WO2001018304A1 - Abrasion- and wrinkle-resistant finish for textiles - Google Patents
Abrasion- and wrinkle-resistant finish for textiles Download PDFInfo
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- WO2001018304A1 WO2001018304A1 PCT/US2000/024581 US0024581W WO0118304A1 WO 2001018304 A1 WO2001018304 A1 WO 2001018304A1 US 0024581 W US0024581 W US 0024581W WO 0118304 A1 WO0118304 A1 WO 0118304A1
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- 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
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
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- 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
-
- 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
- D06M15/423—Amino-aldehyde resins
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- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- 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
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Definitions
- the present invention relates to textile treatment compositions for imparting water/soil resistance to fibrous substrates, including textiles.
- Repellents based on monomeric hydrocarbon hydrophobes can be broken down into five categories: 1) aluminum and zirconium soaps, 2) waxes and waxlike substances, 3) metal complexes, 4) pyridinium compounds, 5) methylol compounds, and 6) other fiber-reactive water repellents.
- monomeric hydrophobes can penetrate within the fabric to produce a more durable coating.
- One of the oldest water repellents was based on non-covalently applying water-soluble soap to the fibers and precipitating it with an aluminum salt (J. Text. Res. vol. 42, 1951 , p. 691). These coatings dissolved in alkaline detergent solution, therefore washfastness was poor.
- Zirconium soaps were less soluble in detergent solutions (Waterproofing and Water-Repellency, Elsevier Publ. Co., Amsterdam,
- Quilon chrome complexes polymerize to form -Cr-O-Cr- linkages (Tappi vol. 36, 1953, p. 107). Simultaneously, the complex forms covalent bonds with the surface of fibers with hydrophobic chains directed away from the surface to produce a water repellent, semi-durable coating. Quilon solutions require acidic conditions to react, thus causing degradation of the cellulose fibers through cellulose hydrolysis. Fabric colors are limited by the blue-green coloration imparted by the metal complex. The extensive history of pyridinium-type water repellents has been reviewed by Harding (J. Text. Res. vol. 42, 1951 , p. 691).
- N-methylol compounds are prepared by reaction of an amine or amide with formaldehyde.
- Alkyl-N-methylol compounds can be reacted at elevated temperatures in the presence of an acidic catalyst with the hydroxyl groups of textiles to impart durable hydrophobic qualities (Br. Pats. 463,300 and 679,811).
- the reaction is accompanied by formation of non-covalently linked (i.e., non-durable) resinous material, thus decreasing efficiency.
- the high temperature and acid catalyst reduce the strength of the fabric.
- the commercial use of methylol compounds has been waning due to concerns of toxic formaldehyde release from fabrics treated in such a manner.
- This invention is directed to treatment preparations useful for the treatment of textiles and other webs to provide substantially permanent, durable water and soil repellency to keratinous and/or cellulosic textiles and other webs. More particularly, the invention is directed to preparations that comprise a fluorinated polymer and metal atoms, typically as a metal salt.
- the preparations of the invention comprise (a) a fluorinated carboxylate-functionalized fluoropolymer and (b) a metal salt, or mordant.
- this invention comprises a solution, emulsion or suspension of (a) a fluorinated polymer that contains functional moieties or reactive groups that can complex with metal atoms that have a formal charge of 2 or greater, and (b) one or more metal atoms that have a formal charge of 2 or greater.
- fluorinated polymer or “fluoropolymer” is meant that the polymer will contain some perfluorinated or partially fluorinated alkyl chains to impart water and oil repellency to coated objects. It may additionally be advantageous for the polymer to contain other groups such as normal alkyl chains; groups that can increase the water solubility or stability of the suspension of the polymer, such as chains of polyethylene glycol or other polar groups; one or more different groups that can crosslink to each other or to the material being coated; or groups that increase polymer flexibility, flame retardancy, the softness of a textile, or resistance to bacteria or mildew.
- groups such as normal alkyl chains; groups that can increase the water solubility or stability of the suspension of the polymer, such as chains of polyethylene glycol or other polar groups; one or more different groups that can crosslink to each other or to the material being coated; or groups that increase polymer flexibility, flame retardancy, the softness of a textile, or resistance to bacteria or mildew.
- the metal atoms in the solution of the second embodiment can come from two sources. Either they are part of a monomer that is copolymerized to become part of the polymer, such as calcium, magnesium, aluminum, or chromium acrylate; or they are added in the form of a compound that has a metal with a formal charge of 2 or greater. This addition of the metal can take place before polymerization, during polymerization, or after polymerization. Without being bound by theory, it is believed that the metal atoms may complex with keratinous textiles or any other textiles that contain free carboxyl groups. By “complexing" is meant that the polymer will form a coordination bond with the metal and the metal will form a coordination bond to the fiber, textile, or web to be treated.
- the metal atoms may act to crosslink the polymer to itself and to other chains to make the polymer insoluble in the textile or web.
- the resulting water/soil repellent preparation has more durable water and soil repellency in and/or on the textile or web fiber structure while retaining the natural properties of the textile.
- This invention is further directed to a novel block copolymer containing i) one or more blocks composed primarily of acrylic acid, methacrylic acid, maleic anhydride, maleic acid, crotonic acid, itaconic acid, or other acid-containing monomers and ii) one or more blocks that contain a significant amount of a fluorinated monomer that is capable of binding to wool or other textiles with a metal. They may further comprise a monomer that contains a metal, such as calcium, magnesium, aluminum, potassium, or chromium acrylates or styrene sulfonates.
- a metal such as calcium, magnesium, aluminum, potassium, or chromium acrylates or styrene sulfonates.
- This invention is further directed to the yarns, fibers, fabrics, textiles, finished metal. They may further comprise a monomer that contains a metal, such as calcium, magnesium, aluminum, potassium, or chromium acrylates or styrene sulfonates.goods, or nonwovens (encompassed herein under the terms “textiles” and “webs”) treated with the water- and soil-resistant preparations of the invention.
- a metal such as calcium, magnesium, aluminum, potassium, or chromium acrylates or styrene sulfonates.goods, or nonwovens (encompassed herein under the terms “textiles” and “webs”) treated with the water- and soil-resistant preparations of the invention.
- Such textiles and webs exhibit a greatly improved, durable water and soil repellency.
- durable water and soil repellency is meant that the textile or web will exhibit a repellency or resistance to water and oily soils even after multiple launderings.
- Methods are provided for treating fabrics with permanent water/soil repellent coatings.
- the preparations of the invention comprise a combination of metal atoms, typically as a metal salt, and a metal-reactive fluorinated polymer capable of imparting a water/soil-resistant property to textiles.
- the metal imparts greater stability and durability to the polymer when the polymer is immobilized on the textile than when the metal is not present.
- the fluorinated monomers, oligomers or macromonomers of the durable water/soil-resistant fluoropolymer are selected from those groups that will provide the necessary water/soil resistance and can be polymerized. Examples include fluorinated monomers of acrylates, methacrylates, alkenes, alkenyl ethers, styrenes, and the like. Monomers that contain carbon-fluorine bonds that would be useful in this invention include, but are not limited to, Zonyl TA-N (an acrylate from DuPont), Zonyl TM (a methacrylate from DuPont), FX-13 (an acrylate from 3M), and FX-14 (a methacrylate from 3M).
- the fluoropolymers may include -CF 3 and -CHF 2 end groups, perfluoroisopropoxy groups (-OCF(CF 3 ) 2 ), 3,3,3-trifluoropropyl groups, and the like.
- the polymers may include vinyl ethers having perfluorinated or partially fluorinated alkyl chains.
- the fluoropolymer preferably comprises one or more fluoroaliphatic radical-containing monomers having the structure of Formula I, below:
- R is a linear, branched, or cyclic fluorocarbon, including fully or partially fluorinated hydrocarbons, wherein R may be, for example, a Ci to C 30 fluorocarbon;
- W is hydrogen or CrC lower alkyl
- the preferred embodiment of this invention is a fluoropolymer prepared by the emulsion process in water or in a mixture of water and an organic solvent that is then dissolved or suspended in water or into a solution in which water is a significant component.
- the reactive groups on the water/soil-resistant fluoropolymer are selected from those groups that will coordinately bind strongly with a metal.
- Such moieties include, but are not limited to, carboxyl, carboxylate, sulfate, sulfonate, phosphate, and phosphonate groups.
- the metal-reactive monomers may be selected from groups that contain carboxylates such as acrylic acid, methacrylic acid, bisacrylamidoacetic acid, 3-butene-1 ,2,3-tricarboxylic acid, maleic acid, 2- carboxyethyl acrylate, itaconic acid, 4-vinylbenzoic acid, and the like; or sulfonates such as 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methyl-2-propene-1- sulfonic acid, 2-propene-1-suIfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, vinylsulfonic acid, styrene sulfonic acid, styrene sulfonic acid (sodium salt), and the like; or phosphates or phosphonates such as vinyl phosphonic acid or vinyl phosphoric acid, and the like.
- particularly useful monomers such as acrylic acid, meth
- a monomer such as styrene sulfonate or potassium acrylate may be used where an additional metal atom with a formal charge of 2 or greater may be added before, during, or after polymerization.
- the actual metal-polymer salt would be water-soluble or at least have some water solubility. When dried properly, hydrophobic groups in the polymer would orient themselves in such a way as to imbed or surround metal-anion complexes. When metals with a formal charge of 2 or greater are used, polymer crosslinking-providing added stability, could result.
- the metal salt is chosen from those that form an insoluble or nearly insoluble complex with the polymer, especially when the polymer is dried or cured.
- metal salts that also react or complex with the surface of the fiber of the textile or web.
- metal salts that can be added to the polymer prior to, during or after polymerization include calcium (II), magnesium (II), zirconium (IV), aluminum (III), and chromium (III) salts such as calcium chloride (CaCI 2 ), calcium sulfate (CaSO ), calcium nitrate (Ca(NO 3 ) 2 ), magnesium chloride (MgCI 2 ), magnesium sulfate (MgSO ), magnesium nitrate (Mg(NO 3 ) 2 ), zirconium oxychloride (ZrOCI 2 ), zirconium nitrate (Zr(NO 3 ) 4 ), zirconium sulfate (Zr(SO ) 2 ), zirconyl nitrate (ZrO(NO 3 ) 2 ), aluminum sulfate (AI 2 (SO 4 ) 3 ), aluminum potassium sulfate (AI
- one or more surfactants will be present during the polymerization and with the dissolved or suspended polymer.
- the surfactant will keep water-insoluble monomers in solution during polymerization, and later to keep the entire polymer in solution.
- the non-ionic surfactants such as those with the structures CH 3 (CH 2 ) n CO(OCH 2 CH 2 ) m OH (such as, for example, polyethylene oxide (14) monostearate, CH 3 (CH 2 ) n (OCH 2 CH 2 ) m OH, and those with trade names that include "Tween", or "Triton". It is also possible to add additional monomers into the polymer.
- These monomers may act as dyes, pH indicators, softeners, compounds that would give the textile resistance to fungi or bacteria, spacers to make the polymer more flexible, components to increase the solubility of the polymer in a carrier solvent system (e.g., mixtures of water, polar organic solvents, and surfactants) from which the polymer is deposited onto the textiles, or components (non-fluorinated) that add hydrophobicity.
- a carrier solvent system e.g., mixtures of water, polar organic solvents, and surfactants
- Such monomers are known to those of skill in the art.
- Examples of potential softeners that could soften the polymer and are commercially available include acrylic acid and methacrylic acid esters of alkyl chains or siloxane oligomers or polymers.
- the treatment is selected from random copolymers consisting of a fluoroacrylate (e.g., FX-13, 3M; or Zonyl TA-N, DuPont) containing at least two carboxyl-containing monomers, e.g., acrylic acid, per molecule, some vinylidene chloride, and/or PEG-acrylate, and the metal salt is ZrO(NO 3 ) 2 .
- the metal salt and the fluoropolymer are added from an aqueous solution to the keratinous fabric in the normal manner (e.g., padding on of an aqueous solution containing the salt and the polymer, followed by drying at 90°C to 175°C for about 30 seconds to about 5 min).
- the zirconium salt complexes with carboxyl or carboxylate groups from aspartic acid and glutamic acid residues in the keratinous textile while at the same time it reacts with the carboxyl-containing polymer, thus serving as a coordination bridge between the wool and the water/soil resistant polymer.
- the polymer may be linked by one or multiple carboxyls to the wool through the metal.
- the polymer may be crosslinked to itself and to other polymer chains by the mordant. It may also be that the mordant does not bind the polymer to the wool, but rather simply renders the polymer insoluble.
- This invention is further directed to a diblock copolymer that contains one or more blocks of an acidic monomer, such as acrylic acid, along with one or more blocks of fluorinated monomers.
- This polymer is useful to coat fabrics using a metal.
- the hydrophilic monomers are concentrated to one end of the macromolecule. It is believed that this will increase its water solubility and improve its ability to bind to fabrics.
- a chain transfer agent that contains a sulfhydryl group and an amine group
- Two commercially available compounds that have amino and thiol groups are 1-amino-2-methyl-2-propanethiol (sold by Aldrich as the hydrochloride) and 2-(butylamino)ethanethiol.
- Step 2) Reacting the amine-terminated polymer produced in Step 1) with a compound (such as N-acetyl homocysteine thiolactone or 2-iminothiolane, for example) that will convert the amine-terminated polymer into a sulfhydryl-terminated polymer. 3) Performing a polymerization in the presence of the sulfhydryl-terminated polymer produced in Step 2) with a monomer different from the monomer used in Step 1).
- the sulfhydryl-terminated polymer generated in Step 2) acts as a chain transfer agent for the polymer created in Step 3) and caps it, creating a block copolymer.
- a graft copolymer may be made, where the grafted portion is either carboxyl groups or fluorinated material or another material, such as metal-containing monomers or oligomers. It is also possible to make a polymer using some or all of monomers that are themselves oligomers.
- the present invention is further directed to the yarns, fibers, fabrics, finished goods, or other textiles (encompassed herein under the terms “textiles” and webs") treated with the permanent or substantially durable water/soil-resistant fluoropolymer. These textiles or webs will display comparable textile performance of the untreated textile without the wetting/staining of traditional textiles.
- These textiles can be used in a variety of ways including, but not limited to various articles of clothing, including informal garments, daily wear, workwear, activewear and sportswear, especially those for, but not limited to easily wet or stained clothing, such as formal garments, coats, hats, shirts, pants, gloves, and the like; other textiles subject to wetting or staining, such as interior furnishings and upholstery therefor, carpets, awnings, draperies, upholstery for outdoor furniture, protective covers for barbecues and outdoor furniture, automotive and recreational vehicle upholstery, sails for boats, and the like; and industrial uses, such as those listed in Adanur, S., Wellington Sears Handbook of Industrial Textiles, pp. 8-11 (Technomic Publishing Co., Lancaster, PA, 1995).
- the durable water/soil-resistant webs of the present invention are intended to include fabrics and textiles, and may be a sheet-like structure (woven, knitted, tufted, stitch-bonded, or non-woven) comprised of fibers or structural elements. Included with the fibers can be non-fibrous elements, such as particulate fillers, binders, sizes, and the like.
- the textiles or webs include fibers, woven and non-woven fabrics derived from natural or synthetic fibers or blends of such fibers, as well as cellulose- based papers, and the like. They can comprise fibers in the form of continuous or discontinuous monofilaments, multifilaments, staple fibers, and yarns containing such filaments and/or fibers, which fibers can be of any desired composition.
- the fibers can be of natural, manmade, or synthetic origin. Mixtures of natural fibers, manmade fibers, and synthetic fibers can also be used. Examples of natural fibers include cotton, wool, silk, jute, linen, and the like. Examples of man-made fibers include regenerated cellulose rayon, cellulose acetate and regenerated proteins. Examples of synthetic fibers include polyesters (including polyethyleneterephthalate and polypropyleneterephthalate), polyamides (including nylon), acrylics, olefins, aramids, azlons, modacrylics, novoloids, nytrils, aramids, spandex, vinyl polymers and copolymers, vinal, vinyon, Kevlar ® , and the like.
- the fiber, the yarn, the fabric, or the finished good is exposed (by methods known in the art such as by soaking, spraying, dipping, fluid-flow, padding, and the like) to the metal salt and to the water/soil-resistant fluoropolymer, each of which has been dissolved, suspended, or emulsified in an aqueous solution in either a one-step or a two-step process.
- the textile-reactive metals of the metal salts may react with the web by coordinate bonding and the water/soil-resistant polymer reacts with the metals, by coordinate bonding, to permanently attach to the web.
- the metals may crosslink the polymer chains to form an insoluble compound that is non- covalently bound to the web.
- the treated web is then removed from the solution, dried, and cured.
- the invention is further directed, in a presently preferred embodiment to the process for treating textiles and other webs with water/soil repellent coatings durable to repeated cleanings, wherein the polymer and the metal of the coating are applied to the fiber, yarn, or textile simultaneously, that is, in a one-step process.
- the metal salt and the fluoropolymer are mixed together in an aqueous solution and the fiber, the yarn, the fabric, or the finished good is exposed simultaneously to both, by methods known in the art such as by soaking, spraying, dipping, fluid-flow, padding, and the like.
- the treated web is then removed from the solution, dried, and, if desired, cured.
- the fiber, the yarn, the fabric, or the finished good is exposed to the metal salt dissolved or suspended in an aqueous solution.
- the textile-reactive metals of the metal salts may react with the web by coordinate bonding.
- the article is then dried, followed by exposure to the permanent water/soil resistant fluoropolymer suspended in an aqueous solution by methods known in the art such as by soaking, spraying, dipping, fluid-flow, padding, and the like.
- the water/soil resistant polymer reacts with the metals on the web, by coordinate bonding, to permanently attach to the web.
- the treated web is then removed from the solution, dried, and cured.
- the concentration of the metal, nor the concentration of the group that the metal complexes with be so high as to cause precipitation of the suspended or dissolved polymer. It is also essential that enough metal atoms and metal-complexing groups be present to cause the polymer to be insoluble or substantially insoluble in solvents such as water and tetrachloroethylene, which are used to clean textiles, after the polymer has been dried or cured on a textile.
- concentrations of the metals and the complexing groups will depend both on the amount of surfactant that may be present in the solution as well as on the number of other polar groups that may be present on the polymer.
- the concentration of the metal salt in solution can be from about 0.05M to about 1 M, preferably from about 0.1 M to about 0.4M, more preferably about 0.25M; depending, however, on the characteristics of the particular web to be treated and the particular water/soil resistant fluoropolymer to be attached.
- the concentration of the water/soil resistant fluoropolymer in solution can be from about 0.1 % to about 25%, preferably from about 1% to about 5%, more preferably about 2.5%; depending, however, on the characteristics of the particular permanent water/soil resistant polymer selected (such as molecular weight or material).
- the ratio of fluorinated monomer to acidic monomer can vary from about 1 :0.75 to about 1 :5, preferably from about 1 :2.5 to about 1 :4, more preferably about 1 :3.
- the process temperature for either the one- or 2-step process can vary widely, depending on the affinity of the salt for the textile substrate and for the water/soil resistant fluoropolymer. However, the temperature should not be so high as to decompose the reactants or so low as to cause inhibition of the reaction or freezing of the solvent. Unless specified to the contrary, the processes described herein take place at atmospheric pressure over a temperature range from ambient temperature to an elevated temperature that is below the boiling point of the solvent used, preferably from about 10°C to about 110°C, more preferably from about 20°C to about 60°C, and most preferably at 20°C. Conveniently, the processes will be at ambient temperature.
- the time required for the processes herein will depend to a large extent on the temperature being used and the relative reactivities of the starting materials. Therefore, the time of exposure of the textile to the metal salt and the polymer in solution can vary greatly, for example from about a few seconds to about two hours. Normally, the exposure time will be from a few seconds to ten minutes. Drying is carried out at ambient temperature or at a temperature above ambient, up to about 220°C.
- the pH of the solution will be dependent on the textile being treated. For example, the pH should be kept at neutral to acid or perhaps mildly basic when treating wool, because wool will degrade in strong base, whereas when treating cotton the pH should be kept at mildly acidic to neutral to basic, keeping in mind that metal salts often are insoluble in alkali.
- the solution pH's will probably not be too critical when the textile is exposed for only a brief time and if the curing temperature is not too high.
- the deposition of water/soil-resistant polymer with charged groups e.g., carboxylates, sulfonates, and the like
- Salts such as, for example, NaCI, Na 2 SO , etc.
- the process times and conditions are intended to be approximate.
- Example 1 3.603 Grams of acrylic acid, 8.931 g FX-13 (3M), 0.106 g AIBN, and 0.483 g mercaptosuccinic acid were dissolved in 29.565 g THF. While stirring, the reaction vessel was purged with nitrogen for a few minutes. The mixture was then heated and held at reflux for 16 hours. The THF/polymer solution may either be used directly or the THF may be removed by rotary evaporation, leaving the "20-mer" polymer behind.
- Example 2 A 0.232 M solution of ZrO(NO 3 ) 2 in 95% water/5% isobutanol was padded onto wool. The wool was then dried at 90°C. Next, a solution of 1.76 g fluoropolymer (4 parts acrylic acid, 1 part FX-13, 1% mercaptosuccinic acid, "100- mer"; prepared following the procedure of Example 1) at pH 6.9 in 95% water/5% isobutanol was padded onto wool. The wool was again dried at 90°C. The material was then rinsed for 3 minutes under flowing tap water and dried in the oven at 90°C. The sample was immersed (overnight) in a stirred vessel containing tetrachloroethylene to test the stability of the coating. It was then removed and allowed to dry in the air.
- Test for repellency showed that dodecane, water, and an 81 % methanol/water mixture beaded up on the surface. Decane wet it.
- Zonyl TA-N (a fluorochemical acrylate from DuPont), 18 g stearyl acrylate, 15 g polyethylene glycol monoacrylate (Aldrich, M n ⁇ 375), 3 g calcium acrylate, 0.5 g dodecanethiol, 8 g POE(14) monostearate, 1 g 2,2'-azobis(2- methylpropionamidine) dihydrochloride, 100 g isopropyl alcohol, and 100 g water were homogenized. The calcium acrylate was dissolved in water before it was added. The mixture was then homogenized and heated under nitrogen to 70 - 80°C for about 2 hr.
- the oil repellency (OR) of a treated substrate is measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test Method No. 118-1983, which test is based on the resistance of treated substrate to penetration by oils of varying surface tensions. Treated substrates resistant only to Nujol.RTM mineral oil (the least penetrating of the test oils) are given a rating of 1 , whereas treated substrates resistant to heptane (the most penetrating of the test oils) are given a rating of 8. Other intermediate values are determined by use of other pure oils or mixtures of oils, as shown in the following Table.
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00961641A EP1226301A1 (en) | 1999-09-10 | 2000-09-08 | Abrasion- and wrinkle-resistant finish for textiles |
AU73563/00A AU7356300A (en) | 1999-09-10 | 2000-09-08 | Abrasion- and wrinkle-resistant finish for textiles |
US10/084,031 US20020120988A1 (en) | 1999-09-10 | 2002-02-27 | Abrasion-and wrinkle-resistant finish for textiles |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15337599P | 1999-09-10 | 1999-09-10 | |
US60/153,375 | 1999-09-10 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/084,031 Continuation US20020120988A1 (en) | 1999-09-10 | 2002-02-27 | Abrasion-and wrinkle-resistant finish for textiles |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001018304A1 true WO2001018304A1 (en) | 2001-03-15 |
WO2001018304A9 WO2001018304A9 (en) | 2001-06-14 |
Family
ID=22546954
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/024581 WO2001018304A1 (en) | 1999-09-10 | 2000-09-08 | Abrasion- and wrinkle-resistant finish for textiles |
Country Status (4)
Country | Link |
---|---|
US (1) | US20020120988A1 (en) |
EP (1) | EP1226301A1 (en) |
AU (1) | AU7356300A (en) |
WO (1) | WO2001018304A1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7862624B2 (en) * | 2004-04-06 | 2011-01-04 | Bao Tran | Nano-particles on fabric or textile |
US7671398B2 (en) * | 2005-02-23 | 2010-03-02 | Tran Bao Q | Nano memory, light, energy, antenna and strand-based systems and methods |
US8404341B2 (en) | 2006-01-26 | 2013-03-26 | Outlast Technologies, LLC | Microcapsules and other containment structures for articles incorporating functional polymeric phase change materials |
US9234059B2 (en) | 2008-07-16 | 2016-01-12 | Outlast Technologies, LLC | Articles containing functional polymeric phase change materials and methods of manufacturing the same |
US20100016513A1 (en) * | 2008-07-16 | 2010-01-21 | Outlast Technologies, Inc. | Functional Polymeric Phase Change Materials and Methods of Manufacturing the Same |
US20070173154A1 (en) * | 2006-01-26 | 2007-07-26 | Outlast Technologies, Inc. | Coated articles formed of microcapsules with reactive functional groups |
US20100012883A1 (en) | 2008-07-16 | 2010-01-21 | Outlast Technologies, Inc. | Functional Polymeric Phase Change Materials |
US20100015430A1 (en) | 2008-07-16 | 2010-01-21 | Outlast Technologies, Inc. | Heat Regulating Article With Moisture Enhanced Temperature Control |
US8221910B2 (en) | 2008-07-16 | 2012-07-17 | Outlast Technologies, LLC | Thermal regulating building materials and other construction components containing polymeric phase change materials |
US8673448B2 (en) | 2011-03-04 | 2014-03-18 | Outlast Technologies Llc | Articles containing precisely branched functional polymeric phase change materials |
US10003053B2 (en) | 2015-02-04 | 2018-06-19 | Global Web Horizons, Llc | Systems, structures and materials for electrochemical device thermal management |
US10431858B2 (en) | 2015-02-04 | 2019-10-01 | Global Web Horizons, Llc | Systems, structures and materials for electrochemical device thermal management |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB816330A (en) * | 1954-11-08 | 1959-07-08 | Egon Eloed | Improvements in and relating to the resin treatment of textiles |
GB1059543A (en) * | 1963-02-01 | 1967-02-22 | Hoechst Ag | Compositions for rendering textile materials resistant to creasing |
US3350162A (en) * | 1963-01-28 | 1967-10-31 | Staley Mfg Co A E | Method of creaseproofing and stiffening cellulose textile with dimethylol ethylene urea and amylopectin size |
DE1804968A1 (en) * | 1964-09-15 | 1970-06-11 | Riegel Textile Corp | Permanent creased garments by impregnating with an |
US3606992A (en) * | 1967-08-28 | 1971-09-21 | Warnaco Inc | Abrasion and wrinkle resistant cotton containing fabric and method of manufacture |
GB1424698A (en) * | 1972-04-20 | 1976-02-11 | Intercooperation Krereskedelem | Production of an improved finish in textile products |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4292111A (en) * | 1979-01-31 | 1981-09-29 | American Cyanamid Company | Method of adhesion of rubber to reinforcing materials |
US4396391B2 (en) * | 1982-06-30 | 1993-03-16 | Treating cellulose textile fabrics with dimenthylol dihydroyethyleneuree-polyol | |
US5614591A (en) * | 1994-12-15 | 1997-03-25 | The Virkler Company | Process and composition for imparting durable press properties to textile fabrics |
US5879749A (en) * | 1997-09-16 | 1999-03-09 | National Starch And Chemical Investment Holding Corporation | Crosslinkable fabric care compositions |
US6497733B1 (en) * | 2000-04-03 | 2002-12-24 | Nano-Tex, Llc | Dye fixatives |
-
2000
- 2000-09-08 AU AU73563/00A patent/AU7356300A/en not_active Abandoned
- 2000-09-08 EP EP00961641A patent/EP1226301A1/en not_active Withdrawn
- 2000-09-08 WO PCT/US2000/024581 patent/WO2001018304A1/en not_active Application Discontinuation
-
2002
- 2002-02-27 US US10/084,031 patent/US20020120988A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB816330A (en) * | 1954-11-08 | 1959-07-08 | Egon Eloed | Improvements in and relating to the resin treatment of textiles |
US3350162A (en) * | 1963-01-28 | 1967-10-31 | Staley Mfg Co A E | Method of creaseproofing and stiffening cellulose textile with dimethylol ethylene urea and amylopectin size |
GB1059543A (en) * | 1963-02-01 | 1967-02-22 | Hoechst Ag | Compositions for rendering textile materials resistant to creasing |
DE1804968A1 (en) * | 1964-09-15 | 1970-06-11 | Riegel Textile Corp | Permanent creased garments by impregnating with an |
US3606992A (en) * | 1967-08-28 | 1971-09-21 | Warnaco Inc | Abrasion and wrinkle resistant cotton containing fabric and method of manufacture |
GB1424698A (en) * | 1972-04-20 | 1976-02-11 | Intercooperation Krereskedelem | Production of an improved finish in textile products |
Also Published As
Publication number | Publication date |
---|---|
US20020120988A1 (en) | 2002-09-05 |
WO2001018304A9 (en) | 2001-06-14 |
EP1226301A1 (en) | 2002-07-31 |
AU7356300A (en) | 2001-04-10 |
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