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WO1998050619A1 - Traitement de substrats fibreux visant a leur conferer des proprietes hydrofuges, anti-taches et anti-salissures - Google Patents

Traitement de substrats fibreux visant a leur conferer des proprietes hydrofuges, anti-taches et anti-salissures Download PDF

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Publication number
WO1998050619A1
WO1998050619A1 PCT/US1998/008211 US9808211W WO9850619A1 WO 1998050619 A1 WO1998050619 A1 WO 1998050619A1 US 9808211 W US9808211 W US 9808211W WO 9850619 A1 WO9850619 A1 WO 9850619A1
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WO
WIPO (PCT)
Prior art keywords
substrate
fluorochemical
treating
contact angle
receding contact
Prior art date
Application number
PCT/US1998/008211
Other languages
English (en)
Inventor
John C. Clark
John C. Newland
Robert F. Kamrath
Malcolm B. Burleigh
Kevin R. Schaffer
Original Assignee
Minnesota Mining And Manufacturing Company
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 Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to CA2287494A priority Critical patent/CA2287494C/fr
Priority to JP54813598A priority patent/JP2001526739A/ja
Priority to EP98918639A priority patent/EP0980449B1/fr
Priority to AU71526/98A priority patent/AU736286B2/en
Priority to BR9808724-0A priority patent/BR9808724A/pt
Publication of WO1998050619A1 publication Critical patent/WO1998050619A1/fr

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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
    • 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
    • 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
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • D06M15/412—Phenol-aldehyde or phenol-ketone resins sulfonated

Definitions

  • This invention relates generally to carpet treatments, and in particular to a method for imparting repellency, stain-resistance and soil-resistance to carpets by applying to the carpet an aqueous treating solution comprising a fluorochemical and/or hydrocarbon agent, a stainblocking material, and a salt.
  • U.S. Pat. No. 4,875,901 discloses a method for providing fibrous polyamide substrates with stain resistance by contacting the substrate with an aqueous solution comprising a normally solid, water-soluble, partially sulfonated novolac resin and a water-soluble polyvalent metal salt.
  • U.S. Pat. No. 4,940,757 (Moss et al.) and its continuation-in-part, U.S. Pat. No. 5,310,828 (Williams et al.), describe polymeric compositions that impart stain resistance to polyamide fibers.
  • the compositions are made by polymerizing an ⁇ -substituted acrylic acid or ester in the presence of a sulfonated aromatic formaldehyde condensation polymer.
  • this polymer can be combined with certain halogenated polymers such as perfluorinated urethanes and acrylates, and a small amount of a divalent metal salt, such as a magnesium salt, can be applied along with the stain resistant composition.
  • U.S. Pat. No. 4,822,373 (Olson et. al) describes treated fibrous polyamide substrates having applied thereto a partially sulfonated novolac resin and methacrylic acid-containing polymers.
  • U.S. Pat. No. 5,001,004 (Fitzgerald et al.) describes stain-resistant, polyamide textile substrates treated with compositions comprising hydrolyzed ethylenically unsaturated aromatic/ maleic anhydride polymers.
  • a polyfluoroorganic oil-, water- and/or soil-repellent can be applied before, during, or after the application of the polymer.
  • the hydrolyzed polymers can be applied to textile substrates in a variety of ways, e.g., during conventional beck and continuous dyeing processes, and are normally applied at an acidic pH.
  • WO 93/19238 discloses a stain- resist which can be applied to polyamide textiles by padding or spraying comprising blends of maleic anhydride/alpha-olefin polymers with sulfonated phenol-formaldehyde condensation products.
  • a polyfluoroorganic oil- , water- and/or soil-repellent can be applied before, during, or after the application of the polymer.
  • U.S. Pat. No. 4,925,707 describes the coapplication of fluorochemical anti-soilants with stainblockers to nylon carpet which is installed.
  • U.S. Pat. No. 5,252,232 describes an improved process for preparing a freeze-thaw stable aqueous composition comprising an aqueous perfluoroalkyl ester of citric acid and a hydrolyzed styrene/maleic anhydride copolymer which, when applied to an installed nylon carpet in such a way to thoroughly wet the pile fibers, imparts stain and soil resistance.
  • 5,073,442 (Knowlton et al.) describes a method for enhancing the soil- and/or stain-resistant characteristics of polyamide and wool fabrics by applying an aqueous solution containing various combinations of sulfonated phenolic compounds, compounds of sulfonated phenolics and aldehydes, fluorochemicals, modified wax emulsions, acrylics, and organic acids of low molecular weight.
  • U.S. Pat. No. 5,520,962 (Jones) describes a method and composition for treating carpet yarn to enhance its repellency and stain resistance by treating by immersion in an acidic aqueous medium containing an anionic or nonionic fluorochemical, heating, and removing the excess water.
  • U.S. Pat. No. 4,680,212 (Blyth et al.) describes undyed stain-resistant nylon fibers having coated on their surface one or more stainblockers and one or more fluorochemicals to impart stain resistance after trafficking.
  • the coating is preferably applied to the nylon fibers as an aqueous spin finish during the melt spinning process used to prepare the fibers.
  • U.S. Pat. No. 5,516,337 describes a method for improving stain resistance to fibers, especially wool, by (a) treating the fibers with a mordant, (b) treatment with a combination of sulfonated or disulfonated surfactant together with a stain resist chemical, and (c) providing treatment with a fluorochemical in either step (a) or (b) in an amount sufficient to improve stain resist properties.
  • EP-A-797699 describes an aqueous treating composition for providing stain release properties to fibrous materials comprising (a) polymethacrylic acid [homopolymers] or copolymers containing methacrylic acid, (b) a partially sulfonated novolak resin, (c) a sulfated surfactant and (d) water, which can also contain divalent metal salts and can be coapplied with a fluorochemical composition.
  • U.S. Pat. No. 4,839,212 (Blyth et al.) describes nylon fibers coated with a sulfonated condensation product stainblocker and optional fluorochemical.
  • U.S. Pat. No. 4,959,248 (Oxenrider et al.) describes a process for imparting stain resisting properties to fibers formed from thermoplastic polymers by treating the fibers with a combination of a phenol condensation stainblocker and a fluorochemical anti-soiling agent made by reacting pyromellitic anhydride with fluorinated alcohol and an oxirane.
  • European Patent Application 0 353 080 (Ingham et al.) describes a process for improving the stain resistance of polyamide and keratinous fibers by treating the fibers in an aqueous dye bath at a long liquor ratio firstly with a fluorochemical composition and subsequently with a stainblocker.
  • the reference states that the applicants found that simultaneous application results in interference between the fluorocarbon and the stainblocker.
  • U.S. Pat. No. 2,876,140 (Sheehan) describes softening agents for textile materials having improved soil resistance which are a combination of barium sulfate and cationic softening agents. These softening agents are of the higher fatty acid amide type, such as the reaction products of polybasic organic acids with dialkylol substituted carbamido compounds carrying side chains containing polyamino acid radicals and their salts.
  • U.S. Pat. No. 4,076,631 (Caruso et al.) describes treating compositions for textiles to provide an antistatic, dirt repellent finish consisting essentially of (1) a fatty amide antistatic agent, (2) an aqueous dispersion of hard particles, such as polystyrene, polymethyl methacrylate or colloidal hydrous metal oxide, (3) a fluorine-free inorganic or organic monobasic or polybasic acid, (4) an antimicrobial agent, and (5) a fluorocarbon agent which provides a low free surface energy.
  • a fatty amide antistatic agent such as polystyrene, polymethyl methacrylate or colloidal hydrous metal oxide
  • a fluorine-free inorganic or organic monobasic or polybasic acid such as polystyrene, polymethyl methacrylate or colloidal hydrous metal oxide
  • a fluorine-free inorganic or organic monobasic or polybasic acid such as polystyrene, polymethyl methacryl
  • U.S. Pat. No. 4,144,026 (Keller et al.) describes a process for simultaneously providing textile materials with an antistatic and dirt-repellent finish by treating the textile materials with an aqueous solution containing (a) a copolymer of an , ⁇ -unsaturated dicarboxylic acid or the anhydride thereof and at least one other ethylenically unsaturated compound, and (b) a fatty acid/alkanolamine reaction product or an alkylene oxide adduct of this reaction product, and subsequently drying them.
  • U.S. Pat. No. 4,329,390 (Danner) describes aqueous dispersions of a microcrystalline wax, optionally together with one or more non-oxidized paraffins, having a cationic surfactant used as a dispersing agent,. These aqueous dispersions, when applied to textile substrates such as carpet via impregnation or exhaust processes, provide a textile substrate with improved sewability and less damage by high-speed sewing machines.
  • U.S. Pat. No. 5,491,004 (Mudge et al) describes a method for applying a low soil finish to spun synthetic textile fibers by applying a dry, way solid component comprising a fatty bisamide, a block copolymer of ethylene oxide and propylene oxide, the reaction product of a saturated fatty alcohol, a saturated fatty amine or an ethoxylated phenol, and/or a fatty acid ester.
  • the present invention relates to a treatment for carpets and other fibrous substrates which imparts to the substrate exceptional dynamic water and oil repellency, in-depth stain resistance, and excellent durable anti-soiling performance.
  • the substrate is treated with a (typically aqueous) mixture comprising (1) a repellent material selected from the group consisting of glassy fluorochemicals having a receding contact angle to n- hexadecane of greater than 53° (preferably, 65° or higher, and more preferably, at least 70° or higher) and glassy hydrocarbons having a receding contact angle to n-hexadecane of 35° or higher; (2) a stainblocking material; and (3) an exhausting aid selected from the group consisting of metal salts and acids.
  • a repellent material selected from the group consisting of glassy fluorochemicals having a receding contact angle to n- hexadecane of greater than 53° (preferably, 65° or higher, and more preferably, at least 70
  • the aqueous mixture is typically applied by contacting the fibrous substrate with the treatment solution in such a way as to fully contact all fibers of the substrate with the solution.
  • the wet treated substrate is then exposed to steam or other water- saturated atmosphere for a sufficient period of time, and at a sufficiently high temperature, to affix the treating materials onto the fibrous substrate.
  • the wet treated substrate is then rinsed with water and dried in an oven at a high enough temperature to activate the materials.
  • the present invention relates to fibrous substrates treated in accordance with the method described above which exhibit excellent anti-soiling, anti-staining and repellency performance.
  • the fibrous substrate having had total penetration of the fluorochemical, hydrocarbon and stainblocking materials into and throughout each fiber, exhibits excellent dynamic water resistance (i.e., resistance to penetration by water-based drinks spilled from a height), greatly resists staining by aqueous acid staining agents such as red KOOL-AIDTM drink, prevents oil penetration into any portion of the fiber, and in the case of carpet offers significant protection again dry soiling when compared to untreated carpet as demonstrated by several cycles of "walk- on” tests.
  • the present invention relates to a method for identifying hydrocarbon and fluorochemical materials which will exhibit good anti-soiling properties when applied to a fibrous substrate.
  • fluorochemicals having a receding contact angle to n-hexadecane of at least about 53°, preferably greater than about 65°, and more preferably at least about 70° are found to exhibit particularly good anti-soiling properties.
  • hydrocarbon materials having a receding contact angle to n-hexadecane of at least about 35° are found to exhibit particularly good anti-soiling properties.
  • the fluorochemical or hydrocarbon materials are hard, glassy, non-tacky, non-cationic materials having a glass transition temperature of from about 20°C to about 130°C.
  • the present invention relates to an immersion process for treating carpets and other fibrous substrates to improve, for example, their anti-soiling properties, wherein the treating solution comprises a material that contains both fluorochemical and hydrocarbon moieties. Substrates treated in accordance with the method exhibit excellent anti-soiling properties, but at generally greater fluorine efficiency than treatments using similar materials that lack hydrocarbon groups.
  • the present invention relates to an immersion process for treating carpets and other fibrous substrates to improve, for example, their anti-soiling properties, wherein the treating solution comprises a blend of fluorochemical and hydrocarbon materials. Substrates treated in accordance with the method exhibit excellent anti-soiling properties, but at generally greater fluorine efficiency than treatments using only fluorochemical materials.
  • the present invention pertains to a method for treating carpets and other fibrous substrates with a composition comprising a hydrocarbon material and, preferably, a stainblocker.
  • the hydrocarbon material preferably has a receding contact angle to n-hexadecane of at least about 35°.
  • FIG. 1 is a graph of dynamic repellency as a function of pH for carpets treated in accordance with the method of the present invention
  • FIGS. 2-5 are micrographs of treated fibers which illustrate the effects of the concentration of magnesium salt on treatment process of the present invention
  • FIG. 6 is a micrograph of a carpet fiber treated by a typical spray application process.
  • the present invention relates to a treatment for carpets and other fibrous substrates which imparts to the substrate exceptional dynamic water and oil repellency, in-depth stain resistance, and excellent durable anti-soiling performance.
  • the substrate is treated with a (typically aqueous) composition comprising (1) a repellent material selected from the group consisting of glassy fluorochemicals having a receding contact angle to n-hexadecane of 65° or higher and glassy hydrocarbons having a receding contact angle to n-hexadecane of 35° or higher; (2) a stainblocking material; and (3) an exhausting aid selected from the group consisting of metal salts (preferably polyvalent metal salts) and acids.
  • a repellent material selected from the group consisting of glassy fluorochemicals having a receding contact angle to n-hexadecane of 65° or higher and glassy hydrocarbons having a receding contact angle to n-hexadecane of 35° or higher
  • the aqueous mixture is typically applied by contacting the fibrous substrate with the treatment solution in such a way as to fully contact all fibers of the substrate with the solution.
  • the wet treated substrate is then exposed to steam or other water-saturated atmosphere for a sufficient period of time, and at a sufficiently high temperature, to affix the treating materials onto the fibrous substrate.
  • the wet treated substrate is then rinsed with water and dried in an oven at a high enough temperature to activate the materials.
  • exhaustion processes can be used to apply the treatment solution of the present invention to a fibrous substrate, the function of the exhaustion process being to totally contact the entirety of each fiber of the fibrous substrate with stainblocking material and the repellent fluorochemical material and/or hydrocarbon material.
  • suitable exhaustion processes include immersion, flooding, and foam application.
  • Useful processes and equipment include Kuster's FlexnipTM equipment, Kuster's foam applicator, FluiconTM flood applicator, Beck vat process, FluidyeTM unit, hot otting, puddle foamer and padding.
  • application at a sufficient high bath temperature e.g., over 200°F
  • FLUOROCHEMICAL MATERIALS FLUOROCHEMICAL MATERIALS
  • the treatments of this invention must contain certain repellent fluorochemical material and/or hydrocarbon material.
  • Suitable fluorochemicals for use in the present invention should exhibit a receding contact angle to n- hexadecane of at least 53° or higher, preferably at least 65° or higher, and more preferably at least 70° or higher, as measured by the Receding Contact Angle Test described herein.
  • suitable fluorochemical materials are hard, glassy, non-tacky, non-cationic materials having a glass transition temperature ranging from about 20°C to about 130°C.
  • the fluorochemical material can be from any chemical class, but fluorochemical urethanes are preferred.
  • the fluorochemical material preferably contains a fluoroaliphatic group, and most preferably, a perfluoroaliphatic group.
  • concentration of fluorochemical material should be at least 0.03% SOF (solids on fiber) and preferably is at least 0.1 % SOF.
  • SOF solids on fiber
  • F-3 - ScotchgardTM Carpet Protector FC-358 - a fluorochemical carbodiimide, commercially available as a 20% (wt) solids aqueous emulsion from Minnesota Mining and Manufacturing Company.
  • F-9 - ScotchgardTM Carpet Protector FC-1374 - a fluorochemical urethane, commercially available as a 31% (wt) solids aqueous emulsion from Minnesota Mining and Manufacturing Company.
  • F-10 - ScotchgardTM Carpet Protector FC-1395 - a fluorochemical urethane, commercially available as a 31%> (wt) solids aqueous emulsion from Minnesota Mining and Manufacturing Company.
  • F-ll - DuratechTM carpet treatment believed to be a fluorochemical urethane/urea, commercially available as a 30%) (wt) solids aqueous emulsion from E.I. duPont de Nemours & Co., Wilmington, Delaware
  • F-ll A - NRD-372 carpet treatment believed to be a fluorochemical urethane/urea, commercially available as a 27% (wt) solids aqueous emulsion from E.I. duPont de Nemours & Co.
  • F-12 - ZonylTM 8779 carpet treatment commercially available as an
  • F-13 - SoftechTM 97H carpet treatment believed to be a fluoroalkyl acrylate polymer, commercially available as a 15% (wt) solids aqueous emulsion from Dyetech, Inc., Dalton, Georgia F-14 - Sha guardTM 353 fluoroalkyl acrylate copolymer - commercially available as a 13% (wt) solids aqueous emulsion from Shaw Industries, Inc.
  • Another mixture consisting of 500 g of water and 5 g of SiponateTM DS-10 surfactant (commercially available from Rhone-Poulenc Corp., Cranberry, New Jersey) was heated to 70°C to dissolve the surfactant.
  • the two liquids were mixed with stirring and were subjected to 12 minutes of emulsification using a Branson SonifierTM Ultrasonic Horn 450 (commercially available from VWR Scientific).
  • the solution was stripped of organic solvent on a rotary evaporator.
  • the MIBK was co-distilled with a certain amount of water. When inspection revealed the there was no longer any odor of solvent, the amount of solids was measured and sufficient water was added to bring the final emulsion weight percent solids to 14.6%. .
  • Suitable hydrocarbon materials for use in the present invention exhibit a receding contact angle to «-hexadecane of at least 35° or higher as measured by the Receding Contact Angle Test described herein.
  • suitable hydrocarbon materials are hard, glassy, non-tacky, non-cationic, fluorine-free materials having at least one aliphatic group and having a glass transition temperature ranging from about 20°C to about 130°C.
  • the aliphatic group is preferably a long-chain aliphatic group containing at least 10 carbon atoms, and more preferably containing between about 12 and about 24 carbon atoms.
  • the hydrocarbon material can be from any chemical class, but hydrocarbon urethanes and amides are preferred.
  • the concentration of hydrocarbon material should be at least 0.1% SOF and is preferably at least 0.2% SOF. The following is a list of hydrocarbons which are referred to in the Examples:
  • H-2 Hexadecyl urethane of DesmodurTM NlOO - Essentially the same procedure for synthesis and emulsification was used to prepare H-2 as was used to prepare H-l except that 272 g (1.12 eq) of hexadecanol replaced 285 g (1.06 eq) of octadecanol. The final emulsion weight percent solids was 20.0%.
  • H-3 Tetradecyl urethane of DesmodurTM NlOO -
  • 256 g (1.20 eq) of tetradecanol replaced 285 g (1.06 eq) of octadecanol and 244 g (1.28 eq) rather than 228 g (1.12 eq) of DesmodurTM NlOO triisocyanate was used.
  • the final emulsion weight percent solids was 20.0%.
  • H-4A Octadecyl urethane of DesmodurTM N75 -
  • H-4A Octadecyl urethane of DesmodurTM N75 -
  • 284 g (1.10 eq) of DesmodurTM N75 replaced 228 g (1.12 eq) of DesmodurTM NlOO triisocyanate.
  • the final emulsion weight percent solids was 18.0%).
  • H-5 Octadecyl urethane of isophorone diisocyanate -
  • H-5 Essentially the same procedure for synthesis and emulsification was used to prepare H-5 as was used to prepare H-l except that 348 g (1.29 eq) rather than 285 g (1.06 eq) of octadecanol was used and 152 g (1.37 eq) of isophorone diisocyanate replaced 228 g (1.12 eq) of DesmodurTM NlOO triisocyanate.
  • the final emulsion weight percent solids was 20.0%.
  • H-6 Hexadecyl urethane of isophorone diisocyanate -
  • H-5 was used to prepare H-l except that 336 g (1.39 eq) of hexadecanol replaced 285 g (1.06 eq) of octadecanol and 164 g (1.47 eq) of isophorone diisocyanate replaced 228 g (1.12 eq) of DesmodurTM NlOO triisocyanate.
  • the final emulsion weight percent solids was 20.0%).
  • the mixture was poured into shallow pans in an oven for 6 hours at 125°C.
  • the material was collected as a hard white glassy material and was emulsified as described in the preparation of Hydrocarbon Material H-l.
  • the reaction was cooled to 130°C and 107.6 g of melted octadecylamine (equivalent weight of 269) was added to the reaction. The reaction exothermed to 163°C and then cooled to 125°C. Finally, the reaction was heated at 125°-135°C for 1.5 hours. The reaction was cooled to room temperature and 307g of a glassy solid was collected.
  • a one pint aluminum can was equipped with an overhead stirrer and a nitrogen purge line.
  • the flask was charged with 146 g of EPONTM 828 and 50 g of bisphenol A.
  • the reaction was heated to 125°C while being purged with nitrogen.
  • 4 g, of bisphenol A and 0.25 g of phosphonium iodide were charged to the flask.
  • the reaction was heated to 145°C.
  • the reaction exothermed to 175°C and was held at this temperature for 1 hour.
  • the reaction was cooled to 130°C and 82.8 g of melted octadecylamine (equivalent weight of 269) was added to the reaction.
  • the reaction exothermed to 163°C and then cooled to 125°C.
  • the reaction was heated at 125°-135°C for 1.5 hours.
  • the reaction was cooled to room temperature and 282g of a glassy solid was collected.
  • reaction was cooled and allowed to stand at room temperature over the weekend. Then the reaction was heated to 210°C for one hour and then cooled. 2271 g of a white solid was collected, and its identification was confirmed an infra red and 13 C NMR spectra. The melting point was measured to be 85°C.
  • a three-necked 1000 mL flask was equipped with a Dean-Stark trap and an overhead stirrer.
  • 94 g (0.5 mol) of azelaic acid and 170 g (1.0 mol) of isophorone diamine was added to the reaction flask.
  • the flask was heated to 190°C for 2 hours.
  • the required amount of water (18 g) had been collected in the Dean-Stark trap.
  • 284 g (1.0 mol) of stearic acid was added to the reaction.
  • the reaction was heated at 210°C for 1 hour.
  • the reaction was cooled and 500 g of a glassy solid was collected.
  • Product identification was confirmed by an infrared spectrum.
  • a three necked 1000 mL flask was equipped with a Dean-Stark trap and an overhead stirrer. 284 g (1.0 mol) of stearic acid, 1.4 g of IrganoxTM 245 (commercially available from Ciba Specialty Chemicals) was added to the reaction flask. The reaction flask was purged with nitrogen for 30 minutes. Next, the flask was slowly heated to 100°C, at which point all of the stearic acid had melted. 63g (0.54 mol) of DytekTM A diamine (commercially available from E. I. duPont de Nemours, Wilmington, Delaware) was added to the reaction and the reaction was heated to 170-180°C.
  • H-15 - Hexadecyl urea of VestanatTM T1890 triisocyanate Essentially the same procedure for synthesis and emulsification was used to prepare H-l 5 as was used to prepare H-14, except that 75.0 g (0.071 eq) instead of 70.0 g (0.067 eq) of VestanatTM T1890 was used and 51.6 g (0.214 eq) of ArmeenTM 16D flake (cetylamine, commercially available from Akzo Nobel Corp.) was used instead of 53.8 g (0.20 eq) of ArmeenTM 18D flake.
  • H-l 7 - KenamideTM E-180 - stearyl erucamide commercially available from Witco Corp., Memphis, Tennessee.
  • H-18 - KenamideTM E-221 - erucyl erucamide commercially available from Witco Corp., Memphis, Tennessee.
  • the material used in the present invention to impart oil repellency, water repellency and soil resistance to a fibrous substrate can be a hybrid of the fluorochemicals and hydrocarbons previously mentioned.
  • Such materials may be, for example, the reaction product of a fluorochemical with a hydrocarbon material.
  • the resulting material must be a hard, glassy, non-tacky material having a glass transition temperature ranging from about 20°C to about 130°C.
  • hybrid materials which are referred to in the Examples:
  • FH-4 - Urethane Reaction Product of Desmodur N-75 with 10% (mol) of MeFOSE and 90% (mol) of stearyl alcohol Essentially the same procedure for synthesis and emulsification was used to prepare FH-4 as was used to prepare FH-1, except that 37 g (0.07 eq) of MeFOSE alcohol, 258 g (0.96 eq) of octadecanol, 273 g (1.05 eq) of DesmodurTM N75 triisocyanate and 432 g MIBK were used. The final emulsion weight percent solids was 15.3%).
  • the treatment solution of the present invention will include at least one stainblocker.
  • the stainblocker may be omitted entirely without significantly affecting oil and water repellency (see Table 14).
  • Table 14 oil and water repellency
  • FC-369 a stainblocking material for carpet comprised of sulfonated phenolic resins, commercially available from Minnesota Mining and Manufacturing Company as a 34% (wt) solids aqueous emulsion
  • FX-670 - a stainblocking material for carpet comprised of acrylic resins, commercially available from Minnesota Mining and Manufacturing Company as a 30% (wt) solids aqueous emulsion S-6 - SR-300 - a stainblocking material consisting of a blend of sulfonated aromatic compound and hydrolyzed copolymer of unsaturated aromatic monomer and maleic anhydride, commercially available as a 30% (wt) solids solution from E.I. duPont de Nemours & Co.
  • S-7 - a stainblocking material which is the sodium salt of hydrolyzed styreneimaleic anhydride copolymer (SMA-1000, commercially available from Elf Atochem, Birdsboro, Pennsylvania), which can be prepared using the procedure described in Example 1 of the U.S. Pat. No. 5,001,004 (Fitzgerald et al).
  • SMA-1000 hydrolyzed styreneimaleic anhydride copolymer
  • Various salts may be used in the present invention to improve the deposition of fluorochemical or hydrocarbon onto the fibrous substrate.
  • Divalent metal salts e.g., MgSO 4
  • MgSO 4 is generally preferred, although good results can also be obtained under certain conditions through the use of monovalent salts or polyvalent salts.
  • Suitable salts for use in the present invention include LiCl, NaCl, NaBr, Nal, KC1, CsCl, Li 2 SO 4 , Na 2 SO 4 , NH 4 C1, (NH 4 ) 2 SO 4 , (CH 3 ) 4 NC1, MgCl 2 , MgSO 4 , CaCl 2 , Ca(Ch 3 COO) 2 , SrCl 2 , BaCl 2 , ZnCl 2 , ZnSO 4 , FeSO 4 , and CuSO 4 .
  • the pH of the treatment solution e.g., by making it more acidic
  • Suitable acids that may be used in this regard include sulfuric acid, sulfamic acid, citric acid, hydrochloric acid, oxalic acid, and autoacid (a mixture of urea and sulfuric acid). While the optimal pH for the treatment solution may vary depending on the choice of materials, optimal results are generally obtained with a pH of less than about 5, and more preferably, a pH of less than about 3.
  • the color of the carpet is Vellum and is designated by the color code 76113
  • a carpet sample measuring approximately 5 inches by 4 inches (13 cm x 10 cm) is immersed in deionized water at room temperature until dripping wet. Water is extracted from the wet sample by spinning in a Bock Centrifugal Extractor until the sample is damp. The damp carpet sample is then steamed for 2 minutes at atmospheric pressure, at a temperature of 90-100°C, and 100% relative humidity in an enclosed steam chamber.
  • the carpet sample After steaming, the carpet sample is allowed to cool to near room temperature, and the aqueous treating composition is applied by placing the carpet sample, carpet fiber side down, in a glass tray containing the treating composition.
  • the treating composition contains sufficient glassy fluorochemical and/or hydrocarbon material and sufficient stainblocking material to give the desired percent solids on fiber (% SOF) and is prepared by dissolving or dispersing the two types of materials and (optionally) the desired amount of salt in deionized water and adjusting the pH to a value of 2 (unless specified otherwise) using 10% aqueous sulfamic acid.
  • the weight of the aqueous treating solution in the glass tray is approximately 3.5 to 4 times the weight of the carpet sample.
  • the carpet sample absorbs the entire volume of treating solution over a 1 to 2 minute period to give a percent wet pickup of 350-400%).
  • wet treated carpet sample is steamed a second time for 2 minutes (using the same conditions and equipment as described above), is immersed briefly in a 5-gallon bucket half full of deionized water, is rinsed thoroughly under a deionized water stream to remove residual, excess treating composition, is spun to dampness using the centrifugal extractor, and is allowed to air-dry overnight at room temperature before testing.
  • the aqueous treating solution is applied to the carpet via spraying to about 15%> by weight wet pickup, using a laboratory-sized spray booth with conveyor belt designed to mimic the performance of a large-scale commercial spray boom as is conventionally used in carpet mills.
  • the wet sprayed carpet is then dried at 120°C until dry (typically for 10-20 minutes) in a forced air oven.
  • the application rate (in %> SOF) is controlled by varying the conveyor belt speed.
  • the foamer applicator used in the present invention consists of a foam preparation device and a vacuum frame device.
  • the foam preparation device is a Hobart Kitchen-AidTM mixer made by the Kitchen- Aid Division of Hobart Corporation, Troy, Ohio.
  • the vacuum frame device is a small stainless steel bench with a vacuum plenum and a vacuum bed.
  • the carpet to be treated is placed on the bed, along with the foamed material to be deposited onto the carpet.
  • the vacuum bed forms a bench that has an exhaust port fitted to a Dayton TradesmanTM 25 gallon Heavy Duty Shop Vac.
  • the size of the bed is 8" x 12" x 1.5" (20 cm x 30 cm x 4 cm).
  • the plenum is separated from the rest of the bed by an aluminum plate in which closely spaced 1/16" (1.7 mm) holes are drilled.
  • the plate is similar in structure to a colander.
  • the portion of carpet to be treated is weighed.
  • the carpet may then be pre- wetted with water.
  • blow ratio foam volume/foam weight
  • the foam should be adjusted so that the wet pick-up of foam is about 60% that of the dry carpet weight, although other values for the wet pick-up may be employed as required for a particular application.
  • a doctor blade can be prepared out of any thin, stiff material. Thin vinyl sheeting, approximately 100 mil (2.5 mm) thick, is especially suitable, since it can be cut easily to any size. The notch part of the blade should be about 8" (20 cm) wide so as to fit into the slot of the vacuum bed.
  • liquid to be foamed is put into the bowl of the Kitchen- AidTM mixer.
  • the wire whisk attachment is used and the mixer is set to its highest speed (10).
  • About 2-3 minutes are allowed for the foam to form and stabilize at a certain blow ratio.
  • the blow ratio may be calculated by placing volume marks on the side of the bowl.
  • Treated ca ⁇ et samples were evaluated for water repellency using 3M Water Repellency Test V for Floorcoverings (February 1994), available from Minnesota Mining and Manufacturing Company.
  • treated carpet samples are challenged to penetrations by blends of deionized water and isopropyl alcohol (IPA). Each blend is assigned a rating number as shown below:
  • a treated ca ⁇ et sample is placed on a flat, horizontal surface and the ca ⁇ et pile is hand-brushed in the direction giving the greatest lay to the yarn.
  • Five small drops of water or a water/IPA mixture are gently placed at points at least two inches apart on the ca ⁇ et sample. If, after observing for ten seconds at a 45° angle, four of the five drops are visible as a sphere or a hemisphere, the ca ⁇ et is deemed to pass the test.
  • the reported water repellency rating corresponds to the highest numbered water or water/IPA mixture for which the treated ca ⁇ et sample passes the described test.
  • Treated ca ⁇ et samples were evaluated for oil repellency using 3M Oil Repellency Test III (February 1994), available from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota. In this test, treated ca ⁇ et samples are challenged to penetration by oil or oil mixtures of varying surface tensions. Oils and oil mixtures are given a rating corresponding to the following:
  • Oil Repellency Test is run in the same manner as is the Water Repellency Test, with the reported oil repellency rating corresponding to the highest oil or oil mixture for which the treated ca ⁇ et sample passes the test.
  • Dynamic water resistance was determined using the following test procedure.
  • a treated ca ⁇ et sample (15.2 cm x 15.2 cm) is inclined at an angle of 45° from horizontal and 20 mL of deionized water is impinged onto the center of the ca ⁇ et sample through a glass tube with 5 mm inside diameter positioned 45.7 cm above the test sample.
  • the increase in weight (g) of the test sample is measured, with lower weight gains indicating better dynamic water repellency properties.
  • Stain resistance was determined using the following test procedure.
  • a treated 13 cm x 10 cm ca ⁇ et sample is stained for 2 minutes by immersing the ca ⁇ et sample in an aqueous solution of 0.007%) (wt) of Red Dye FD&C #40 in deionized water adjusted to a pH of 2.8 with 10% aqueous sulfamic acid.
  • the dye solution is warmed to a temperature of 55-70°C.
  • the treated and stained ca ⁇ et sample is then immersed briefly in a 5-gallon bucket half full of deionized water, followed by rinsing under a stream of deionized water until the water runs clear.
  • the wet ca ⁇ et sample is then extracted to dampness using a Bock Centrifugal Extractor and is air-dried overnight at room temperature.
  • the degree of staining of the ca ⁇ et sample is determined numerically by using a Minolta 310 Chroma MeterTM compact tristimulus color analyzer.
  • the color analyzer measures red stain color autochromatically on the red-green color coordinate as a "delta a" ( ⁇ a) value as compared to the color of an unstained and untreated ca ⁇ et sample. Measurements reported in the tables below are given to one place following the decimal point and represent the average of 3 measurements, unless stated otherwise. A greater ⁇ a reading indicates a greater amount of staining from the red dye. ⁇ a readings typically vary from 0 (no staining) to 50 (severe staining).
  • the relative soiling potential of each treatment was determined by challenging both treated and untreated (control) ca ⁇ et samples under defined "walk-on" soiling test conditions and comparing their relative soiling levels.
  • the test is conducted by mounting treated and untreated ca ⁇ et squares on particle board, placing the samples on the floor of one of two chosen commercial locations, and allowing the samples to be soiled by normal foot traffic. The amount of foot traffic in each of these areas is monitored, and the position of each sample within a given location is changed daily using a pattern designed to minimize the effects of position and orientation upon soiling.
  • the treated samples are removed and the amount of soil present on a given sample is determined using colorimetric measurements, making the assumption that the amount of soil on a given sample is directly proportional to the difference in color between the unsoiled sample and the corresponding sample after soiling.
  • the three CIE L*a*b* color coordinates of the unsoiled and subsequently soiled samples are measured using a Minolta 310 Chroma Meter with a D65 illumination source.
  • the color difference value, ⁇ E is calculated using the equation shown below:
  • ⁇ E [( ⁇ L*) 2 + ( ⁇ a*) 2 + ( ⁇ b*) 2 ] ⁇ 2
  • the Receding Contact Angle Test provides a quick and precise prediction of the anti-soiling potential of treated nylon ca ⁇ et. Receding contact angle values measured with H-hexadecane using this test have correlated well with anti- soiling values measured from actual foot traffic using the "Walk-On" Soiling Test.
  • nylon film is prepared as follows. Nylon film is cut into 85 mm x 13 mm rectangular strips. Each strip is cleaned by dipping into methyl alcohol, wiping with a KimwipeTM wiper
  • the strip is immersed in the treating solution, and the strip is then withdrawn slowly and smoothly from the solution.
  • the coated film strip is tilted to allow any solution run-off to accumulate at the corner of the strip, and a KimwipeTM tissue is touched to the corner to pull away the solution buildup.
  • the coated film strip is allowed to air dry in a protected location for a minimum of 30 minutes and then is cured for 10 minutes at 121 °C.
  • n-hexadecane is applied to the treated film and the receding contact angle of the drop of is measured using a CAHN Dynamic Contact Angle Analyzer, Model DCA 322 (a Wilhelmy balance apparatus equipped with a computer for control and data processing, commercially available from ATI, Madison, Wisconsin).
  • the CAITN Dynamic Contact Angle Analyzer is calibrated using a 500 mg weight. An alligator clip is fastened to a piece of coated film strip about 30 mm long, and the clip and film piece are hung from the stirrup of the balance.
  • a 30 mL glass beaker containing approximately 25 mL of «-hexadecane is placed under the balance stirrup, and the beaker is positioned so that the coated film strip is centered over the beaker and its contents but not touching the walls of the beaker.
  • the platform supporting the beaker is carefully raised until the surface of «-hexadecane is 2-3 mm from the lower edge of the film strip.
  • the door to the apparatus is closed, the "Configure” option is chosen from the "Initialize” menu of the computer, the "Automatic” option is chosen from the "Experiment” menu, and the computer program then calculates the time for a total of 3 scans.
  • the result should be a time interval of 1 second and estimated total time of 5 minutes, which are the acceptable settings to show the baseline weight of the sample.
  • the Return Key is then pressed to begin the automatic measurement cycle. 10 readings of the baseline are taken before the scan begins. The apparatus then raises and lowers the liquid so that 3 scans are taken. The "Least Squares" option is then selected from the "Analysis” menu, and the average receding contact angle is calculated from the 3 scans of the film sample.
  • the 95% confidence interval for the average of the 3 scans is typically about ⁇ 1.2°.
  • the level (%> SOF) of either fluorochemical material (F-10) or hydrocarbon material (H-l) required for optimum performance was determined using the Simulated Flex-Nip Coapplication Procedure.
  • the aqueous acidic treating bath was adjusted to apply 0.6% SOF of stainblocking material S-1 and 1.0% SOF of MgSO 4 to Wolf-Laurel Nylon 6 ca ⁇ et.
  • no F-10 or H-l was used.
  • Measured ca ⁇ et performance properties of soil resistance, water repellency, oil repellency, dynamic water repellency and stain resistance are presented in Table 3.
  • Hybrid fluorochemical materials FH-1, FH-2, FH-3 and FH-4 were compared in performance to their non-hybrid analogues, fluorochemical material F-18 and hydrocarbon material H-4A.
  • the various repellent materials were coapplied at a total level of 0.15% SOF with stainblocking material S-1 at 0.6% SOF to Wolf- Laurel nylon 6 ca ⁇ et.
  • the MgSO 4 level was kept at 1.0% SOF throughout the study. Results from this study are presented in Table 5. (Examples 21 and 26, representing 100%) fluorochemical moieties and 100%) hydrocarbon moieties, respectively, were included from Table 4.)
  • Repellent Material Soiling, Water Oil Dyn. Staining.
  • the level (% SOF) of magnesium sulfate required to provide optimum performance in a flex-nip-applied coapplication formulation was determined.
  • the Simulated Flex-Nip Coapplication Procedure was used to apply 0.15% SOF of fluorochemical material F-10 and 0.6% SOF of stainblocking material S-1 to Wolf-Laurel nylon 6 ca ⁇ et, with treating solution pH adjusted to 2 using sulfamic acid.
  • Results showing the effect of magnesium sulfate level on ca ⁇ et water repellency, oil repellency, dynamic water repellency and stain resistance are presented in Table 6.
  • FIGS. 2-5 are micrographs which illustrate the effects of the concentration of magnesium salt on treatment process of the present invention.
  • the concentration of magnesium salt used in the treatment method is too small. Consequently, there is little or no exhaustion of the fluorochemical onto the fiber, resulting in poor water repellency and no oil repellency.
  • FIG. 2 which corresponds to Example 31, the concentration of magnesium salt used in the treatment method is too small. Consequently, there is little or no exhaustion of the fluorochemical onto the fiber, resulting in poor water repellency and no oil repellency.
  • the concentration of magnesium salt is too high, resulting in coagulation of the fluorochemical. This causes a decrease in the dynamic water repellency and slightly less than optimal oil repellency.
  • the concentration of magnesium salt is optimal, resulting in even exhaustion of the fluorochemical onto the fiber surface and optimal performance characteristics.
  • FIG. 5 is a micrograph of a hydrocarbon (H-l) which was exhausted under conditions similar to those for Example 35. As in Example 35, an even coating of hydrocarbon was achieved on the fiber surface, and good performance characteristics were observed.
  • FIG. 6 is a micrograph of a ca ⁇ et treated by a typical spray application process. Upon comparison to FIGS. 4-5, it is apparent that ca ⁇ et fibers treated in accordance with the method of the present invention are coated more evenly, and thus exhibit better antisoiling properties, than ca ⁇ ets treated by a spray application method.
  • the pH required to provide optimum performance in flex-nip-applied fluorochemical or hydrocarbon material-containing coapplication formulations was determined in the absence of a salt.
  • the Simulated Flex- Nip Coapplication Procedure was used to co-apply 0.15% SOF of fluorochemical material F-10 or 0.15 % SOF of hydrocarbon material H-l with 0.6% SOF of stainblocking material S-1 to Wolf-Laurel nylon 6 ca ⁇ et.
  • Stinblocking material was applied.
  • the treating solution was adjusted to various pH values using sulfamic acid. Results showing the effect of pH on ca ⁇ et water repellency, oil repellency, dynamic water repellency and stain resistance are presented in Table 7.
  • the pH required to provide optimum performance in flex-nip-applied fluorochemical or hydrocarbon material-containing coapplication formulations was determined in the presence of magnesium sulfate.
  • the Simulated Flex-Nip Coapplication Procedure was used to co-apply 0.15% SOF of fluorochemical material F-10 or 0.15% SOF of hydrocarbon material H-l with 0.6% SOF of stainblocking material S-1 and 1.0% SOF of MgSO 4 to Wolf-Laurel nylon 6 ca ⁇ et.
  • the treating solution was adjusted to various pH values using sulfamic acid. Results showing the effect of pH on ca ⁇ et water repellency, oil repellency and dynamic water repellency are presented in Table 8. Also presented in Table 8 for Examples 49-59 is the parts per million of fluorine detected on each treated ca ⁇ et as determined using the Fluorine Analysis Combustion Test.
  • the dynamic repellency which is a measure of the instantaneous abso ⁇ tion of water by the substrate, increases more slowly as a function of decreasing pH when a salt (MgSO 4 ) is used than when no salt is used.
  • pH has a lesser effect on dynamic repellency in the process of the present invention when a salt is used.
  • the data also indicate that, at a given pH, the presence of salt improves the dynamic repellency across the board. For materials with good repellency properties, improved dynamic repellency is indicative of improved (e.g., more uniform) application of the fluorochemical or hydrocarbon to the substrate.
  • the presence of a salt improves the application of the fluorochemical or hydrocarbon to the substrate.
  • the improvement in application to the substrate would be expected to impart better antisoiling properties.
  • the level (% SOF) of stainblocking material required to provide optimum performance in a flex-nip-applied coapplication formulation was determined.
  • the Simulated Flex-Nip Coapplication Procedure was used to apply the designated %> SOF of stainblocking material S-1, 0.15%) SOF of fluorochemical material F-10 and 1.0% SOF of MgSO 4 to Wolf-Laurel nylon 6 ca ⁇ et, with treating solution pH adjusted to 2 using sulfamic acid.
  • Results showing the effect of stainblocking material level on ca ⁇ et water repellency, oil repellency, dynamic water repellency and stain resistance on ca ⁇ et are presented in Table 9. Table 9
  • fluorochemical material F-8 was spray applied to the hydrocarbon material-treated ca ⁇ et at theoretical fluorine level of either 250 or 500 ppm. Then the treated ca ⁇ et was subjected to one cycle of the "Walk-On" Soiling Test.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatment Of Fiber Materials (AREA)

Abstract

L'invention concerne un traitement conférant aux tapis d'excellentes propriétés anti-taches, anti-salissures et hydrofuges. Ce traitememt comprend un procédé par épuisement à base d'eau, la solution aqueuse contenant ce qui suit: (1) un composé fluoré vitreux, un hydrocarbure vitreux ou leurs combinaisons; (2) une substance anti-taches; (3) un sel métallique polyvalent, un acide ou leurs combinaisons; et (4) de l'eau. Après ce procédé par épuisement, le tapis humide est chauffé, généralement à un stade de vaporisage, puis rincé et séché dans un four à chaleur sèche.
PCT/US1998/008211 1997-05-05 1998-04-20 Traitement de substrats fibreux visant a leur conferer des proprietes hydrofuges, anti-taches et anti-salissures WO1998050619A1 (fr)

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CA2287494A CA2287494C (fr) 1997-05-05 1998-04-20 Traitement de substrats fibreux visant a leur conferer des proprietes hydrofuges, anti-taches et anti-salissures
JP54813598A JP2001526739A (ja) 1997-05-05 1998-04-20 忌避性、耐着色性、および防汚性を付与する繊維基材処理
EP98918639A EP0980449B1 (fr) 1997-05-05 1998-04-20 Traitement de substrats fibreux visant a leur conferer des proprietes hydrofuges, anti-taches et anti-salissures
AU71526/98A AU736286B2 (en) 1997-05-05 1998-04-20 Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance
BR9808724-0A BR9808724A (pt) 1997-05-05 1998-04-20 Processo para tratar um substrato fibroso

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Cited By (13)

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WO1999057361A1 (fr) * 1998-04-30 1999-11-11 Minnesota Mining And Manufacturing Company Traitement de substrats fibreux pour conferer des proprietes a effet anti-mouillant, anti-tache et anti-salissure aux tapis
US6472019B1 (en) 2001-03-13 2002-10-29 Daikin Industries, Inc. Water- and oil-repellent treatment of textile
US6482911B1 (en) 2001-05-08 2002-11-19 3M Innovative Properties Company Fluoroalkyl polymers containing a cationogenic segment
US6740357B2 (en) 2001-12-25 2004-05-25 Daikin Industries, Ltd. Water-and oil-repellent treatment of textile
US6833082B2 (en) 2001-01-31 2004-12-21 Daikin Industries, Ltd. Stain block treatment of textile
US6939580B2 (en) 2000-03-30 2005-09-06 Daikin Industries, Ltd. Water- and oil-repellent treatment of textile
US7147669B2 (en) 2001-04-25 2006-12-12 Daikin Industries, Ltd. Water- and oil-repellent treatment of textile
US7521410B2 (en) 2004-03-26 2009-04-21 Arrowstar, Llc Compositions and methods for imparting odor resistance and articles thereof
WO2009119910A1 (fr) * 2008-03-28 2009-10-01 Daikin Industries, Ltd. Traitement comprenant un agent à pouvoir hydrofuge et oléofuge
US7678155B2 (en) 2003-04-08 2010-03-16 Daikin Industries, Ltd. Water- and oil-repellent treatment of textile
US7758656B2 (en) 2000-04-20 2010-07-20 Daikin Industries, Ltd. Water-and-oil repellent treatment of textile
EP2638195A4 (fr) * 2010-11-12 2015-08-26 Invista Technologies Srl Formulations antisalissures à pulvériser destinées aux fibres, tapis et tissus
US9945069B2 (en) 2006-10-20 2018-04-17 Daikin Industries, Ltd. Treatment comprising water- and oil-repellent agent

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US20070136953A1 (en) * 2005-12-20 2007-06-21 Materniak Joyce M Stability for coapplication
NZ610055A (en) * 2010-11-12 2015-09-25 Invista Technologies Sarl Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet
CN104711699A (zh) * 2015-03-17 2015-06-17 太仓环球化纤有限公司 一种抗污型尼龙膨体长丝及其生产工艺

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6197378B1 (en) 1997-05-05 2001-03-06 3M Innovative Properties Company Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance
US6613862B2 (en) 1998-04-30 2003-09-02 3M Innovative Properties Company Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance
WO1999057361A1 (fr) * 1998-04-30 1999-11-11 Minnesota Mining And Manufacturing Company Traitement de substrats fibreux pour conferer des proprietes a effet anti-mouillant, anti-tache et anti-salissure aux tapis
US6939580B2 (en) 2000-03-30 2005-09-06 Daikin Industries, Ltd. Water- and oil-repellent treatment of textile
US7758656B2 (en) 2000-04-20 2010-07-20 Daikin Industries, Ltd. Water-and-oil repellent treatment of textile
US6833082B2 (en) 2001-01-31 2004-12-21 Daikin Industries, Ltd. Stain block treatment of textile
US6472019B1 (en) 2001-03-13 2002-10-29 Daikin Industries, Inc. Water- and oil-repellent treatment of textile
US7147669B2 (en) 2001-04-25 2006-12-12 Daikin Industries, Ltd. Water- and oil-repellent treatment of textile
US7717963B2 (en) 2001-04-25 2010-05-18 Daikin Industries Ltd. Water- and oil-repellent treatment of textile
US6482911B1 (en) 2001-05-08 2002-11-19 3M Innovative Properties Company Fluoroalkyl polymers containing a cationogenic segment
US6740357B2 (en) 2001-12-25 2004-05-25 Daikin Industries, Ltd. Water-and oil-repellent treatment of textile
US7678155B2 (en) 2003-04-08 2010-03-16 Daikin Industries, Ltd. Water- and oil-repellent treatment of textile
US7521410B2 (en) 2004-03-26 2009-04-21 Arrowstar, Llc Compositions and methods for imparting odor resistance and articles thereof
US9945069B2 (en) 2006-10-20 2018-04-17 Daikin Industries, Ltd. Treatment comprising water- and oil-repellent agent
WO2009119910A1 (fr) * 2008-03-28 2009-10-01 Daikin Industries, Ltd. Traitement comprenant un agent à pouvoir hydrofuge et oléofuge
EP2638195A4 (fr) * 2010-11-12 2015-08-26 Invista Technologies Srl Formulations antisalissures à pulvériser destinées aux fibres, tapis et tissus

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AU7152698A (en) 1998-11-27
EP0980449B1 (fr) 2011-05-25
EP0980449A1 (fr) 2000-02-23
CA2287494A1 (fr) 1998-11-12
BR9808724A (pt) 2000-07-11
CA2287494C (fr) 2011-11-01
CN1141439C (zh) 2004-03-10
AU736286B2 (en) 2001-07-26
CN1255173A (zh) 2000-05-31
JP2001526739A (ja) 2001-12-18

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