+

WO1992018569A1 - Fibres resistant aux impuretes - Google Patents

Fibres resistant aux impuretes Download PDF

Info

Publication number
WO1992018569A1
WO1992018569A1 PCT/US1992/002826 US9202826W WO9218569A1 WO 1992018569 A1 WO1992018569 A1 WO 1992018569A1 US 9202826 W US9202826 W US 9202826W WO 9218569 A1 WO9218569 A1 WO 9218569A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorochemical
core
inner core
polypropylene
outer core
Prior art date
Application number
PCT/US1992/002826
Other languages
English (en)
Inventor
Ralph R. Sargent
Original Assignee
Peach State Labs, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Peach State Labs, Inc. filed Critical Peach State Labs, Inc.
Priority to JP4510037A priority Critical patent/JPH06506714A/ja
Publication of WO1992018569A1 publication Critical patent/WO1992018569A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

Definitions

  • This invention is in the area of fiber technology, and in particular relates to carpet and textile fibrous compositions prepared by melt extrusion of a polymer with a fluorochemical. Also described are polymeric articles, including thin film and molded objects prepared from polymeric compositions that have a fluorochemical dispersed throughout a polymer.
  • carpet and textile fibers are easily soiled and stained in everyday use.
  • the problem of fiber soiling has become more difficult with the advent of synthetic fibers such as polypropylene, polyamide, polyethylene, and polyester, that are substantially more oleophilic (oil-loving) than traditional natural fibers such as cotton and wool.
  • Soil found on fibers can include a variety of solid particles, such as fly ash or other inorganic particulates; liquids, such as oils and greases; mixtures of solids and liquids, such as soot (that contain particles mixed with oily components); and biological matter such as skin cells and sebum.
  • solid particles such as fly ash or other inorganic particulates
  • liquids such as oils and greases
  • soot that contain particles mixed with oily components
  • biological matter such as skin cells and sebum.
  • Soil typically adheres to the fiber surface by Van der Waals forces, that are effective only over very short distances.
  • the strength of the bond depends on the forces of interaction per unit interfacial area, the area of contact, and whether a liquid is present on the fiber surface. Oily films on the fiber increase soiling. In general, the higher the viscosity of the liquid, the greater the adhesion of the liquid to the fiber. Soil particles can even adhere to initially smooth surfaces, such as polyester and polyethylene film. Soil is not commonly mechanically entrapped in the fiber.
  • Staining of a fiber can occur in a wide variety of ways, including through the ionic or covalent binding of an exogenous colored substance to the fiber.
  • nylon fibers are polya ides with terminal amino and carboxyl end groups.
  • Nylon is commonly stained by acid dyes, which are colored, negatively charged molecules that ionically bind to the protonated terminal amine.
  • staining acid dyes include liquids containing FD&C Red Dye No. 4, wine, and mustard.
  • soil (as opposed to stain) resistance has been imparted to carpet and textile fibers by applying a finish that repels oil and water. Perhaps the first soil resist agent for fibers was starch, that was removed along with the soil when the fiber was washed.
  • Vinyl polymers including acrylics, methacrylics and polymers of maleic acid have also been used as soil release agents.
  • One of the first patents in this area was U.S. Patent No. 3,377,249, issued in 1969 and assigned to Deering Mil ⁇ ken, disclosing and claiming emulsions of copolymers of ethyl acrylate with at least 20% acrylic, methacrylic, or itaconic acid in combination with N-methylol acrylamide.
  • fluorochemical soil release agents have become very popular.
  • the fluorochemical agents are coated onto the fiber to prevent wetting of the surface by minimizing chemical contact between the surface and substances that can soil the carpet, making the substance easier to remove.
  • the first fluorochemical finishes focused on reducing the surface energy of the fiber to prevent the spreading of oily soils. More recently developed fluorochemical finishes have attempted to combine reduction in surface energy with hydrophilicity, as described in U.S. Patent No. 3,728,151. Increased hydrophilicity facilitates the removal of the soil or staining material during washing. Hydrophilic moieties in soil resist finishes include a number of hydrogen bonding groups, including polyalkylene glycols.
  • a number of patents describe fluorinated polymers for use as soil resist coatings for fibers, including U.S. Patent No. 3,759,874 (describing polyurethanes that consist of a combination of an oleophilic fluorine- containing block and a hydrophilic polyethyleneoxide block) and U.S. Patent No. 4,046,944 (describing a fluorinated condensation block copolymer, that include oleophilic fluorinated blocks and hydrophilic polyethyleneoxide blocks connected by urea linkages).
  • Fluorochemical coatings have been used extensively on carpet fibers, either alone (Antron PlusTM carpet manufactured by E. I. DuPont Nemours and Company), or in combination with an acid dye stain resistant polymeric formulation that includes a sulfonated aromatic formaldehyde condensation polymer.
  • Examples of commercially available fluorochemical coatings for carpet fibers include ScotchgardTM 358 and 352 (Minnesota Mining & Mfg. Co.), ZonylTM 5180 Fluorochemical dispersion, and Teflon Tuft Coat Anionic (E.I. Du Pont de Nemours and Company, Inc.).
  • ZonylTM 5180 is an aqueous fluorochemical dispersion containing a 1-10% polyfunctional perfluoroalkyl ester mixture, 10-20% polymethylmethacrylate, and 70-75% water.
  • Teflon Tuftcoat Anionic contains 5-10% perfluoroalkyl substituted urethanes, 1-5 % polyfunctional perfluoroalkyl esters, and 85-90% water.
  • fluorinated finishing coats on fibers do impart an amount of soil resistance to the fiber, they all suffer from the distinct disadvantage that they are removed by routine maintenance of the fiber. None of the fluorochemical finishes available to date provides permanent protection from soiling and staining. This is a particular problem for polypropylene, that is very oleophilic, and that has begun to compete with nylon as a fiber for use in residential carpets.
  • Permanently soil resistant polymeric compositions are prepared by extruding an appropriate polymer, copolymer, or polymer mixture, in combination with a fluorochemical, to produce a fiber that has the fluorochemical dispersed throughout the filament. Fibers produced in this manner have a decreased surface energy and thus decreased tendency to adhere to soiling agents. The fluorochemical is intricately bound with the polymer, imparting to it permanent soil resisting properties.
  • Any polymer, copolymer, or polymer mixture that can be extruded with the desired fluorochemical can be used to prepare the soil resistant fiber.
  • Preferred polymers for melt extrusion are polypropylene, nylon 6, polyester, and polyethylene, or mixtures of these.
  • a preferred fluorochemical is Zonyl FTS Fluorotelomer 5822APP marketed by E. I. Du Pont Nemours and Company.
  • the polymer chip and fluorochemical are blended in a rotary drum dry blender.
  • the blended chips are then poured into a feed hopper, and extruded through a heated temperature chamber and spinneret to form monofilament that is chipped or flaked to an appropriate size.
  • the chips or flakes are then shaped as desired, or extruded into fiber.
  • the polymer fluorochemical chips are blended with other polymer chips that do not contain fluorochemical, and the blend is then extruded to form objects or fibers of a desired size.
  • the polymer in the chip or flake can be the same as or different than the polymer that is later mixed with the chip or flake.
  • the polymer/fluorochemical chips can also be used to coat a polymer fiber to improve its properties.
  • nylon 6 such as polycaprolactam
  • nylon 6 can be coated with a polyester or polypropylene that has a fluorochemical dispersed in it to impart soil resisting properties to the nylon.
  • Thin films of polymer with fluorochemical dispersed in the film can also be prepared that have superior antiwetting properties. These films can be coated with an adhesive shortly after preparation without the need to extensively dry the film.
  • Polypropylene fibers prepared as described herein can be used in residential or commercial carpet to provide a long lasting, durable carpet with permanent soil resistance and low flammability.
  • Polymeric compositions that are permanently soil resistant are prepared that have fluorochemical dispersed throughout the polymer.
  • Caipet and textile fibers prepared in this way have reduced surface energy and low static properties relative to the fiber without the fluorochemical.
  • the fibers represent a significant advance in fiber and textile technology, in that the fluorochemical is dispersed throughout the polymer instead of coated onto the fiber, and is not removed from the fiber on washing.
  • the dispersion of the fluorochemical in the polymer improves characteristics of the polymer other than soil resistance.
  • polypropylene fibers that are extruded without a fluorochemical are highly static.
  • Antistatic agents must be applied to the fiber after extrusion to keep the fiber from breaking or static clinging during later processing steps.
  • the antistatic agents must be removed from the fiber by scouring after the fiber is tufted because they can increase the tendency of the fiber to soil on use. This process is cumbersome and increases the cost of the fiber.
  • Polymers, and in particular polypropylene fibers, extruded with a fluorochemical do not require antistatic agents to facilitate handling, because they have inherently low static energy.
  • Fluorochemicals also impart antiwetting characteristics to polymers that are useful for a number of applications.
  • the fluorochemical can be extruded with a polymer into a thin film that repels water. This is particularly useful for certain manufacturing procedures that require a dry film for the application, for example, addition of an adhesive to a recently extruded film. Dispersion of the fluorochemical into the polymer also decreases the flammabihty and alters the combustion characteristics of the polymer.
  • copolymer as used herein includes polymers formed by the polymerization of at least two different monomers; a monomer and a polymer; or two or more polymers or oligomers.
  • polymer as used herein includes copolymers and mixtures of polymers.
  • Any polymer, copolymer, or mixture of polymers is suitable for use in the soil resistant fiber that can be melt extruded and that is compatible with the desired fluorochemical.
  • Common polymers that are typically melt extruded include nylon 6, polyester, polypropylene, and polyethylene.
  • a polymer should be selected that, when combined with the fluorochemical, has an appropriate viscosity and shear rate on extrusion. It should solidify within a reasonable time to a filament with appropriate characteristics for the desired function, including tensile strength (strain), elongation (stress), modulus, crystallinity, glass transition temperature, and melt temperature. These characteristics can be measured by known methods.
  • fluorochemical refers to an organic nonpolymeric compound in which more than two of the hydrogens atoms attached directly to carbon have been replaced with fluorine, or an organic polymeric compound in which at least one hydrogen attached to a carbon in a monomer used to prepare the polymer or copolymer is replaced with fluorine.
  • Fluorochemicals are sometimes also called fluorocarbons or fluorocarbon polymers. Fluorochemicals can include other halogen atoms bound to carbon, notably chlorine.
  • Fluorochemicals are typically more dense and more volatile than the corresponding hydrocarbons and have lower refractive indices, lower dielectric constants, lower solubilities, and lower surface tensions than the corresponding nonfluorinated compound or polymer.
  • the fluorochemical selected for extrusion with the polymer can be perfluorinated, wherein all of the hydrogens are replaced with fluorine atoms, or semifluorinated, wherein two or more, but not all, of the hydrogens are replaced with fluorine.
  • Suitable fluorochemicals for use in preparation of the soil resistant fibers are small molecules, oligomers, or polymers, or mixtures of these.
  • the fluorochemical can be added to the mechanical blender in a solid or liquid form.
  • the fluorochemical or mixture of fluorochemicals that is selected should not include any moiety that reacts adversely or degrades on extrusion.
  • the fluorochemical must also be compatible with, and not adversely react with, functional or functionalized moieties in the polymer extruded with the fluorochemical.
  • the fluorochemical extruded with the polymer can be homogeneous or can include a mixture of semifluorinated compounds, perfluorinated compounds, or both semifluorinated and perfluorinated compounds.
  • the types of functional groups that can be included in the fluorochemical will depend on the temperature of extrusion, length of time that the material is heated in the extruder, and presence of other components in the extruded material.
  • Nonlimiting examples of functional or functionalized moieties that may be included in the fluorochemical for use under the proper conditions include alcohols, glycols, ketones, aldehydes, ethers, esters, amides, acids, acrylates, urethanes, ureas, alkanes, alkenes, alkynes, aromatics, heteroaromatics, and nitriles.
  • fluorocarbon hydrocarbon polymers including polytetrafluoroethylene, polymers of chlorotrifluoroethylene, fluorinated ethylene-propylene polymers, polyvinylidene fluoride, and poly(hexafluoropropylene).
  • fluorochemicals are available commercially, many from E.I. Du Pont Nemours and Company, Wilmington, Delaware.
  • Zonyl FTS Fluorotelomer 5823 APP A preferred fluorochemical marketed by Du Pont is Zonyl FTS Fluorotelomer 5823 APP, that includes 85-90% perfluoroalkylstearate ((a-fluoro-w-[2-[(l -oxooctadecyl)oxy]ethyl]- poly(difluoromethylene) CAS 65530-65-6); 1-5% fluorinated alcohol mixture (CAS 112-61-8), and 5-10% methyl stearate.
  • Zonyl FTS is a waxy, light brown solid with a melting point between 30 and 45 °C.
  • fluorochemicals that can be used include those that are now used commercially in fluorochemicals coatings, including ScotchgardTM 358 and 352 (Minnesota Mining & Mfg. Co.), ZonylTM 5180 Fluorochemical dispersion, and Teflon Tuft Coat Anionic (E.I. Du Pont de Nemours and Company, Inc.).
  • ZonylTM 5180 is an aqueous fluorochemical dispersion containing a 1-10% polyfunctional perfluoroalkyl ester mixture, 10-20% polymethylmethacrylate, and 70-75% water.
  • Teflon Tuftcoat Anionic contains 5-10% perfluoroalkyl substituted urethanes, 1-5% polyfunctional perfluoroalkyl esters, and 85-90% water.
  • the fluorochemical is obtained as a water based emulsion
  • the emulsifiers and water should be removed before the fluorochemical is added to the blender with the polymer.
  • Extrusion is a process for making continuous-filament synthetic polymeric forms by forcing a polymer through minute holes of a spinneret with a rotating screw.
  • the polymeric composition can be extruded in a thick form and cut into chips or flakes, or extruded in a thin form for use as carpet or textile fiber. Fiber extrusion is often referred to as "spinning" in the industry.
  • the fiber is prepared in a melt spin process, wherein the fiber-forming substance is melted and then extruded through the spinneret into a gas (such as air), or a liquid, to cool and solidify the fiber.
  • a gas such as air
  • Polypropylene, polyethylene, polyamide (nylon), and polyester (for example, Dacron, Terylene, and Vycron) fibers are prepared in this way.
  • the fluorochemical can be extruded neat with the melted polymer. It is important in using this process to choose a polymer that has a melting temperature below that at which the fluorochemical that is extruded with it degrades or reacts.
  • Polypropylene used for continuous filament fiber typically melts at approximately 300 °F.
  • Nylon is typically extruded at a temperature of approximately 490 °F.
  • the melt or degradation temperature of the fluorochemical to be used can be determined easily by known methods.
  • chips or flakes of a desired polymer and fluorochemical are initially prepared by known methods, typically in a dual screw (such as a Farrell) or single screw (such as a Mackie, Barmag, Filtecho, Plantex, Hills Reacher, or Neumag) device.
  • the chips can be used as an additive in a manufacture of wide variety of polymeric articles, including thin film, and thermoplastic or thermoset objects. Alternatively, the chips can be extruded into fiber.
  • the polymer/ fluorochemical chip should be prepared in appropriate size to be used in the desired extrusion, molding, or other equipment.
  • the polymer fluorochemical chips are used in a polymer extrusion feedstock along with chips or flakes of the same or a different polymer to produce a soil resistant fiber.
  • chips can be prepared from nylon and a fluorochemical, and then extruded in combination with polypropylene chips.
  • Soil resistant fibers can also be prepared by thin core coextrusion, that involves the extrusion of an inner core of a polymer with an outer core of a polymer that has fluorochemical embedded in it. Machinery appropriate for thin-core coextrusion is available from Hills Research Corporation in Florida. For durability, an inner polymer core should be chosen that adheres sufficiently to the outer soil resistant polymeric composition. Thin core coextrusion can be used to prepare a wide variety of fibers for varying applications at varying costs. For example, a less expensive polymer can be used as an inner core of the fiber, and the desired polymer with fluorochemical soil protection as the outer core. Alternatively, a soil resistant fiber can be strengthened with a strong inner polymer core.
  • Nonlimiting examples include fibers prepared by coextruding a polypropylene inner core with a polyamide/fluorochemical outer core, a polyamide inner core with a polypropylene/fluorochemical outer core, a polyethylene inner core with a polypropylene/fluorochemical outer core, a polypropylene inner core with a polyethylene/fluorochemical outer core, a polyethylene inner core with a polyamide/fluorochemical outer core, a polyamide inner core with a polyethylene/fluorochemical outer core, a polyester inner core with a polyamide/fluorochemical outer core, a polyamide inner core with a polyester/fluorochemical outer core, a polyethylene inner core and a polyester/fluorochemical outer core, a polypropylene inner core and a polyester/fluorochemical outer core, a polyester inner core and a polyethylene/fluorochemical outer core, a polyester inner core and a polypropylene/fluorochemical outer core, a polyester inner core and a
  • the ratio of polymer to fluorochemical in the chip will vary based on the end use of the chip. In general, if the chip is to be extruded into fiber or made into an article without addition of other polymer chip in the final feedstock, less fluorochemical will be used than if the fluorochemical chip is later diluted with other polymer in the fiber or article formation.
  • a ratio of fluorochemical to polymer should be used that produces a chip with the desired characteristics of melting temperature, strength, processability, soil resistance, and antistatic properties. These characteristics can be measured easily by one skilled in the art of polymer technology.
  • the ratio of polymer to fluorochemical in the chip ranges from 1 :1 to 1000:1 , and more preferably from 20:1 to 1 :1 , for melt extrusion.
  • a feeder chip is prepared with approximately 1 part by weight of fluorochemical to 9 parts by weight of polymer.
  • the 9:1 polymer/fluorochemical chip is then coextruded with polymer chip in a 1 : 1 weightrweight ratio to form a final product with the desired characteristics.
  • the temperature of extrusion will vary depending on the polymer and fluorochemical used in the process. Typical extrusion temperatures vary from 100 °F to 800 °F, however, extrusion temperatures outside this range may be required in certain processes.
  • the fiber denier will also vary depending on the product being prepared, and are typically within the range of 1 to 50,000. Carpet fibers typically range from 900 denier to 8000 denier.
  • a wide variety of textile treatment chemicals can be added to the extrusion process to improve the properties of the product.
  • examples include antioxidants, flame retardants, ultra-violet absorbers, dyes or coloring agents, and microbiocidal agents, including antibacterial agents, antifungals, and antialgals.
  • Any commercially available textile treatment chemical that does not degrade or adversely react in the extrusion process is appropriate.
  • Commercially available flame retardants include alumina trihydrate, calcium carbonate, magnesium carbonate, barium carbonate, metal oxides, borates, sulfonates, and phosphates.
  • Example 1 The procedure of Example 1 is repeated using nylon 6 in place of polypropylene.
  • Polypropylene Zonyl FTS chips prepared as in Example 1 are fed into a single screw extrusion apparatus, passed through a cooling chamber and around heated rollers. The fiber is then passed through forced air and wound onto a cone.
  • Example 3 The procedure of Example 3 is followed with the exception that nylon chips and polypropylene Zonyl FTS chips are used as the feed stock in a 1:1 by weight ratio.
  • Polypropylene chips are fed into a single screw extrusion apparatus manufactured by Hills Research Corporation, and then passed through a solution chamber that includes nylon 6 and Zonyl FTS.
  • the coated fiber is then quenched in a cooling chamber and pulled around heated rollers.
  • the fiber is then passed through forced air and wound onto a cone.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Glass Compositions (AREA)
  • Road Paving Structures (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Artificial Filaments (AREA)
  • Multicomponent Fibers (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

Compositions polymères résistant aux impuretés de façon permanente et contenant un produit chimique fluoré en dispersion dans le polymère. Lesdites compositions sont préparées par extrusion à chaud du produit chimique fluoré avec le polymère souhaité. Les polymères préférés pour l'extrusion avec le produit chimique fluoré sont le polyester, le polypropylène, le polyéthylène et le polyamide.
PCT/US1992/002826 1991-04-11 1992-04-07 Fibres resistant aux impuretes WO1992018569A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4510037A JPH06506714A (ja) 1991-04-11 1992-04-07 耐汚れ性繊維

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68391591A 1991-04-11 1991-04-11
US683,915 1991-04-11

Publications (1)

Publication Number Publication Date
WO1992018569A1 true WO1992018569A1 (fr) 1992-10-29

Family

ID=24745991

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/002826 WO1992018569A1 (fr) 1991-04-11 1992-04-07 Fibres resistant aux impuretes

Country Status (5)

Country Link
EP (1) EP0585312A4 (fr)
JP (1) JPH06506714A (fr)
AU (1) AU1771492A (fr)
CA (1) CA2107777A1 (fr)
WO (1) WO1992018569A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592884A1 (fr) * 1992-09-30 1994-04-20 Minnesota Mining And Manufacturing Company Composition contenant un polymère thermoplastique et un derivé fluoré de pipérazine
EP0599023A3 (fr) * 1992-09-30 1994-11-23 Minnesota Mining & Mfg Aminoalcools fluorochimiques.
EP0708799A4 (fr) * 1993-06-30 1996-10-09 Peach State Labs Inc Fibres resistantes aux salissures
WO1997022660A1 (fr) * 1995-12-21 1997-06-26 E.I. Du Pont De Nemours And Company Sulfone fluore comme additif fondu pour des polymeres thermoplastiques
US5661206A (en) * 1993-06-11 1997-08-26 Mbt Holding Ag Fluidity control of cementitious compositions
WO1997033019A1 (fr) * 1996-03-07 1997-09-12 Minnesota Mining And Manufacturing Company Fil pour moquette ayant une grande resistance aux salissures
US5681963A (en) * 1995-12-21 1997-10-28 E. I. Du Pont De Nemours And Company Fluorinated melt additives for thermoplastic polymers
US5977390A (en) * 1995-12-21 1999-11-02 E. I. Du Pont De Nemours And Company Fluorinated diester melt additives for thermoplastic polymers
US6063474A (en) * 1995-12-21 2000-05-16 E. I. Du Pont De Nemours And Company Fluorinated ester melt additives for thermoplastic fibers
US6426025B1 (en) 1997-05-12 2002-07-30 3M Innovative Properties Company Process for extruding fibers
US6476114B2 (en) 1997-11-19 2002-11-05 3M Innovative Properties Company Thermoplastic polymer film comprising a fluorochemical compound
WO2006019526A1 (fr) 2004-07-15 2006-02-23 3M Innovative Properties Company Libération adhésive d'agents oléofuges et hydrofuges
WO2006021529A1 (fr) * 2004-08-25 2006-03-02 Ciba Specialty Chemicals Holding Inc. Modificateurs de surface
US7230043B2 (en) 2004-09-07 2007-06-12 3M Innovative Properties Company Hydrophilic polymer composition
US20100090182A1 (en) * 2006-06-15 2010-04-15 Ian Robert Tooley Uv Absorbing Composition
US20100264383A1 (en) * 2006-06-15 2010-10-21 Croda International Plc Uv Absorbing Composition
WO2016179384A1 (fr) * 2015-05-05 2016-11-10 Invista Technologies S.Ar.L. Fibres synthétiques ayant une résistance accrue à la salissure, procédés de production et utilisation
CN107075191A (zh) * 2014-08-20 2017-08-18 英威达技术有限公司 具有增强的耐污性的合成纤维及其制备方法
US9777407B2 (en) 2009-03-27 2017-10-03 3M Innovative Properties Company Hydrophilic polyproylene melt additives

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU643386B2 (en) * 1988-08-30 1993-11-11 E.I. Du Pont De Nemours And Company Non-ozone depleting halocarbons for flash-spinning polymeric plexifilaments

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3005795A (en) * 1957-12-10 1961-10-24 Du Pont Thermoplastic resins containing finely divided, fibrous polytetrafluoroethylene
US3679541A (en) * 1969-07-28 1972-07-25 Ici Ltd Sheath/core bicomponent filaments and process of preparing same
US4251200A (en) * 1978-11-30 1981-02-17 Imperial Chemical Industries Limited Apparatus for spinning bicomponent filaments
US4818587A (en) * 1986-10-17 1989-04-04 Chisso Corporation Nonwoven fabrics and method for producing them
JPH0226919A (ja) * 1988-07-15 1990-01-29 Toray Ind Inc 低摩擦特性と防汚性に優れた繊維

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3754026A (en) * 1969-10-17 1973-08-21 Allied Chem Fluorocarbon amides
US4209610A (en) * 1975-06-30 1980-06-24 Frank Mares Partially fluorinated esters or amide/esters of benzene polycarboxylic acids, and dyeable pet and nylon fibers incorporating the same and process of making such fibers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3005795A (en) * 1957-12-10 1961-10-24 Du Pont Thermoplastic resins containing finely divided, fibrous polytetrafluoroethylene
US3679541A (en) * 1969-07-28 1972-07-25 Ici Ltd Sheath/core bicomponent filaments and process of preparing same
US4251200A (en) * 1978-11-30 1981-02-17 Imperial Chemical Industries Limited Apparatus for spinning bicomponent filaments
US4818587A (en) * 1986-10-17 1989-04-04 Chisso Corporation Nonwoven fabrics and method for producing them
JPH0226919A (ja) * 1988-07-15 1990-01-29 Toray Ind Inc 低摩擦特性と防汚性に優れた繊維

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0585312A4 *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592884A1 (fr) * 1992-09-30 1994-04-20 Minnesota Mining And Manufacturing Company Composition contenant un polymère thermoplastique et un derivé fluoré de pipérazine
EP0599023A3 (fr) * 1992-09-30 1994-11-23 Minnesota Mining & Mfg Aminoalcools fluorochimiques.
US5380778A (en) * 1992-09-30 1995-01-10 Minnesota Mining And Manufacturing Company Fluorochemical aminoalcohols
US5451622A (en) * 1992-09-30 1995-09-19 Minnesota Mining And Manufacturing Company Composition comprising thermoplastic polymer and fluorochemical piperazine compound
US5661206A (en) * 1993-06-11 1997-08-26 Mbt Holding Ag Fluidity control of cementitious compositions
EP0708799A4 (fr) * 1993-06-30 1996-10-09 Peach State Labs Inc Fibres resistantes aux salissures
WO1997022660A1 (fr) * 1995-12-21 1997-06-26 E.I. Du Pont De Nemours And Company Sulfone fluore comme additif fondu pour des polymeres thermoplastiques
US6297304B1 (en) 1995-12-21 2001-10-02 E. I. Du Pont De Nemours And Company Fluorinated diester melt additives for thermoplastic polymers
US5681963A (en) * 1995-12-21 1997-10-28 E. I. Du Pont De Nemours And Company Fluorinated melt additives for thermoplastic polymers
US5798402A (en) * 1995-12-21 1998-08-25 E. I. Du Pont De Nemours And Company Fluorinated sulfone melt additives for thermoplastic polymers
CN1080284C (zh) * 1995-12-21 2002-03-06 纳幕尔杜邦公司 热塑性聚合物的氟代砜熔体添加剂
US5977390A (en) * 1995-12-21 1999-11-02 E. I. Du Pont De Nemours And Company Fluorinated diester melt additives for thermoplastic polymers
AU713947B2 (en) * 1995-12-21 1999-12-16 E.I. Du Pont De Nemours And Company Fluorinated sulfone melt additives for thermoplastic polymers
US6063474A (en) * 1995-12-21 2000-05-16 E. I. Du Pont De Nemours And Company Fluorinated ester melt additives for thermoplastic fibers
US6114419A (en) * 1995-12-21 2000-09-05 E. I. Du Pont De Nemours And Company Fluorinated melt additives for thermoplastic polymers
WO1997033019A1 (fr) * 1996-03-07 1997-09-12 Minnesota Mining And Manufacturing Company Fil pour moquette ayant une grande resistance aux salissures
EP1111102A1 (fr) * 1996-03-07 2001-06-27 Minnesota Mining And Manufacturing Company Fil pour tapis ayant une haute résistance à la salissure
US5882762A (en) * 1996-03-07 1999-03-16 Minnesota Mining And Manufacturing Company Carpet yarn having high soil resistance
US6426025B1 (en) 1997-05-12 2002-07-30 3M Innovative Properties Company Process for extruding fibers
US6476114B2 (en) 1997-11-19 2002-11-05 3M Innovative Properties Company Thermoplastic polymer film comprising a fluorochemical compound
WO2006019526A1 (fr) 2004-07-15 2006-02-23 3M Innovative Properties Company Libération adhésive d'agents oléofuges et hydrofuges
WO2006021529A1 (fr) * 2004-08-25 2006-03-02 Ciba Specialty Chemicals Holding Inc. Modificateurs de surface
US7230043B2 (en) 2004-09-07 2007-06-12 3M Innovative Properties Company Hydrophilic polymer composition
US20100090182A1 (en) * 2006-06-15 2010-04-15 Ian Robert Tooley Uv Absorbing Composition
US20100264383A1 (en) * 2006-06-15 2010-10-21 Croda International Plc Uv Absorbing Composition
US9777407B2 (en) 2009-03-27 2017-10-03 3M Innovative Properties Company Hydrophilic polyproylene melt additives
CN107075191A (zh) * 2014-08-20 2017-08-18 英威达技术有限公司 具有增强的耐污性的合成纤维及其制备方法
EP3183296A4 (fr) * 2014-08-20 2018-06-06 INVISTA Textiles (U.K.) Limited Fibres synthétiques à résistance aux taches améliorée et procédés de fabrication de celles-ci
WO2016179384A1 (fr) * 2015-05-05 2016-11-10 Invista Technologies S.Ar.L. Fibres synthétiques ayant une résistance accrue à la salissure, procédés de production et utilisation
CN108138369A (zh) * 2015-05-05 2018-06-08 英威达纺织（英国）有限公司 具有增强的抗污性的合成纤维及其生产和使用方法
AU2016258018B2 (en) * 2015-05-05 2020-05-14 Invista Textiles (U.K.) Limited Synthetic fibers with enhanced soil resistance and methods for production and use thereof

Also Published As

Publication number Publication date
JPH06506714A (ja) 1994-07-28
EP0585312A1 (fr) 1994-03-09
CA2107777A1 (fr) 1992-10-29
AU1771492A (en) 1992-11-17
EP0585312A4 (en) 1994-09-28

Similar Documents

Publication Publication Date Title
US5459188A (en) Soil resistant fibers
WO1992018569A1 (fr) Fibres resistant aux impuretes
EP1838773B1 (fr) Diesters fluores en tant qu'additifs repulsifs pour polymere a l'etat fondu
JP3953107B2 (ja) ブレンドしたポリマー類のプレキシフィラメンタリーストランド
EP0152883A2 (fr) Fibres mouillables en polyoléfine et produits les contenant
EP0904432B1 (fr) Fil pour tapis ayant une haute resistance a la salissure
FR2810988A1 (fr) Compositions polyamides a antistaticite et hydrophilie ameliorees
US20060135673A1 (en) Fluorochemical esters blends as repellent polymer melt additives
US6426025B1 (en) Process for extruding fibers
EP1036223B1 (fr) Procede d'extrusion de fibres
JPH09310281A (ja) 改質モノフィラメントおよびその製造法
AU4090500A (en) Carpet yarn having high soil resistance
JPS6047383B2 (ja) 耐汚染糸類の製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2107777

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1992910817

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1992910817

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1992910817

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载