including about 0.001% to about 2%, about 0.001% to about 0.8%, about 0.005% to about 0.5%, about 0.005% to about 0.15%, about 0.01% to about 1%, about 0.025% to about 0.5%, and about 0.05% to about 0.5%.
  • the concentration is from about 0.005% to about 0.5%, including from about 0.005% to about 0.15% depending on the wet pick-up percentage of the application to the fibers.
  • the weight percent of clay nanoparticle component should remain higher than the weight percent fluorine.
  • Typical weight percent ratios of clay nanoparticles to fluorine range from about 5000:1 to about 2: 1 , including about 3000: 1 , about 1500:1 , about 1000: 1 , about 500: 1 , about 100:1 , about 50:1 , about 25:1 , and about 10:1.
  • the nanoparticles provide soil repellent properties in the absence of a fluorochemical.
  • the nanoparticle acts as a fluorochemical extender allowing anti-soiling properties on the fiber at reduced fluorine levels on weight of fiber.
  • the liquid repellent composition
  • the liquid repellent composition includes a wax. Suitable wax and surfactant components are disclosed in U.S. Patent No. 8,057,693, incorporated herein by reference.
  • the liquid repellent composition can be prepared using techniques known in the art.
  • the total amount of wax present in the liquid repellent composition is from about 1% to about 40% by weight, about 5% to about 35% by weight, about 10% to about 30% by weight, or about 15% to about 25%> by weight of the liquid repellent composition.
  • the wax component is not limited and known wax components can be used.
  • waxes useful herein include, but are not limited to, vegetable waxes such as carnauba wax, haze wax, ouricury wax and esparto wax; animal waxes such as bees wax, insect wax, shellac wax and spermaceti wax; petroleum waxes such as paraffin wax, microcrystal wax, also known as microcrystalline wax, polyethylene wax, ester wax and oxidized wax; mineral waxes such as montan wax, ozokerite and ceresine; modified wax, glyceride, synthetic ketone amine amide, hydrogenated wax, or any combination thereof.
  • the wax component is a higher fatty acid such as palmitic acid, stearic acid, margaric acid and behenic acid; higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, margaryl alcohol, myricyl alcohol and eicosanol; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate and myricyl stearate; amides such as acetamide, propionic acid amide, palmitic acid amide, stearic acid amide and amide wax; higher fatty amines such as stearylamine, behenylamine and palmitylamine, or any combination thereof.
  • higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, margaryl alcohol, myricyl alcohol and eicosanol
  • higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate and my
  • the wax may include a natural wax, a synthetic wax, or a combination thereof.
  • Examples include a vegetable wax, an animal wax, a mineral wax, a petroleum wax, a polyoxyalkylene, or any combination thereof.
  • the wax comprises paraffin wax, candellila wax, and a polyoxyalkylene such as polyethylene oxide (e.g., CarbowaxTM 400).
  • the wax may be included in an amount of about 5% to about 40% by weight of the liquid repellent composition.
  • compositions described herein also include one or more surfactants.
  • the surfactant is anionic, cationic, or neutral.
  • the surfactants are selected such that the first and second surfactant components are compatible with one another (i.e., do not form separate phases when mixed). Examples of combinations of surfactants include anionic/anionic, nonionic/nonionic, nonionic/anionic, cationic/cationic, and cationic/nonionic.
  • the first surfactant and second surfactants are the same or are different. Each of the first surfactant and second surfactant are independently selected from two or more different surfactants or may be the same surfactant.
  • the surfactants are not a mixture of a cationic surfactant and an anionic surfactant.
  • the wax includes paraffin wax, candellila wax, and a polyoxyalkylene
  • the second surfactant comprises a salt of oleic acid.
  • Suitable anionic surfactants include, but are not limited to, alkali metal and
  • anionic sulfonate surfactants include, for example, sodium lauryl sulfate, available as TEXAPONTM L-100 from Henkel Inc., Wilmington, Del., or as
  • POLYSTEPTM B-3 from Stepan Chemical Co, Northfield, III.; sodium 25 lauryl ether sulfate, available as POLYSTEPTM B-12 from Stepan Chemical Co., Northfield, III.; ammonium lauryl sulfate, available as STAN-DAPOLTM A from Henkel Inc., Wilmington, Del.; and sodium dodecyl benzene sulfonate, available as SIPONATETM DS-10 from Rhone-Poulenc, Inc., Cranberry, N.J., dialkyl sulfosuccinates, having the tradename AEROSOLTM OT, commercially available from Cytec Industries, West Paterson, N.J.; sodium methyl taurate (available under the trade designation NIKKOLTM CMT30 from Nikko Chemicals Co., Tokyo, Japan); secondary alkane sulfonates such as HostapurTM SAS which is a Sodium (C14-C17) secondary alkane sulfonates (alpha-
  • LANTHANOLTM LAL sodium laurylsulfoacetate
  • STEPANMILDTM SL3 disodiumlaurethsulfosuccinate
  • the surfactant can be a disodium alpha olefin sulfonate, which contains a mixture of C12 to C16 sulfonates.
  • CALSOFTTM AOS-40 manufactured by Pilot Corp. can be used herein as the surfactant.
  • the surfactant is DOWFAX 2A1 or 2G manufactured by Dow Chemical, which are alkyl diphenyl oxide disulfonates.
  • anionic phosphate surfactants include a mixture of mono-, di- and tri-(alkyltetraglycolether)-o-phosphoric acid esters generally referred to as trilaureth-4- phosphate commercially available under the trade designation HOSTAPHATTM 340KL from Clariant Corp., as well as PPG-5 cetyl 10 phosphate available under the trade designation CRODAPHOSTM SG from Croda Inc., Parsippany, N.J.
  • anionic amine oxide surfactants include those commercially available under the trade designations AMMONYXTM LO, LMDO, and CO, which are lauryldimethylamine oxide, laurylamidopropy-4,5-dimethylamine oxide, and cetyl amine oxide, all from Stepan Company.
  • the nonionic surfactants include the condensation products of a higher aliphatic alcohol, such as a fatty alcohol, containing about 8 to about 20 carbon atoms, in a straight or branched chain configuration, condensed with about 3 to about 100 moles, preferably about 5 to about 40 moles, most preferably
  • TergitolTM 15-S series from Union Carbide and BrijTM surfactants from ICI.
  • TergitolTM 15-S Surfactants include CHC15 secondary alcohol polyethyleneglycol ethers.
  • BrijTM 97 surfactant is polyoxyethylene(10) oleyl ether;
  • BrijTM 58 surfactant is
  • polyoxyethylene(20) cetyl ether and BrijTM 76 surfactant is polyoxyethylene(10) stearyl ether.
  • Another useful class of nonionic surfactants include the polyethylene oxide condensates of one mole of alkyl phenol containing from about 6 to 12 carbon atoms in a straight or branched chain configuration, with about 3 to about 100 moles, preferably about 5 to about 40 moles, most preferably about 5 to about 20 moles of ethylene oxide to achieve the above defined HLB.
  • nonreactive nonionic surfactants are the IgepalTM CO and CA series from Rhone- Poulenc.
  • IgepalTM CO surfactants include nonylphenoxy poly (ethyleneoxy)ethanols.
  • IgepalTM CA surfactants include octylphenoxy poly(ethyleneoxy)ethanols.
  • hydrocarbon nonionic surfactants include block copolymers of ethylene oxide and propylene oxide or butylene oxide with HLB values of about 6 to about 19, preferably about 9 to about 18, and most preferably about 10 to about 6.
  • nonionic block copolymer surfactants are the PluronicTM and TetronicTM series of surfactants from BASF.
  • PluronicTM surfactants include ethylene oxide-propylene oxide block copolymers.
  • Tetronic surfactants include ethylene oxide-propylene oxide block copolymers.
  • the nonionic surfactants include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters and polyoxyethylene stearates having HLBs of about 6 to about 19, about 9 to about 18, and about 10 to about 16.
  • fatty acid ester nonionic surfactants are the SpanTM, TweenTM, and MyrjTM surfactants from ICI.
  • SpanTM surfactants include C 12 -C 18 sorbitan monoesters.
  • TweenTM surfactants include poly(ethylene oxide) C 12 -C 8 sorbitan monoesters.
  • MyjTM surfactants include poly(ethylene oxide) stearates.
  • the nonionic surfactant can include polyoxyethylene alkyl ethers, polyoxyethylene alkyl-phenyl ethers, polyoxyethylene acyl esters, sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol laurate, polyethylene glycol stearate, polyethylene glycol distearate, polyethylene glycol oleate, oxyethylene-oxypropylene block copolymer, sorbitan laurate, sorbitan stearate, sorbitan distearate, sorbitan oleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan laurate, polyoxyethylene
  • propylenediamine dioleate ethoxylated tetramethyldecynediol, fluoroaliphatic polymeric ester, polyether-polysiloxane copolymer, and the like.
  • the disclosed soil repellency aqueous dispersion can be applied to various types of fibers as a surface treatment.
  • the fiber can be any natural or synthetic fiber, including cotton, silk, wool, rayon, polyamide, acetate, olefin, acrylic, polypropylene, and polyester.
  • the fiber can also be polyhexamethylene adipamide, polycaprolactam, Nylon 6,6 or Nylon 6.
  • the fibers can be spun into yarns or woven into various textiles. Yarns can include low oriented yarn, partially oriented yarn, fully drawn yarn, flat drawn yarn, draw textured yarn, air-jet textured yarn, bulked continuous filament yarn, and spun staple.
  • Textiles can include carpets and fabrics, wherein carpets can include cut pile, twisted, woven, needlefelt, knotted, tufted, flatweave, frieze, berber, and loop pile.
  • the disclosed soil repellency aqueous dispersions can be applied to a yarn or textile, instead of the fiber.
  • the disclosed soil repellency aqueous dispersions can be applied to a fiber using various techniques known in the art. Such techniques include spraying, dipping, coating, foaming, painting, brushing, and rolling the soil repellency aqueous dispersion on to the fiber.
  • the soil repellency aqueous dispersions can also be applied on the yarn spun from the fiber or a textile made from the fiber. After application, the fiber, yarn, or textile is than heat cured at a temperature of from about 25° C. to about 200° C, including from about 150° C. to about 160° C; and a time of from about 10 seconds to about 40 minutes, including 5 minutes.
  • the clay nanoparticle component can be present in an amount from about 200 ppm to about 4000 ppm OWF, including from about 500 ppm to about 1500 ppm OWF, from about 500 ppm to about 1000 ppm OWF, from about 1000 ppm to about 1500 ppm OWF, from about 1000 ppm to about 2000 ppm OWF and from about 1500 ppm to about 2000 ppm OWF, on the surface of the fiber, yarn or textile. If included in the composition, the
  • fluorochemical can also be present in an amount that results in an elemental fluorine content of from about 25 ppm to about 1000 ppm OWF, including from about 25 ppm to about 500 ppm OWF, from about 75 ppm to about 150 ppm OWF, from about 75 ppm to about 200 ppm OWF, from about 100 ppm to about 200 ppm OWF, and from about 140 ppm to about 150 ppm OWF, on the surface of the fiber, yarn or textile.
  • the OWF of the clay nanoparticle component should remain higher than the OWF of fluorine, if fluorine is indeed present.
  • Typical OWF ratios of nanoparticles to fluorine can range from about 80:1 to about 1.5:1 , including about 27: 1 , about 20: 1 , about 13:1 , about 0: 1 , about 7.5: 1 , and about 5:1. Fibers, yarns, and textiles with these surface concentrations have a delta E of from about 15 to about 23 when measured using ASTM D6540.
  • Additional components can be added to the soil repellency composition or the liquid repellency composition disclosed above.
  • Such components can include silicones, optical brighteners, antibacterial components, anti-oxidant stabilizers, coloring agents, light stabilizers, UV absorbers, base dyes, and acid dyes.
  • Optical brighteners can include a triazine type, a coumarin type, a benzoxazole type, a stilbene type, and 2,2'-(1 ,2-ethenediyldi-4,1
  • Antimicrobial components can include silver containing compounds, where the antimicrobial component is present in an amount by weight of total composition from about 2 ppm to about 1%.
  • Adapted Procedure - Orient all carpet pieces for the batch so that the pile lies down towards the left. Fluff the carpet against the pile lay and measure the L*a*b* values of the carpet with a calibrated chromameter. Condition the carpet samples at a temperature of ⁇ 70 °C with a humidity of ⁇ 65% for at least 10 hours. Mount the test specimens to the backing sheet in the drum soiler with double sided tape. Ensure that the pile lay is in the same direction for all specimens. Pour 250g of soiled pellets (3:1000 carpet soikzytel nylon pellets) and steel balls into the drum soiler with the carpet samples. Tumble the drum on the mill for 15 minutes. Then rotate the direction of the drum and tumble for another 15 minutes.
  • a result of F represents a carpet surface for which 100% deionized water cannot remain above the surface for at least 10 seconds.
  • a result of 0 represents a carpet surface for which 100% deionized water remains above the surface for at least 10 seconds, but a solution of 98% deionized water and 2% isopropylalcohol cannot remain above the surface for at least 10 seconds.
  • the microcrystalline paraffin wax was obtained from IGI Wax (product number 5897A).
  • the candelilla wax, oleic acid, triethanolamine, and polyethylene glycol 400 were all obtained from Sigma-Aldrich.
  • the Dowfax 2A1 a surfactant, was obtained from DowCorning.
  • S815 is a stain blocker which is obtained through INVISTA Dalton facilities.
  • the carpet used for testing was a 995 saxony carpet with 9/16 of an inch pile height, 13-14 stitches per inch, and 1/8 of an inch gauge.
  • the weight of one square inch of the carpet without backing is 46 ounces. Wax icroemulsion
  • a wax microemulsion solution was formulated with the four steps outlined below.
  • Part 1 - Microcrystalline paraffin wax 142.1 g was heated in a kettle, around 95 °C, until melted. While stirring, candelilla wax (52.9 g) was slowly added to the melt, followed by oleic acid (22.7 g).
  • Part 3 In another kettle, water (372.7 g) and polyethylene glycol 400 (2.5 g) were heated to a temperature of 92 °C. The wax solution from part 2 was very slowly added to the kettle and a homogenizer was used to form a microemulsion. After 15 minutes of homogenization, the solution was allowed to cool to 32 °C. The solution remained at 32 °C for 10 hours.
  • Part 4 After sitting at 32 °C for 10 hours, the solution had formed a thin top foam layer. The top foam layer was carefully removed from the container, and the bottom layer of the solution was filter through a GF/A glass filter.
  • An application solution of the microemulsion wax was formulated, such that the concentration of wax resulted in either 1 % weight on fiber or 2% weight on fiber for carpet samples 1-1 , 1-2, 1-3, and 1-4.
  • the pH of the application solution was dropped to a pH of 2.
  • the carpet sample was dipped in the application solution and allowed to wick up the solution, such that the solution was evenly distributed across the carpet sample.
  • the carpet sample was conditioned by steaming for 10 minutes and cooling to room temperature. The carpet was then rinsed with deionized water and centrifuged to remove excess water. The carpet was allowed to dry at room temperature.
  • carpet samples 1-1 , 1-2, 1-3, and 1-5 were dried at room temperature.
  • carpet samples 1-3 and 1-5 were oven cured for 10 minutes at 150 °C, removed from the oven, and dried at room temperature.
  • An application solution of the microemulsion wax was formulated, such that the concentration of wax resulted in 2% weight on fiber for carpet samples 2-1 , 2-2, and 2-3.
  • An application solution of the stain blocker was formulated, such that the concentration of stain blocker resulted in 4% weight on fiber for carpet samples 2-1 and 2-5.
  • An application solution of the synthetic clay was formulated, such that the concentration of synthetic clay resulted in 1.2% weight on fiber for carpet sample 2-1.
  • a two component application solution (carpet sample 2-2) or a three component application solution (carpet sample 2-1 ) was prepared. The pH of the application solution was dropped to a pH of 2.
  • the carpet fiber was dipped in the application solution and allowed to wick up the solution, such that the solution was evenly distributed across the carpet sample.
  • the carpet sample was then conditioned by steaming for 10 minutes and cooling to room temperature.
  • the carpet was then rinsed with deionized water and centrifuged to remove excess water.
  • the carpet was allowed to dry at room temperature.
  • An application solution of the microemulsion wax was formulated, such that the concentration of wax resulted in either 1% weight on fiber or 2% weight on fiber for carpet samples 3-1 , 3-2, 3-3, and 3-4.
  • An application solution of the stain blocker was formulated, such that the concentration of stain blocker resulted in 4% weight on fiber for carpet samples 3- 1 , 3-2, and 3-5.
  • a two component application solution (carpet samples 3-1 and 3-2) was prepared.
  • the pH of the application solution was dropped to a pH of 2.
  • the carpet fiber was dipped in the application solution and allowed to wick up the solution, such that the solution was evenly distributed across the carpet sample.
  • the carpet sample was then conditioned by steaming for 10 minutes and cooling to room temperature.
  • the carpet was then rinsed with deionized water and centrifuged to remove excess water.
  • the carpet was allowed to dry at room temperature.
  • aqueous 80 ppm synthetic clay solution was added to a spray container, and synthetic clay was sprayed onto dry carpet samples (3-1 , 3-2, and 3-3) or a damp carpet sample (3-4), such that 15% wet pick up with a 1.2% weight on fiber was achieved.
  • the carpet was oven cured for 10 minutes at 150 °C, removed from the oven, and dried at room temperature.
  • control carpet in this example is an unbacked, nylon 6,6 carpet treated with a stain blocker.
  • Sequapel® 417 wax emulsion An application solution of Sequapel® 417 wax emulsion was formulated, such that the concentration of wax resulted in 1 % weight on fiber for carpet samples 4-1 and 4-2.
  • the pH of the application solution was dropped to a pH of 2.
  • the carpet fiber was dipped in the application solution and allowed to wick up the solution, such that the solution was evenly distributed across the carpet sample.
  • the carpet sample was then conditioned by steaming for 10 minutes and cooling to room temperature.
  • the carpet was then rinsed with deionized water and centrifuged to remove excess water. The carpet was allowed to dry at room temperature.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
PCT/US2013/024092 2012-01-31 2013-01-31 Liquid and soil repellent compositions for fibers WO2013116486A1 (en)

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EP13743033.6A EP2809840A4 (en) 2012-01-31 2013-01-31 LIQUID AND DIRT PROOF COMPOSITIONS FOR FIBERS
IN1670MUN2014 IN2014MN01670A (US07829477-20101109-C00007.png) 2012-01-31 2013-01-31
US14/375,867 US9657436B2 (en) 2012-01-31 2013-01-31 Liquid and soil repellent compositions for fibers
CN201380017429.5A CN104169490A (zh) 2012-01-31 2013-01-31 用于纤维的斥液斥污组合物
CA2863525A CA2863525C (en) 2012-01-31 2013-01-31 Liquid and soil repellent compositions for fibers
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