US20160032518A1 - Soil Repellency, Aqueous Dispersions, Soil Repellant Soft Articles, and Methods of Making the Same - Google Patents
Soil Repellency, Aqueous Dispersions, Soil Repellant Soft Articles, and Methods of Making the Same Download PDFInfo
- Publication number
- US20160032518A1 US20160032518A1 US14/884,011 US201514884011A US2016032518A1 US 20160032518 A1 US20160032518 A1 US 20160032518A1 US 201514884011 A US201514884011 A US 201514884011A US 2016032518 A1 US2016032518 A1 US 2016032518A1
- Authority
- US
- United States
- Prior art keywords
- fluorochemical
- clay nanoparticle
- soil
- nanoparticle component
- weight
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating 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
- D06M11/77—Treating 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating 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 nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
- D06M13/428—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes containing fluorine atoms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/01—Stain or soil resistance
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/06—Processes in which the treating agent is dispersed in a gas, e.g. aerosols
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0063—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf
- D06N7/0065—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by the pile
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Definitions
- the invention relates to soil repellency aqueous dispersions comprising a colloidal dispersion of clay nanoparticles and an aqueous fluorochemical.
- Soil repellant soft articles that have been modified by the soil repellency aqueous dispersions, which result in having improved anti-soil properties, are also disclosed.
- the soft articles can comprise fibers, yarns, and textiles. Also disclosed herein are processes for making the soil repellency aqueous dispersions and soil repellant soft articles.
- Sub-micron particles of inorganic oxides i.e. silica
- silica have been applied topically to polyamide fibers in the past to provide anti-soil deposition benefits, but have suffered from poor durability and harsh texture. Additionally, the silica treated surfaces can have an unappealing white haze at certain deposition concentrations. Fluorochemical resin emulsions have been used to create low soiling soft surfaces.
- U.S. Pat. No. 6,225,403 teaches the use of surface treating compositions comprised of a blend of fluorochemical resins with colloidal sol dispersions of organosiloxane co-polymers. This blend allows for significantly reduced add-on levels of fluorochemicals on soft-surfaces to achieve acceptable soil repellency.
- colloidal siloxane fluorine extenders can impart a harsh feel to the soft surface which is undesirable.
- the invention disclosed herein provides soil repellency aqueous dispersions comprising aqueous dispersions of clay nanoparticles that can be combined with traditional fluorochemicals.
- the clay nanoparticles can be added to anti-soil formulations and water/oil repellant formulations.
- Fibers treated with the disclosed dispersions show superior anti-soil deposition and dry soil repellency properties over prior fluorochemical and silicone treated fibers. Treated fibers also show softer hand feel and better durability over prior fluorochemical or silicone treated fibers.
- the nanoparticles are shown to act as a fluorochemical extender allowing anti-soiling properties on the fiber at reduced fluorine levels on the weight of fiber.
- methods of making the disclosed aqueous dispersions and treated fibers Further provided are yarns and textiles, such as fabrics and carpets, made with various aspects of the treated fibers.
- Clay nanoparticles can be effective diluents for fluorochemicals in fluorochemical water and oil repellency treatment compositions directed to fibrous soft surfaces. Specifically, the amount of fluorochemical required for a given anti-soil effect is surprisingly reduced by inclusion of clay nanoparticles in the fluorochemical formulation or emulsion, resulting in effective soil repellency at substantially reduced fluorine levels compared to the prior formulations.
- the clay particles are essentially hydrophilic but are still effective as extenders of the hydrophobic properties that would otherwise be expected to depend on the fluorochemical concentration alone. Under certain conditions, aqueous dispersions of clay nanoparticles are shown to impart many of the same benefits expected from fluorochemicals alone.
- an aqueous dispersion for soil repellency comprising at least one clay nanoparticle component and a fluorochemical.
- the clay nanoparticle component can be either natural or synthetic.
- the fluorochemical can comprise any chemical containing a carbon-fluorine moiety.
- a fiber comprising a surface treatment comprising at least one clay nanoparticle component and a fluorochemical
- the fiber can be any natural or synthetic fiber, including cotton, silk, wool, rayon, polyamide, acetate, olefin, acrylic, polypropylene, and polyester.
- the fiber can be spun into a yarn or manufactured into a textile.
- a textile comprising at least one fiber treated with a soil repellency aqueous dispersion comprising at least one clay nanoparticle component and a fluorochemical.
- the textile can be any woven fabric or carpet.
- the carpet can include cut pile, twisted, woven, needlefelt, knotted, tufted, flatweave, frieze, berber, and loop pile.
- a process of making a soil repellency aqueous dispersion comprises contacting at least one clay nanoparticle component with a solvent to form an aqueous clay nanoparticle solution, and contacting said aqueous clay nanoparticle solution with a fluorochemical to form the soil repellency aqueous dispersions.
- a process of making a soil repellant fiber using soil repellency aqueous dispersions discussed above comprises applying said aqueous dispersions onto said fiber in an amount resulting in said at least one clay nanoparticle component present in an amount from about 200 ppm (parts per million-particle weight per weight of the fiber) 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, 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; and said fluorochemical 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 to about 500 ppm OWF, from about 75 ppm to about 150 ppm OWF, from
- 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
- a soil repellency aqueous dispersion comprising at least one clay nanoparticle component and a fluorochemical.
- the clay nanoparticle component can refer to particles substantially comprising minerals of the following geological classes: smectites, kaolins, illites, chlorites, and attapulgites.
- the clay nanoparticles can be either synthetic or natural, including synthetic hectorite, and Laponite® from Rockwood Additives Ltd.
- the Laponite® clay nanoparticles can be Laponite RD®, Laponite RDS®, Laponite JS®, and Laponite S482®.
- the fluorochemicals can include any liquid containing at least one dispersed or emulsified fluorine containing polymer or oligomer.
- the liquid can also contain other non-fluorine 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 4,147,85; fluorochemical urethanes disclosed in U.S. Pat. No. 3,398,182; fluorochemical carbodiimides disclosed in U.S. Pat. No.
- 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 techniques.
- 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) can also be used to disperse the clay.
- 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 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% weight fluorine atoms present in 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 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.
- 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.
- 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.
- 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 10:1, 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 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 benzoxaxole type, a stilbene type, and 2,2′-(1,2-ethenediyldi-4,1 phenylene)bisbenzoxazole, where the brightener is present in an amount by weight of total composition from about 0.005% to about 0.2%.
- 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%.
- the nanoparticles are shown to act as a fluorochemical extender allowing anti-soiling properties on the fiber at reduced fluorine levels on the weight of fiber.
- Drum soiling is recorded as Delta E and measured according to ASTM D6540 and D1776.
- Table 1 lists the various carpet samples: (1) treated with the various aspects of the disclosed soil repellency composition (Samples 1-12); (2) treated with a standard fluorochemical emulsion treatment (Sample 13—comparative); and (3) untreated (Sample 14—untreated).
- Samples 1-7 were all prepared in a similar manner, with the main difference being the weight percent and type of stock Laponite® solution made and the addition of Capstone® RCP to Samples 4-7.
- the solution was shaken, poured into the reservoir of an 8 ounce spray bottle, and primed into a waste container.
- the spray bottle was clamped onto a ring stand approximately 12 inches from the base and aimed at a downward angle.
- the spray pattern was tested and centered on a grid. A tare weight for the carpet was obtained, then the carpet was placed on the grid so that the bottom right corner of the carpet would be contacted by the spray.
- the carpet was then moved so that the bottom half of the carpet would be sprayed.
- the carpet was again moved so that the left bottom corner was sprayed, then the left half, then top left corner, top half, top right corner, and right half, followed by a spray aimed at the center to achieve full coverage.
- the carpet was cured in a convection oven at 150° C. for 5 minutes.
- the resulting dispersions when sprayed on the Sample at about 5% WPU, resulted in 1500 ppm OWF of clay nanoparticles and 150 ppm OWE of elemental flourine on the surface of the Sample.
- Samples 8-12 were prepared in a similar manner, except that the resulting dispersions, when sprayed on the Samples at 10% WPU, resulted in from about 1000-2000 ppm OWF of clay nanoparticles and from about 75 ppm-200 ppm OWF elemental fluorine, on the surface of the Samples.
- Sample 13 was prepared with a 13.3 wt % Capstone® RCP solution and following a spray pattern similar to the method described above at a 10% wet-pick up, which resulted in 640 ppm OWF of elemental fluorine on the surface.
- each drum load contained at least one piece of untreated control carpet (“Control”).
- Table 2 compares the Delta E values for Samples 1-7, and 13 with the Control described in the previous paragraph.
- Table 3 compares Samples 8-12 with Sample 13, which is the fluorine only treated carpet.
- Samples 1-7 show between a 17% to 31% decrease in soil retained verses the Control.
- Samples 8-12 when compared to Sample 13, show the benefit of the clay nano-particles, which result in about the same Delta E to 1.0 decrease in Delta E over a carpet with 3 ⁇ the fluorine and no clay nano-particles (Sample 13).
- a more environmentally friendly carpet fiber with the same or improved drum soiling, can be achieved with the disclosed soil repellency aqueous dispersions.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
A soil repellency aqueous dispersion for treating various fibers, yarns, and textiles is disclosed. The dispersion provides superior soil resistance when compared to known fluorochemical and silicone fiber treatments. The dispersion comprises clay nanoparticle components and fluorochemicals that can be applied to the fibers, yarns, and textiles using known methods.
Description
- This application claims benefit of priority from U.S. Provisional Application No. 61/285,425 filed Dec. 10, 2009.
- The invention relates to soil repellency aqueous dispersions comprising a colloidal dispersion of clay nanoparticles and an aqueous fluorochemical. Soil repellant soft articles that have been modified by the soil repellency aqueous dispersions, which result in having improved anti-soil properties, are also disclosed. The soft articles can comprise fibers, yarns, and textiles. Also disclosed herein are processes for making the soil repellency aqueous dispersions and soil repellant soft articles.
- Sub-micron particles of inorganic oxides (i.e. silica) have been applied topically to polyamide fibers in the past to provide anti-soil deposition benefits, but have suffered from poor durability and harsh texture. Additionally, the silica treated surfaces can have an unappealing white haze at certain deposition concentrations. Fluorochemical resin emulsions have been used to create low soiling soft surfaces.
- U.S. Pat. No. 6,225,403 teaches the use of surface treating compositions comprised of a blend of fluorochemical resins with colloidal sol dispersions of organosiloxane co-polymers. This blend allows for significantly reduced add-on levels of fluorochemicals on soft-surfaces to achieve acceptable soil repellency. However, these colloidal siloxane fluorine extenders can impart a harsh feel to the soft surface which is undesirable.
- There is a desire to reduce the overall usage of fluorochemicals for environmental and cost reasons. Thus, it can be understood that soil repellency compositions that reduce the amount of fluorochemicals used, but still retain good soil-resistance, are in demand.
- Therefore, it is desirable to further extend the effectiveness of fluorochemicals and to produce a softer hand fiber while retaining desirable soil-resistant attributes.
- The invention disclosed herein provides soil repellency aqueous dispersions comprising aqueous dispersions of clay nanoparticles that can be combined with traditional fluorochemicals. The clay nanoparticles can be added to anti-soil formulations and water/oil repellant formulations. Fibers treated with the disclosed dispersions show superior anti-soil deposition and dry soil repellency properties over prior fluorochemical and silicone treated fibers. Treated fibers also show softer hand feel and better durability over prior fluorochemical or silicone treated fibers. The nanoparticles are shown to act as a fluorochemical extender allowing anti-soiling properties on the fiber at reduced fluorine levels on the weight of fiber. Also provided are methods of making the disclosed aqueous dispersions and treated fibers. Further provided are yarns and textiles, such as fabrics and carpets, made with various aspects of the treated fibers.
- Clay nanoparticles can be effective diluents for fluorochemicals in fluorochemical water and oil repellency treatment compositions directed to fibrous soft surfaces. Specifically, the amount of fluorochemical required for a given anti-soil effect is surprisingly reduced by inclusion of clay nanoparticles in the fluorochemical formulation or emulsion, resulting in effective soil repellency at substantially reduced fluorine levels compared to the prior formulations. When fibers are treated with the disclosed aqueous dispersions, the clay particles are essentially hydrophilic but are still effective as extenders of the hydrophobic properties that would otherwise be expected to depend on the fluorochemical concentration alone. Under certain conditions, aqueous dispersions of clay nanoparticles are shown to impart many of the same benefits expected from fluorochemicals alone.
- In one aspect, an aqueous dispersion for soil repellency comprising at least one clay nanoparticle component and a fluorochemical is provided. The clay nanoparticle component can be either natural or synthetic. The fluorochemical can comprise any chemical containing a carbon-fluorine moiety.
- In another aspect, a fiber comprising a surface treatment comprising at least one clay nanoparticle component and a fluorochemical is provided. The fiber can be any natural or synthetic fiber, including cotton, silk, wool, rayon, polyamide, acetate, olefin, acrylic, polypropylene, and polyester. The fiber can be spun into a yarn or manufactured into a textile.
- In a further aspect, a textile comprising at least one fiber treated with a soil repellency aqueous dispersion comprising at least one clay nanoparticle component and a fluorochemical is provided. The textile can be any woven fabric or carpet. The carpet can include cut pile, twisted, woven, needlefelt, knotted, tufted, flatweave, frieze, berber, and loop pile.
- In yet another aspect, a process of making a soil repellency aqueous dispersion is provided. Such process comprises contacting at least one clay nanoparticle component with a solvent to form an aqueous clay nanoparticle solution, and contacting said aqueous clay nanoparticle solution with a fluorochemical to form the soil repellency aqueous dispersions.
- In yet a further aspect, a process of making a soil repellant fiber using soil repellency aqueous dispersions discussed above is provided. Such process comprises applying said aqueous dispersions onto said fiber in an amount resulting in said at least one clay nanoparticle component present in an amount from about 200 ppm (parts per million-particle weight per weight of the fiber) 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, 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; and said fluorochemical 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 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 said fiber. The fiber is then cured. (Curing refers to the process of drying the solvent used to carry the solution onto the fiber. This can optionally be done using a heating step.) The same process can be applied to yarns and textiles.
- While mostly familiar to those versed in the art, the following definitions are provided in the interest of clarity.
- Nanoparticle: A multidimensional particle in which one of its dimensions is less than 100 nm in length.
- OWF (On weight of fiber): The amount of solids that were applied after drying off the solvent.
- WPU (Wet Pick-up): The amount of solution weight that was applied to the fiber before drying off the solvent.
- A soil repellency aqueous dispersion is disclosed comprising at least one clay nanoparticle component and a fluorochemical. The clay nanoparticle component can refer to particles substantially comprising minerals of the following geological classes: smectites, kaolins, illites, chlorites, and attapulgites. These classes include specific clays such as montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, suscovite, paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, and polygorskyte. The clay nanoparticles can be either synthetic or natural, including synthetic hectorite, and Laponite® from Rockwood Additives Ltd. The Laponite® clay nanoparticles can be Laponite RD®, Laponite RDS®, Laponite JS®, and Laponite S482®.
- The fluorochemicals can include any liquid containing at least one dispersed or emulsified fluorine containing polymer or oligomer. The liquid can also contain other non-fluorine containing compounds. Examples of 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 4,147,85; 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 techniques. 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) can also be used to disperse the clay. 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%. When Laponite® is used as the clay nanoparticle, 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 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% weight fluorine atoms present in 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%. When Capstone RCP® is used as the fluorochemical, 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. When formulating the aqueous dispersions, 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 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. Alternatively, 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.
- Once applied, 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. 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. When applying the aqueous dispersions, the OWF of the clay nanoparticle component should remain higher than the OWF of fluorine. 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 10:1, 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 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 benzoxaxole type, a stilbene type, and 2,2′-(1,2-ethenediyldi-4,1 phenylene)bisbenzoxazole, where the brightener is present in an amount by weight of total composition from about 0.005% to about 0.2%. 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%.
- The nanoparticles are shown to act as a fluorochemical extender allowing anti-soiling properties on the fiber at reduced fluorine levels on the weight of fiber.
- The following are examples of Nylon 6,6 46 ounce cut-pile carpet treated with the soil repellency aqueous dispersions disclosed above compared to a standard fluorochemical emulsion treatment (comparative), and no treatment. Selection of alternative fluorochemicals, clay nanoparticles, fibers and textiles having different surface chemistries will necessitate minor adjustments to the variables herein described.
- Drum soiling is recorded as Delta E and measured according to ASTM D6540 and D1776.
- Table 1, below, lists the various carpet samples: (1) treated with the various aspects of the disclosed soil repellency composition (Samples 1-12); (2) treated with a standard fluorochemical emulsion treatment (Sample 13—comparative); and (3) untreated (Sample 14—untreated).
-
TABLE 1 ppm OWF (on ppm OWF weight of fiber) elemental Sample # Clay Nanoparticle clay flourine 1 Laponite ® RD 1750 0 2 Laponite ® RDS 1740 0 3 Laponite ® JS 1950 0 4 Laponite ® RD 1700 150 5 Laponite ® RDS 1800 150 6 Laponite ® JS 1830 140 7 Laponite ® RDS 1500 150 8 Laponite ® RDS 1000 75 9 Laponite ® RDS 2000 75 10 Laponite ® RDS 1500 150 11 Laponite ® RDS 1000 200 12 Laponite ® RDS 2000 200 13 (comparative) NA 0 640 14 (untreated) NA 0 0 - Samples 1-7 were all prepared in a similar manner, with the main difference being the weight percent and type of stock Laponite® solution made and the addition of Capstone® RCP to Samples 4-7. For illustrative purposes only, the following describes the method of preparing Sample 7: A 5% by weight stock solution of Laponite® RDS was made by incrementally adding the nanoclay to stirring water that was heated to about 38° C. After addition was completed, the vessel was moved to a cool stir plate and continued to stir until the solution was dispersion clear and at room temperature. In a bottle were combined 6 wt % Capstone® RCP, 60 wt % of the Laponite® dispersion, and the remainder dionized water. The solution was shaken, poured into the reservoir of an 8 ounce spray bottle, and primed into a waste container. The spray bottle was clamped onto a ring stand approximately 12 inches from the base and aimed at a downward angle. The spray pattern was tested and centered on a grid. A tare weight for the carpet was obtained, then the carpet was placed on the grid so that the bottom right corner of the carpet would be contacted by the spray. The carpet was then moved so that the bottom half of the carpet would be sprayed. The carpet was again moved so that the left bottom corner was sprayed, then the left half, then top left corner, top half, top right corner, and right half, followed by a spray aimed at the center to achieve full coverage. After spraying on the carpet surface, the carpet was cured in a convection oven at 150° C. for 5 minutes. The resulting dispersions, when sprayed on the Sample at about 5% WPU, resulted in 1500 ppm OWF of clay nanoparticles and 150 ppm OWE of elemental flourine on the surface of the Sample.
- Samples 8-12 were prepared in a similar manner, except that the resulting dispersions, when sprayed on the Samples at 10% WPU, resulted in from about 1000-2000 ppm OWF of clay nanoparticles and from about 75 ppm-200 ppm OWF elemental fluorine, on the surface of the Samples.
- Sample 13 was prepared with a 13.3 wt % Capstone® RCP solution and following a spray pattern similar to the method described above at a 10% wet-pick up, which resulted in 640 ppm OWF of elemental fluorine on the surface.
- The Samples were then soiled according to ASTM D6540. For Samples 1-7 and 13, each drum load contained at least one piece of untreated control carpet (“Control”).
- Tables 2 and 3, below, lists the Delta E values for Samples 1-14. Table 2 compares the Delta E values for Samples 1-7, and 13 with the Control described in the previous paragraph. Table 3 compares Samples 8-12 with Sample 13, which is the fluorine only treated carpet.
-
TABLE 2 Sample Delta E with Control Delta E % soil retained Sample # Std. Dev. with Std. Dev. vs. Control 1 15.7 ± 0.6 19.6 ± 0.6 80 2 15.1 ± 1.2 18.7 ± 0.6 81 3 15.5 ± 0.3 18.6 ± 0.1 83 4 14.9 ± 1.0 19.6 ± 0.6 76 5 14.1 ± 0.8 18.7 ± 0.6 75 6 14.3 ± 0.7 18.6 ± 0.1 77 7 16.1 ± 1.0 23.4 ± 0.5 69 13 (compara- 16.0 ± 0.8 20.1 ±. 0.5 80 tive) 14 (untreated) 21.9 ± 1.0 NA NA - Samples 1-7 show between a 17% to 31% decrease in soil retained verses the Control.
-
TABLE 3 Sample Delta E with Sample # Std. Dev. Delta E difference to Sample 13 8 18.1 ± 0.7 −2.1 9 16.5 ± 1.6 −0.5 10 15.0 ± 0.6 +1.0 11 17.0 ± 1.2 −1.0 12 15.5 ± 0.8 +0.5 13 (comparative) 16.0 ± 0.8 — 14 (untreated) 21.9 ± 1.0 +5.9 - Samples 8-12, when compared to Sample 13, show the benefit of the clay nano-particles, which result in about the same Delta E to 1.0 decrease in Delta E over a carpet with 3× the fluorine and no clay nano-particles (Sample 13). Thus, a more environmentally friendly carpet fiber, with the same or improved drum soiling, can be achieved with the disclosed soil repellency aqueous dispersions.
- The invention has been described above with reference to the various aspects of the disclosed soil repellency aqueous dispersions, treated fibers, yarns, and textiles, and methods of making the same. Obvious modifications and alterations will occur to others upon reading and understanding the proceeding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the claims.
Claims (23)
1. An aqueous dispersion for soil repellency comprising:
at least one clay nanoparticle component; and a fluorochemical, wherein said fluorochemical is selected from the group consisting of fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, and fluorochemical guanidines and wherein said fluorochemical has less than or equal to six fluorinated carbons per fluorinated side-chain, and wherein said at least one clay nanoparticle component is selected from the group consisting of montmorillonite, hectorite, saponite, nontronite, beidellite and combinations thereof.
2-3. (canceled)
4. The aqueous dispersion of claim 1 , wherein said at least one clay nanoparticle component is synthetic.
5. The aqueous dispersion of claim 1 , wherein said at least one clay nanoparticle component is synthetic hectorite.
6-7. (canceled)
8. The aqueous dispersion of claim 1 , wherein said fluorochemical is a fluorochemical urethane.
9. The aqueous dispersion of claim 1 , wherein said at least one clay nanoparticle component is present in an amount from about 0.01% to about 25% weight in dispersion.
10. The aqueous dispersion of claim 1 , wherein said fluorochemical is present in an amount from about 0.0001% to about 5% weight fluorine atoms present in the dispersion.
11. The aqueous dispersion of claim 1 , wherein said at least one clay nanoparticle component is synthetic hectorite present in an amount from about 0.05% to about 15% weight in the dispersion; and said fluorochemical has per fluorinated side-chains with less than or equal to six fluorinated carbons and is present in an amount from about 0.005% to about 0.5% weight fluorine atoms present in the dispersion; and further wherein the weight percent ratio of said clay nanoparticle component to said fluorine ranges from about 5000:1 to about 2:1.
12-31. (canceled)
32. A method of making a soil repellency aqueous dispersion comprising:
a) contacting at least one clay nanoparticle component with a solvent to form an aqueous clay nanoparticle solution, wherein said at least one clay nanoparticle component is selected from the group consisting of montmorillonite, hectorite, saponite, nontronite, beidellite and combinations thereof; and
b) contacting said aqueous clay nanoparticle solution with a fluorochemical to form said soil repellency aqueous dispersion, wherein said fluorochemical is selected from the group consisting of: fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, and fluorochemical guanidines.
33. (canceled)
34. The method of claim 32 , wherein said at least one clay nanoparticle component is synthetic.
35. The method of claim 32 , wherein said at least one clay nanoparticle component is synthetic hectorite.
36. (canceled)
37. The method of claim 32 , wherein said fluorochemical is a fluorochemical urethane.
38. The method of claim 32 , wherein said at least one clay nanoparticle component is present in an amount from about 0.01% to about 25% weight in solution.
39. The method of claim 32 , wherein said fluorochemical is present in an amount from about 0.0001% to about 5% weight fluorine atoms present in solution.
40. The method of claim 32 , wherein said at least one clay nanoparticle component is synthetic hectorite present in an amount from about 0.05% to about 15% weight in solution; and said fluorochemical has per fluorinated side-chains with less than or equal to six fluorinated carbons and is present in an amount from about 0.005% to about 0.5% weight fluorine atoms present in the dispersion; and further wherein the weight percent ratio of said clay nanoparticle component to said fluorine ranges from about 5000:1 to about 2:1.
41. (canceled)
42. The method of claim 32 , wherein said soil repellant composition is applied using a technique selected from the group consisting of: spraying, dipping, coating, foaming, painting, brushing, and rolling.
43. The method of claim 42 , wherein said soil repellant composition is applied by spraying.
44-47. (canceled)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/884,011 US20160032518A1 (en) | 2009-12-10 | 2015-10-15 | Soil Repellency, Aqueous Dispersions, Soil Repellant Soft Articles, and Methods of Making the Same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28542509P | 2009-12-10 | 2009-12-10 | |
US12/965,395 US9194078B2 (en) | 2009-12-10 | 2010-12-10 | Soil repellency aqueous dispersions, soil repellant soft articles, and methods of making the same |
US14/884,011 US20160032518A1 (en) | 2009-12-10 | 2015-10-15 | Soil Repellency, Aqueous Dispersions, Soil Repellant Soft Articles, and Methods of Making the Same |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/965,395 Division US9194078B2 (en) | 2009-12-10 | 2010-12-10 | Soil repellency aqueous dispersions, soil repellant soft articles, and methods of making the same |
Publications (1)
Publication Number | Publication Date |
---|---|
US20160032518A1 true US20160032518A1 (en) | 2016-02-04 |
Family
ID=44146204
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/965,395 Expired - Fee Related US9194078B2 (en) | 2009-12-10 | 2010-12-10 | Soil repellency aqueous dispersions, soil repellant soft articles, and methods of making the same |
US14/884,011 Abandoned US20160032518A1 (en) | 2009-12-10 | 2015-10-15 | Soil Repellency, Aqueous Dispersions, Soil Repellant Soft Articles, and Methods of Making the Same |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/965,395 Expired - Fee Related US9194078B2 (en) | 2009-12-10 | 2010-12-10 | Soil repellency aqueous dispersions, soil repellant soft articles, and methods of making the same |
Country Status (10)
Country | Link |
---|---|
US (2) | US9194078B2 (en) |
EP (1) | EP2510074B1 (en) |
JP (2) | JP6480095B2 (en) |
CN (1) | CN102639673B (en) |
AU (1) | AU2010327975B2 (en) |
CA (1) | CA2782134C (en) |
DK (1) | DK2510074T3 (en) |
ES (1) | ES2749998T3 (en) |
NZ (1) | NZ600351A (en) |
WO (1) | WO2011072223A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018226562A1 (en) | 2017-06-07 | 2018-12-13 | Fortus Medical, Inc. | Connective tissue progenitor cell aspiration and processing system |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9217094B2 (en) * | 2011-07-28 | 2015-12-22 | The Board Of Trustees Of The University Of Illinois | Superhydrophobic compositions |
US9364859B2 (en) | 2011-07-28 | 2016-06-14 | Kimberly-Clark Worldwide, Inc. | Superhydrophobic surfaces |
WO2013048946A2 (en) * | 2011-09-26 | 2013-04-04 | Invista Technologies S.A R.L. | Processes to dye and treat bcf yarn |
EP2809840A4 (en) * | 2012-01-31 | 2015-12-09 | Invista Technologies Srl | Liquid and soil repellent compositions for fibers |
WO2014059415A1 (en) * | 2012-10-12 | 2014-04-17 | Invista Technologies S.A.R.L. | Surface modified nanoparticle aqueous dispersions for treating cellulose fiber products |
WO2014059413A1 (en) * | 2012-10-12 | 2014-04-17 | Invista Technologies S.A R.L. | Oil and grease repellant aqueous dispersions, oil and grease repellant cellulose fiber articles, and methods of making the same |
US9803100B2 (en) | 2013-04-30 | 2017-10-31 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic surfaces |
US10005917B2 (en) | 2013-04-30 | 2018-06-26 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic compositions |
CA2930467A1 (en) * | 2013-11-14 | 2015-05-21 | Invista Technologies S.A R.L. | Soil repellant fiber and methods of making the same |
ES2716080T3 (en) * | 2014-04-09 | 2019-06-10 | Invista Textiles Uk Ltd | Water-resistant and dirt-resistant fluorine-free compositions |
WO2016138272A1 (en) | 2015-02-27 | 2016-09-01 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic compositions |
AU2017269291A1 (en) * | 2016-05-24 | 2018-12-13 | Invista Textiles (U.K.) Limited | Compositions for the treatment of articles, and articles treated thereform |
CN106917170A (en) * | 2017-04-20 | 2017-07-04 | 湖北名仁纺织科技有限公司 | A kind of mould carbon fiber polyester thread of anti-soil and its production method |
US20210102145A1 (en) | 2017-11-06 | 2021-04-08 | Gpcp Ip Holdings Llc | Formulation for cleaning hard surfaces |
WO2020084457A1 (en) | 2018-10-24 | 2020-04-30 | Invista Textiles (U.K.) Limited | Method and products to impart stain protection |
CN112376281B (en) * | 2020-11-05 | 2022-12-30 | 广州市新志能服装有限公司 | Antifouling and oil-resistant textile fabric and preparation method thereof |
JP7458304B2 (en) * | 2020-11-26 | 2024-03-29 | 三菱マテリアル電子化成株式会社 | Air filter and its manufacturing method |
CN113308757B (en) * | 2021-06-08 | 2022-07-19 | 杭州诗蓝过滤科技有限公司 | Preparation method of filter cotton with good antibacterial performance |
Family Cites Families (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3398182A (en) | 1962-06-22 | 1968-08-20 | Minnesota Mining & Mfg | Fluorocarbon urethane compounds |
NL268543A (en) * | 1962-06-22 | 1900-01-01 | ||
GB1215861A (en) | 1967-02-09 | 1970-12-16 | Minnesota Mining & Mfg | Cleanable stain-resistant fabrics or fibers and polymers therefor |
US3434281A (en) * | 1967-06-05 | 1969-03-25 | Gen Dynamics Corp | Standby automatic water-methanol system for multiengine aircraft |
US4024178A (en) | 1972-03-06 | 1977-05-17 | Minnesota Mining And Manufacturing Company | Fluoroaliphatic radical containing carbodiimides |
US4147851A (en) | 1978-06-13 | 1979-04-03 | E. I. Du Pont De Nemours And Company | Fluorine-containing oil- and water-repellant copolymers |
US4540497A (en) | 1982-11-09 | 1985-09-10 | Minnesota Mining And Manufacturing Company | Fluoroaliphatic radical-containing, substituted guanidines and fibrous substrates treated therewith |
US4606737A (en) | 1984-06-26 | 1986-08-19 | Minnesota Mining And Manufacturing Company | Fluorochemical allophanate compositions and fibrous substrates treated therewith |
US5888290A (en) * | 1996-05-24 | 1999-03-30 | Minnesota Mining And Manufacturing Company | Composition and process for imparting durable repellency to substrates |
JP3389017B2 (en) * | 1995-07-10 | 2003-03-24 | 鐵也 田野島 | Culture soil using peat moss, method for producing the same, and seedling mat for raising seedlings |
US6225403B1 (en) | 1999-02-03 | 2001-05-01 | Barry R. Knowlton | Method and composition for treating fibrous substrates to impart oil, water and dry soil repellency |
JP4395628B2 (en) * | 1999-05-19 | 2010-01-13 | 株式会社ソフト99コーポレーション | Treatment method of automobile paint surface |
US6710123B1 (en) * | 1999-11-12 | 2004-03-23 | Atofina Chemicals, Inc. | Fluoropolymers containing organo-silanes and methods of making the same |
CA2410362C (en) * | 2000-06-14 | 2008-08-12 | The Procter & Gamble Company | Long lasting coatings for modifying hard surfaces and processes for applying the same |
US6803109B2 (en) * | 2001-03-09 | 2004-10-12 | 3M Innovative Properties Company | Water-and oil-repellency imparting urethane oligomers comprising perfluoroalkyl moieties |
JP4974315B2 (en) * | 2001-06-01 | 2012-07-11 | フマキラー株式会社 | Anti-fogging agent |
US20030148684A1 (en) * | 2002-01-30 | 2003-08-07 | The Procter & Gamble Company | Method for hydrophilizing materials using charged particles |
US7893014B2 (en) * | 2006-12-21 | 2011-02-22 | Gregory Van Buskirk | Fabric treatment for stain release |
JP4329559B2 (en) * | 2003-05-02 | 2009-09-09 | ダイキン工業株式会社 | Surface treatment agent comprising fluorine-containing polymer |
DE10331484A1 (en) * | 2003-07-11 | 2005-03-03 | Construction Research & Technology Gmbh | Polyurethane-polymer hybrid dispersion with improved surface properties, process for their preparation and their use |
US20050266753A1 (en) * | 2004-05-26 | 2005-12-01 | Xinggao Fang | Textile treatment and resulting textile |
US7579397B2 (en) * | 2005-01-27 | 2009-08-25 | Rensselaer Polytechnic Institute | Nanostructured dielectric composite materials |
JP4491639B2 (en) * | 2005-03-28 | 2010-06-30 | 平岡織染株式会社 | Flexible antifouling film |
KR20070071767A (en) * | 2005-12-30 | 2007-07-04 | 주식회사 효성 | The manufacturing method of contamination and bacteria resistance ultrafiltration membrane and microfiltration membrane |
US20080277346A1 (en) * | 2006-02-13 | 2008-11-13 | Advanced Materials Technology, Inc. | Process for preparing substrates with porous surface |
JP2007247089A (en) * | 2006-03-15 | 2007-09-27 | Toray Ind Inc | Fiber structure |
DE102006046368A1 (en) * | 2006-09-29 | 2008-04-03 | Construction Research & Technology Gmbh | New functionalized polyurethane resins, based on fluoro-modified, stabilized oligo- or polyurethane binder, useful for permanent oil-, water- and dirt-repellent coating of surfaces |
US7879743B2 (en) * | 2006-10-01 | 2011-02-01 | Bigsky Technologies Llc | Stain and soil resistant textile article |
JP2008223003A (en) * | 2006-12-28 | 2008-09-25 | Toto Ltd | Self-cleaning member and coating composition |
EP2146953A4 (en) * | 2007-05-18 | 2014-03-12 | Invista Tech Sarl | Method and composition for treating fibrous substrates |
CN100567623C (en) * | 2007-06-12 | 2009-12-09 | 东华大学 | A kind of organic and inorganic composite self-cleaning finishing agent and application thereof |
WO2009002994A1 (en) | 2007-06-26 | 2008-12-31 | Naturalnano Research, Inc. | Nanoclay filled fluoropolymer dispersions and method of forming same |
US9314544B2 (en) * | 2007-08-17 | 2016-04-19 | Kemal Vatansever Catalan | Durable hydrophilic coating compositions |
WO2009075387A1 (en) * | 2007-12-13 | 2009-06-18 | Daikin Industries, Ltd. | Fluorine-containing polymer and aqueous treatment agent |
JP2009191101A (en) * | 2008-02-12 | 2009-08-27 | Fujifilm Corp | Surface treatment agent composition containing fluorine-containing polyfunctional silicon compound |
CN101250596A (en) * | 2008-03-13 | 2008-08-27 | 陕西科技大学 | Preparation method of self-cleaning leather or product containing nano functional material |
US20100215894A1 (en) * | 2009-02-02 | 2010-08-26 | INVISTA North America S.ar.I | Compositions of surface modified nanoparticles |
CA2841073C (en) * | 2011-07-05 | 2019-08-20 | Luna Innovations Incorporated | Fluid-resistant textile fabrics and methods |
EP2809840A4 (en) * | 2012-01-31 | 2015-12-09 | Invista Technologies Srl | Liquid and soil repellent compositions for fibers |
US20140102651A1 (en) * | 2012-10-12 | 2014-04-17 | Georgia-Pacific Chemicals Llc | Greaseproof paper with lower content of fluorochemicals |
-
2010
- 2010-12-10 CN CN201080055884.0A patent/CN102639673B/en not_active Expired - Fee Related
- 2010-12-10 JP JP2012543309A patent/JP6480095B2/en not_active Expired - Fee Related
- 2010-12-10 US US12/965,395 patent/US9194078B2/en not_active Expired - Fee Related
- 2010-12-10 NZ NZ600351A patent/NZ600351A/en not_active IP Right Cessation
- 2010-12-10 ES ES10836752T patent/ES2749998T3/en active Active
- 2010-12-10 EP EP10836752.5A patent/EP2510074B1/en not_active Not-in-force
- 2010-12-10 CA CA2782134A patent/CA2782134C/en not_active Expired - Fee Related
- 2010-12-10 WO PCT/US2010/059888 patent/WO2011072223A2/en active Application Filing
- 2010-12-10 AU AU2010327975A patent/AU2010327975B2/en not_active Ceased
- 2010-12-10 DK DK10836752.5T patent/DK2510074T3/en active
-
2015
- 2015-10-15 US US14/884,011 patent/US20160032518A1/en not_active Abandoned
-
2016
- 2016-06-08 JP JP2016114340A patent/JP6430440B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018226562A1 (en) | 2017-06-07 | 2018-12-13 | Fortus Medical, Inc. | Connective tissue progenitor cell aspiration and processing system |
Also Published As
Publication number | Publication date |
---|---|
DK2510074T3 (en) | 2019-10-14 |
JP2013513702A (en) | 2013-04-22 |
US9194078B2 (en) | 2015-11-24 |
JP6430440B2 (en) | 2018-11-28 |
AU2010327975A1 (en) | 2012-06-21 |
CN102639673A (en) | 2012-08-15 |
AU2010327975B2 (en) | 2015-10-22 |
CA2782134C (en) | 2016-12-13 |
EP2510074A4 (en) | 2016-05-18 |
EP2510074A2 (en) | 2012-10-17 |
US20110311757A1 (en) | 2011-12-22 |
WO2011072223A2 (en) | 2011-06-16 |
ES2749998T3 (en) | 2020-03-24 |
CN102639673B (en) | 2016-03-09 |
JP2016216723A (en) | 2016-12-22 |
CA2782134A1 (en) | 2011-06-16 |
WO2011072223A3 (en) | 2011-10-06 |
JP6480095B2 (en) | 2019-03-06 |
NZ600351A (en) | 2015-01-30 |
EP2510074B1 (en) | 2019-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9194078B2 (en) | Soil repellency aqueous dispersions, soil repellant soft articles, and methods of making the same | |
CA2863525C (en) | Liquid and soil repellent compositions for fibers | |
AU2014348468B2 (en) | Soil repellant fiber and methods of making the same | |
AU2015243869B2 (en) | Water repellent, soil resistant, fluorine-free compositions | |
JP5216850B2 (en) | Methods and compositions for treating fibrous substrates | |
US11352740B2 (en) | Compositions for the treatment of articles, and articles treated therefrom | |
WO2014059413A1 (en) | Oil and grease repellant aqueous dispersions, oil and grease repellant cellulose fiber articles, and methods of making the same | |
JP2021503051A (en) | Non-fluorinated fiber and textile treatment compositions and their uses |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |