US20180023246A1 - Textile process and product - Google Patents

Textile process and product Download PDF

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Publication number
US20180023246A1
US20180023246A1 US15/550,997 US201615550997A US2018023246A1 US 20180023246 A1 US20180023246 A1 US 20180023246A1 US 201615550997 A US201615550997 A US 201615550997A US 2018023246 A1 US2018023246 A1 US 2018023246A1
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textile material
barrier film
coating layer
textile
formaldehyde
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US15/550,997
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Richard Edwards
John Belk
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Zero Point Zero LLC
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Zero Point Zero LLC
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Priority to US15/550,997 priority Critical patent/US20180023246A1/en
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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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • 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
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • 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
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • 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
    • D06M15/59—Polyamides; Polyimides
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • 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
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • 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

Definitions

  • the present invention relates generally to textile processes and products. Specifically, the present invention provides textile processes and products that are essentially (i.e., completely free of) formaldehyde or formaldehydic compounds or release very little formaldehyde or formaldehydic compounds.
  • Formaldehyde is a toxic Volatile Organic Compound, which is grouped in the same class of drugs as cyanide and arsenic—deadly poisons.
  • Formaldehyde is commonly used in several textile production processes; for example after treatment of substantive dyeing, hardening of casein fibres, as a wool protection agent, anti mould and above all as a cross linking agent in resin finishing. See, for example, Piccinini, C. Senaldi, C. Summa, European survey on the release of formaldehyde from textiles, European Commission, Directorate-General Joint Research Centre, Institute for Health and Consumer Protection 2007. When added to clothing, it releases formaldehyde fumes. Unfortunately for people, formaldehyde, a known “human carcinogen,” is a slow and quiet killer, and little has been done to combat its usage in the fabrics that touch our skin—even in the face of research documenting its relationship to cancer.
  • Formaldehyde is directly linked to leukemia, so not only is it critical to keep it off the skin of children suffering from cancer, but all children. This is particularly true when children are the most vulnerable. Treatment options are improving, but prevention is much preferred.
  • allergic contact dermatitis can be attributed to clothing treated with textile finish resins (TFRs), also named durable press resins or permanent press clothing resins. Under normal and foreseeable use, the majority of these resins can release formaldehyde. TFRs are widely used for cotton, cotton/polyester or wrinkle-resistant linen. (Le Coz C., Clothing. In: Textbook of Contact Dermatitis 3rd edition. Rycroft R J G, Menne T, Frosch P J, Lepoittevin JP (Eds), pp. 727-749. Springer, Berlin, Heidelberg, Germany) The frequency of ACD due to textile formaldehyde resins has been reported to be between 0.2% and 4.2% after 1990.
  • the process of producing a garment generally includes, using a cotton garment as an example, planting seeds, watering and otherwise tending the crop while reducing the adverse impact of bugs, disease, and weeds on the crop, harvesting the crop, cleaning the cotton fiber from the bales of cotton, producing thread from these individual fibers, weaving these threads into a cloth, bleaching and/or coloring the cloth, applying any additional treatments to the cloth to stabilize the color, provide resistance to wrinkling, repelling water, or provide other value to the processing or user, then cutting the cloth and sewing pieces of processed cloth into a garment, possibly applying additional treatments to the entire garment as a whole, packaging the garment for sale and shipping, and then shipping the garment.
  • the opportunities for intrusion of harmful materials like formaldehyde into the process of producing a garment or other textile-based product are plentiful.
  • the invention is directed to textile processes and the product formed thereby.
  • the process and the resulting product are characterized in that no formaldehyde or formaldehydic compounds are used in the treatment compositions and a formaldehyde scavenger can be included in at least one of the treatment compositions.
  • the textile process described herein includes forming a barrier film or coating layer to reduce or inhibit (e.g. lock in) release of formaldehyde or formaldehydic compounds from the treated textile material.
  • the resulting textile material is environmentally friendly and exhibits a high degree of oleophobic, superoleophobic, hydrophobic, superhydrophobic, omniphobic, hydrophilic/wicking, abrasion resistance, electrical conductivity, thermal conductivity, anti-fungal, anti-bacterial and/or de-icing properties textile surfaces.
  • the resulting textile material exhibits a high degree of oleophobic, superoleophobic, hydrophobic, superhydrophobic, hydrophilic, superhydrophilic and/or omniphobic textile surfaces which repels soil and water at extremely low-surface-tension without sacrificing aesthetic qualities.
  • FIG. 1 is a schematic representation of a coated textile material according to an embodiment of the invention.
  • FIG. 2 is a schematic representation of a coated textile material according to an embodiment of the invention.
  • FIG. 3 is schematic representation of a metal coated textile material according to an embodiment of the invention.
  • FIG. 4 is a representation of the shape of cotton. As seen cotton has a “bean shape” which means that a simple circle provides for a low surface area estimate for coatings.
  • FIG. 5 is a schematic representation of a nanoparticle coated textile material according to an embodiment of the invention.
  • compositions, methods, and respective component(s) thereof are used in reference to compositions, methods, and respective component(s) thereof, that are essential to the invention, yet open to the inclusion of unspecified elements, whether essential or not.
  • “decrease” , “reduced”, “reduction” “decrease” or “inhibit” are all used herein generally to mean a decrease by a statistically significant amount. However, for avoidance of doubt, “reduced”, “reduction” or “decrease” or “inhibit” means a decrease by at least 10% as compared to a reference level, for example a decrease by at least about 20%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90% or up to and including a 100% decrease (e.g. absent level as compared to a reference sample), or any decrease between 10-100% as compared to a reference level.
  • a 100% decrease e.g. absent level as compared to a reference sample
  • the terms “increased”, “increase” or “enhance” or “activate” are all used herein to generally mean an increase by a statically significant amount; for the avoidance of any doubt, the terms “increased”, “increase” or “enhance” or “activate” means an increase of at least 10% as compared to a reference level, for example an increase of at least about 20%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90% or up to and including a 100% increase or any increase between 10-100% as compared to a reference level, or at least about a 2-fold, or at least about a 3-fold, or at least about a 4-fold, or at least about a 5-fold or at least about a 10-fold increase, or any increase between 2-fold and 10-fold or greater as compared to a reference level.
  • statically significant refers to statistical significance and generally means at least two standard deviation (2SD) away from a reference level.
  • the term refers to statistical evidence that there is a difference. It is defined as the probability of making a decision to reject the null hypothesis when the null hypothesis is actually true.
  • microscale as used herein comprises a surface having a measurable feature in the range of from 1 to 999 ⁇ m.
  • nanoscale as used herein comprises a surface having a measurable feature in the range of from 1 to 999 nm.
  • multiscale as used herein comprises a surface having two or more measurable features.
  • Pillar as used herein comprises a measurable surface feature having an aspect ratio of height to narrowest width (or diameter) of greater than 1, greater than 1.5, greater than 2, greater than 3, greater than 4, greater than 5, greater than 10, greater than 15, greater than 20 or in the range of from 1 to 20, 1.5 to 18 or 2 to 15. Pillars can be square, rectangular or cylindrical in cross- sectional shape and may have a uniform cross-sectional shape along at least a portion of their height.
  • Nanoparticle as used herein comprises a nanoscale deposit of a homogenous or heterogeneous material. Nanoparticles may be regular or irregular in shape and may be formed from a plurality of co-deposited particles that form a composite nanoscale particle. Nanoparticles may be generally spherical in shape or have a composite shape formed from a plurality of co-deposited generally spherical particles. Exemplary shapes for the nanoparticles include, but are not limited to, spherical, rod, elliptical, cylindrical, disc, and the like. In some embodiments, the nanoparticles have a substantially spherical shape.
  • textile material is used in a broad sense to encompass any suitable fibrous material which may be woven or non-woven or of any other appropriate construction.
  • the material forming the textile material can be natural fibers, mineral fibers, glass fibers, carbon fibers, fibers composed of synthetic products and/or fibers composed of synthesized polymers.
  • the textile material includes natural materials, synthetic materials, and materials that contain synthetic fibers.
  • the textile material can be in any size, shape or form.
  • Natural fibers refer to fibers which are obtained from natural sources, such as cellulosic fibers and protein fibers, or which are formed by the regeneration of or processing of natural occurring fibers and/or products. Natural fibers are not intended to include fibers formed from petroleum products. Natural fibers include fibers formed from cellulose, such as cotton fiber and regenerated cellulose fiber, commonly referred to as rayon, or acetate fiber derived by reacting cellulose with acetic acid and acetic anhydride in the presence of sulfuric acid.
  • natural fibers are intended to include natural fibers in any form, including individual filaments, and fibers present in yarns, fabrics and other textiles, while “individual natural fibers” is intended to refer to individual natural filaments.
  • cellulosic fibers are intended to refer to fibers comprising cellulose, and include, but are not limited to, bamboo, cotton, linen, flax, rayon, cellulose acetate, cellulose triacetate, hemp and ramie fibers.
  • rayon fibers is intended to include, but is not limited to, fibers comprising viscose rayon, high wet modulus rayon, cuprammonium rayon, saponified rayon, modal rayon and lyocell rayon.
  • protein fibers are intended to refer to fibers comprising proteins, and include, but are not limited to, wools, such as sheep wool, alpaca, vicuna, mohair, cashmere, guanaco, camel and llama, as well as furs, suedes, silks, and manmade materials.
  • synthetic fibers refer to those fibers that are not prepared from naturally occurring filaments and include, but are not limited to, fibers made from simple components by polymerization, polycondensation or polyaddition.
  • Materials for forming the synthetic fibers include, but are limited to, polyesters, polyamides such as nylons, polyacrylics, polyurethanes such as spandex, elastanes, elastodienes, fluoro fibers, acrylics, modacrylics, aramids, polyvinyl chlorides, polyvinylidene chloride, polyethylenes, polypropylenes and vinylals.
  • Synthetic fibers include fibers formed from petroleum products. Synthetic-fiber containing materials are those that contain both the purely synthetic fiber and also natural materials.
  • the textile material can comprise a material selected from the group consisting of polyester, wool, cotton, bamboo, silk, cellulose, nylon, aramid, acetate, acrylic, jute, sisal, sea grass, coir, polyamide, polyolefin, polyacrylamide, polypropylene, polyaramide, and blends thereof.
  • the textile material is a fibrous material.
  • fibrous material means any material having a ligneous (fibrous) component.
  • fibrous materials are materials that comprise fibers or materials that are fibers themselves.
  • the textile material can comprise components other than the matrix material of the textile material distributed in the matrix of the textile material.
  • Such materials can include, but are not limited to nanocomposites, nanoparticles, dyes, antibacterial, antifungal agents, metals, metal alloys, carbon nanotubes, graphene, reduced graphene oxide (rGO), nanoclays, metallic fibers and particles (catalysts), and the like.
  • a formaldehyde scavenger can be present or distributed in the textile material.
  • exemplary formaldehyde scavengers include, but are not limited to, urea, ethylene urea 4,5-dihydroxyl ethylene urea, ammonium phosphate monobasic and ammonium phosphate dibasic, FREETEX® HFSE, and tannin.
  • Additional formaldehyde scavengers amenable to the present invention include those described, for example, in U.S. Pat. No. 5,194,674 and US Patent Publication No. 2009/0014034, the contents of which are incorporated herein by reference in their entirety.
  • chlorine bleach can be used to break down or scavenge the formaldehyde.
  • a material having antibacterial or antifungal properties can be present or distributed in the textile material.
  • Exemplary materials having antibacterial or antifungal properties include, but are not limited to, TiO 7 , quaternary ammonium salts, silver and silver containing compounds, zinc and zinc containing compounds, copper and copper containing compounds, quaternary ammonium containing materials such as BARDAC/BARQUAT® from Lonza, quaternary silanes such as DC5700® from Dow Corning, polyhexamethylene biguanide available from Zeneca, halamines from Halosource, chitosan, and derivatives thereof, as well various other materials.
  • nanoparticles or microparticles can be present or distributed in the textile material.
  • the textile material comprises a dye distributed in the textile material.
  • dye means substances which impart color to a substrate by selective absorption of light.
  • the textile material comprises a brightener component distributed in the textile material.
  • Brightener components useful in the present invention include one or more optical brighteners or whiteners.
  • optical brighteners and whiteners are used interchangeably and are taken to mean organic compounds that absorb the invisible ultraviolet (UV) portion of the daylight spectrum and convert this energy into the longer-wavelength visible portion of the spectra.
  • optical brighteners include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in “The Production and Application of Fluorescent Brightening Agents,” M. Zahradnik, published by John Wiley & Sons, New York (1982).
  • optical brighteners useful in the present invention are those identified in the Wixon U.S. Pat. No. 4,790,856. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Arctic White CWD, the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles; 4,4′-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4′-bis(styryl)bisphenyls; and the amino-coumarins.
  • these brighteners include 4-methyl7-diethyl-amino coumarin; 1,2-bis(benzimidazol-2-yl)ethylene, 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth[1,2-d]oxazole, and 2-(stilben-4-yl)-2H-naptho[1,2-d]triazole. Additional known brighteners are disclosed in the Hamilton U.S. Pat. No. 3,646,015.
  • the textile material is a fiber.
  • the term “fiber” refers to any slender, elongated structure that can be carded, combed, or otherwise formed into a thread. Examples include “staple fibers”, a term that is well-known in the textile art.
  • a reference to “fiber” of “fibers” may mean or include individual fibers or a plurality or bulk of fibers as the situation requires.
  • a plurality of fibers may comprise fibers of different compositions or may be substantially uniform in composition.
  • natural fiber or “synthetic fiber” may mean and may include a single fiber of such type, or may mean any quantity or plurality of such fibers and they may be comprised in threads, felts, yarns, fabrics materials etc., all as will be apparent from the context.
  • the fiber can be a synthetic fiber or a natural or organic fiber.
  • smoothness of the outer surfaces is significantly varied between different fibers. Accordingly, the outer surface of the fiber can be smooth or rough.
  • manmade fibers such as polyester fibers
  • natural fibers such as cotton
  • rough outer surface One consequence of the roughness of the outer surface is that rough surfaces take more fluid to completely cover the surface per unit diameter.
  • the fiber can have desired cross-sectional shape, including but not limited to, round, star, elliptical, the shape of cotton shown in FIG. 4 , or other geometrical or non-geometrical shape.
  • desired cross-sectional shape including but not limited to, round, star, elliptical, the shape of cotton shown in FIG. 4 , or other geometrical or non-geometrical shape.
  • cross-sectional shape of natural fibers such as shape of cotton fiber is a less efficient shape for coating and increases the fluid intake.
  • the cross-sectional diameter or size of the fiber can range from a few microns to hundreds of millimeters.
  • the textile material is a thread.
  • thread refers to continuous or discontinuous elongated strands formed by carding or otherwise joining together one or more different kinds of fibers.
  • threads may be incorporated into yarns or other structures comprising a plurality of threads, before being woven to form fabrics.
  • the thread comprises two or more different types of fibers.
  • Yarn refers to a structure comprising a plurality of strands that have been twisted, spun or otherwise joined together to form the yarn and may include spun yarns, continuous filament yarns, and yarns of core spun construction. Yarns according to the invention may be manufactured using virtually any yarn-forming process known in the art, including but not limited to, by spinning or stretch broken spinning.
  • the textile material is a fabric.
  • the term “fabric” is to be understood in its widest meaning.
  • the term “fabric” may be used for all structures composed of fibers which have been manufactured according to a surface-forming method. Fabrics include materials where one or more different types of yarns, threads, filaments, or fibers that have been woven, knitted, felted, wrapped, spun, co-mingled, coated, coextruded, braided, entangled, applied or otherwise assembled into a desired material.
  • the fabric has a structure which comprises a series of meshes or openings and filament bundles which define the mesh boundaries, such as woven, knitted, knotted, interwoven or tufted structures.
  • the term “fabric” is intended to include woven fabrics, yarn sheets, knitted fabrics and non-woven fabrics. Further, the fabrics may be constructed from a combination of fibers, threads or yarns. Fabrics comprising different fibers, threads or yarns are also referred to as fabric blends herein.
  • the textile material is a cloth.
  • cloth refers to any textile fabric woven, nonwoven, felted, knitted or otherwise formed from any filament or fiber or plurality of filaments or fibers, including but not limited to thread yarn, monofilaments, and ribbons. Further, the term cloth is intended to include within its scope not only woven, knitted, non-woven, and felted materials, but also sheet materials.
  • the textile material is a garment.
  • the term “garment” refers to any item that is worn by a user to cover or protect some region of the user's body from weather or other factors in the environment outside the body.
  • Exemplary garments include, but are not limited to, coats, jackets, pants, hats, gloves, shoes, socks, shirts, etc. . . . It is noted that the term “garment” is intended to cover clothing for human or animal use.
  • the disclosure provides textile materials that are essentially free of formaldehyde or formaldehydic compounds or release formaldehyde or formaldehydic compounds at very low rates or amounts relative to textile materials known in the art.
  • the term “essentially free” means that the no more than trace amounts of the indicated component may be present. Generally, “essentially free” means that the indicated component is well below 0.05%, preferably below 0.01%, and more preferably below 0.005%. Most preferably no amount of the indicated component can be detected with standard analytical methods used for detecting said component.
  • compositions and process that are essentially free of formaldehyde or formaldehydic compounds are used in preparing the textile materials.
  • this can be expensive and time consuming since many of the compositions and process currently in use require use of preservative, such as formaldehyde.
  • Compositions that are free of preservatives, such as formaldehyde have shorted shelf and recycling life. As such, these compositions need to be changed more often, thereby increasing the cost.
  • the invention provides a method for treating a textile material for reducing the amount of formaldehyde or formaldehydic compounds present in the textile material.
  • the method comprises washing the textile material with a composition that is essentially free of formaldehyde or formaldehydic compounds.
  • a composition comprising a formaldehyde or formaldehydic compound scavenger before the wash step.
  • the method comprises contacting the textile material with a composition comprising a compound that neutralizes or binds with formaldehyde or formaldehydic compound present in the textile material.
  • the method comprises contacting the textile material with chlorine bleach.
  • the textile fabric can be treated to inhibit or reduce the release or diffusion of the formaldehyde or formaldehydic compounds from the textile material.
  • barrier films or coating layers are used to reduce or inhibit the rate or amount of an undesired material into substrate. Barrier films or coating layers are also used in the art to retain a desired material in a substrate. For example, one needs to keep out oxygen and biological material from food when a long shelf life is for the food is required.
  • Hybrid Plastics created a fine sausage casing which keeps out CO 2 using a polyhedral oligomeric silsesquioxanes (POSS)-filled polymer—Nanoreinforced® Polyamide 6. See for example, hybridplastics.com/wp-content/uploads/sites/57/2015/04/Hybrid-Plastics % C2% AE-Packaging-Case-Study.pdf.
  • PES polyhedral oligomeric silsesquioxanes
  • metalized Mylar is commonly used to keep helium balloons to keep them afloat when the metal layer acts as a barrier film.
  • nanoclays are used to make helium-filled pockets for tennis shoes mimicking Nike Air Jordan's (air pockets). Montmorillonite nanoclays are also used as barrier materials in several applications including for structural composites. See for example, Ogasawara et al., Composites Part A: Applied Science and Manufacturing (2005), 37(12): 2236-2240.
  • the invention provides a method for reducing or inhibiting the release or diffusion out of a molecule from the textile material.
  • the method comprises contacting the textile material with a composition to form a barrier film or coating layer on a surface of the textile material.
  • the contacting of the textile material with the composition can be accomplished by any art-known method.
  • the contacting can be, but is not limited to, spraying, painting, rinsing, washing, dipping in the composition, and the like.
  • the barrier film or the coating layer is only present on a part of the surface or the textile material.
  • the textile material is encapsulated in the barrier film or the coating layer.
  • the term “encapsulation” means that the whole surface of the textile material is covered with the barrier film or the coating layer.
  • the barrier film or the coating can impart a desired characteristic or property to the textile surface
  • exemplary characteristics or properties include, but are not limited to, oleophobic, hydrophobic, superoleophobic, superhydrophobic, omniphobic, hydrophilic/wicking, superhydrophylic, abrasion resistance, electrical conductivity, thermal conductivity, anti-fungal and/or anti-bacterial properties.
  • any material that can inhibit or reduce the release or diffusion of an unwanted molecule from the textile material can be used for forming the barrier film or coating layer.
  • the material used to form the barrier film or the coating layer is a polymeric material or a material capable of forming a polymer.
  • the barrier film or the coating layer is made from a material selected from the group consisting of carbohydrate polymers, proteins, silk fibroin, polydimethylsiloxane, polyimide, polyethylene, polypropylene, terephthalate, polymethylmethacrylate, urethanes (such as polyurethane), polyvinylchloride, polystyrene polysulfone, polycarbonate, polymethylpentene, polypropylene, a polyvinylidine fluoride, polysilicon, polytetrafluoroethylene, polysulfone, acrylonitrile butadiene styrene, polyacrylonitrile, polybutadiene, poly(butylene terephthalate), poly(ether sulfone), poly(ether ether ketones), poly(ethylene glycol), styrene-acrylonitrile resin, poly(trimethylene terephthalate), polyvinyl butyral, polyvinylidenedifluor
  • suitable polymers which can be used for forming the barrier film or the coating layer include, but are not limited to, one or a mixture of polymers selected from the group consisting of carbohydrate polymers; silk; glycosaminoglycan; fibrin; poly-ethyleneglycol (PEG); C2 to C4 polyalkylene glycols (e.g., propylene glycol); polyhydroxy ethyl methacrylate; polyvinyl alcohol; polyacrylamide; poly (N-vinyl pyrolidone); poly glycolic acid (PGA); poly lactic-co-glycolic acid (PLGA); poly e-carpolactone (PCL); polyethylene oxide; poly propylene fumarate (PPF); poly acrylic acid (PAA); hydrolysed polyacrylonitrile; polymethacrylic acid; polyethylene amine; polyanhydrides; polyhydroxybutyric acid; polyorthoesters; polysiloxanes; polycaprolactone; poly(lactic-co-glycolic acid); poly(lactic-
  • the barrier film or the coating layer is made from a biocompatible material.
  • biocompatible material refers to any polymeric material that does not deteriorate appreciably and does not induce a significant immune response or deleterious tissue reaction, e.g., toxic reaction or significant irritation, over time when implanted into or placed adjacent to the biological tissue of a subject, or induce blood clotting or coagulation when it comes in contact with blood.
  • Suitable biocompatible materials include derivatives and copolymers of a polyimides, poly(ethylene glycol), polyvinyl alcohol, polyethyleneimine, and polyvinylamine, polyacrylates, polyamides, polyesters, polycarbonates, and polystyrenes.
  • the barrier film or the coating layer is made from a material selected from the group consisting of acrylics; fluoropolymers, polyesters; polyimides; POSS® polymers (silesquioxanes); urethanes (such as polyurethanes); biologically-compatible polymers, such as, polycarbonates, polymers based on propylene (such as polypropylenes), and polymers based on ethylene (such as polyethylenes); ultra-high molecular weight polyethelynes (UHMWPE); and any combinations thereof.
  • the barrier film or the coating layer comprises acrylic, or nanoclay filled acrylic.
  • the barrier film or the coating layer comprises a non-fluoropolymer.
  • Non-fluoropolymers, such as polyurethanes, are available from DuPont.
  • the barrier film or the coating layer is made from two or more different materials.
  • at least one of the material in forming the barrier film or the coating layer is a fluoropolymer.
  • fluoropolymer refers to a polymer comprising recurring units derived from at least one fluorinated monomer.
  • at least one fluorinated monomer means that the polymer may comprise recurring units derived from one or more than one fluorinated monomers. Exemplary fluoropolytners amenable to the invention are described, for example, in U.S. Pat. No. 7,829,477.
  • the barrier film or the coating layer is a nanocomposite dielectric coating. Nanocomposite dielectric coatings are described, for example in U.S. Pat. No. 8,470,459, content of which is incorporated herein by reference in its entirety.
  • the barrier film or the coating layer comprises a glass/silica based paint.
  • the barrier film or the coating layer can be of any desired thickness.
  • the barrier film or the coating can have a thickness of a few nanometers to a few millimeters.
  • the barrier film or the coating thickness can range from about 0.1 nm to about 1000 ⁇ m.
  • the barrier film or the coating thickness can be based on the material used for the barrier film or the coating.
  • the barrier film or the coating comprises a metal or is metallic the thickness can be under 25 microns.
  • the thickness can range from about 5 microns to about 100 microns. It is noted that the thickness can be varied as desired,
  • the barrier film or the coating is very, very thin and does not show up on a simple light microscope.
  • the barrier film or the coating may be seen as a film bridging the gaps between threads in a woven substrate as shown in FIG. 1 .
  • the barrier film or the coating can be a thin or ultrathin coating on the shape, e.g., cylindrical, of the fiber.
  • An exemplary embodiment of coated fiber is shown schematically in FIG. 2 .
  • the barrier film or the coating layer comprises a metal coating layer on a surface of the barrier film or the coating layer.
  • metal coating means applying to a surface of the barrier film or the coating layer a metal.
  • any metal can be used for forming the metal coating layer.
  • Exemplary metals include, but are not limited to gold, silver, copper, nickel, iron, cobalt, zinc, titanium, platinum, palladium, aluminum, tin, lead, and other metals or any combination of metals to make a metal alloy.
  • Metal coating layer can formed using known metal coating or metal plating processes such as spraying, vapor deposition, powder coating, immersion processes, solution dipping processes, electroless plating and electroplating.
  • the barrier film or the coating layer comprises a metal coating layer on a surface of the barrier film or the coating layer.
  • a metal coating layer on a surface of the barrier film or the coating layer.
  • FIG. 3 An exemplary embodiment of this is shown schematically in FIG. 3 .
  • carbon coating generally includes two to four covalently linked carbon (C), hydrogen (H), silicon (Si), and oxygen (O) atoms.
  • the metal coating layer can be of any desired thickness.
  • the metal coating can have a thickness of a few nanometers to a few millimeters.
  • the metal coating thickness can range from about 0.1 nm to about 1000 ⁇ m.
  • the metal coating thickness can be of the same thickness as the barrier film or the coating layer, larger than the thickness of the barrier film or the coating layer, or smaller than the thickness of the barrier film or the coating layer. In some embodiments, the metal coating thickness is about from 5 microns to about 15 microns.
  • the barrier film or the coating layer comprises a carbon coating layer on a surface of the barrier film or the coating layer.
  • carbon coating generally includes two to four covalently linked carbon (C), hydrogen (H), silicon (Si), and oxygen (O) atoms.
  • the carbon coating layer can be of any desired thickness.
  • the carbon coating can have a thickness of a few nanometers to a few millimeters.
  • the carbon coating thickness can range from about 0.1 nm to about 1000 ⁇ m.
  • the carbon coating thickness can be of the same thickness as the barrier film or the coating layer, larger than the thickness of the barrier film or the coating layer, or smaller than the thickness of the barrier film or the coating layer.
  • the matrix of the barrier film or the coating layer can comprise materials other than the matrix material distributed in the matrix material.
  • Such materials can include, but are not limited to nanocomposites, nanoparticles, dyes, antibacterial or antifungal agents, metals, metal alloys, and the like.
  • the barrier film or the coating layer comprises nanoclays, carbon based materials, e.g., CNTs or graphene platelets, dispersed in the matrix material of the barrier film or the coating layer.
  • nanoclays, CNTs, platelets, graphene platelets and particles in the barrier film or coating layer can provide an arduous path for gas or liquid molecules as they outgas from the textile material. Without wishing to be bound by a theory, this can be considered biomimicry when, for example, you combine a polymer film with layered hard platelets like nanoclays as is done in producing abalone shells (using hard salts and soft living proteins) creating impact resistant and flexible structures.
  • the barrier film or the coating layer comprises more than one layer, e.g., two, three, four, five, six, seven, eight, nine, ten or more layers.
  • the different layers can be the same or different.
  • “different” in this context is meant that two layers differ from each other by at least one aspect.
  • the two layers can differ from each other based on the matrix material, components distributed in the matrix material, thickness of the layers, density of the layers, functional properties of the layers, etc. . . .
  • the layers can be individual layers or the same material, e.g., Integran's NANOBATE CoP plating and NANO-Copper plating product.
  • the barrier film or the coating layer comprises particles, such as nanoparticles.
  • the nanoparticles form features such as microscale, nanoscale, mutltiscale or pillars on the surface of the textile material.
  • the nanoparticles form localized deposits on surface of the textile material that act as pillars.
  • the nanoparticles form features, such as those shown in FIG. 5 on the surface of the textile material.
  • the barrier film or the coating layer can inhibit or reduce the release or diffusion out of the undesired molecule, e.g., formaldehyde or formaldehydic compounds from the treated textile material by at least 10% (e.g., at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% and upto and including 100%, i.e., complete inhibition or reduction) relative to release or diffusion from an untreated control textile material.
  • the treated textile material releases no formaldehyde or formaldehydic compounds or only trace amounts that are below the detection limit of the method employed for detecting the release of formaldehyde or formaldehydic compounds.
  • European Ecolabel and Oeko-Tex Standard 100 have set limits for formaldehyde that vary depending on textile categories. In particular, Ecolabel set limits of 30 mg/kg for formaldehyde released from textiles in direct contact with the skin and 300 mg/kg for textiles which have no direct contact with the skin. Oeko-Tex Standard 100 set limits of 75 mg/kg for for formaldehyde released from textiles in direct contact with the skin and 300 mg/kg for textiles which have no direct contact with the skin. In addition, Oeko-Tex Standard 100 established that textiles for babies up to two years old should release less than 20 mg/kg.
  • less than 30 mg/kg e.g., 30 mg/kg, 25 mg/kg, 20 mg/kg, 15 mg/kg, 10 mg/kg, 5 mg/kg or less
  • formaldehyde is released from the treated textile material.
  • Organic nitrogen compounds such as amines, amides, ureides, amino acids, and proteins having hydrogen bonded to the nitrogen, also can react with formaldehyde to provide a useful assay for formaldehyde content.
  • formaldehyde reacts with lower amino acids, such as alanine, asparagine, and glycine in an aqueous solution.
  • the aqueous solutions of these lower amino acids have a slightly acidic or neutral pH.
  • the concentration of formaldehyde can be determined by end point titration of the amino acid-formaldehyde solution with an alkaline solution.
  • Dye color leaching from the textile material during processing or washing is a big concern in the textile industry.
  • the methods disclosed herein can be used to reduce or inhibit the release of dyes from textile material.
  • textile material in the form of cotton thread was treated with an acrylic based fluoropolymer from Clariant to form a barrier film or coating; layer.
  • the release of dyes from the textile material was significantly reduced when compared to non-coated textile material.
  • red dye treated cotton thread was wound onto a spool for further treatment.
  • a special chemical bath of color fixative would then be applied to minimize loss of the red dye into the later expensive treatment fluids for producing softness to the touch, resistance to wrinkle development, repelling water, etc.
  • this step was skipped and a modified Clariant-branded acrylic-based fluoropolymer fluid was applied under heat and pressure.
  • the immediate result was a reduction in the redness of the recovered treatment fluid.
  • This process and chemistry provided a barrier film with both water repellant and fixative benefits with application of one fluid reducing material, labor, and machine-time costs.
  • the invention provides a method for treating a textile material with a composition that is essentially free of formaldehyde or formaldehydic compounds.
  • the method comprises contacting a textile material with a composition that is essentially free of formaldehyde or formaldehydic compounds.
  • the composition imparts superoleophobic, superhydrophobic, omniphobic, hydrophilic/wicking, abrasion resistance, electrical conductivity, thermal conductivity, anti-fungal and/or anti-bacterial characteristics to the textile material.
  • the finishing composition i.e., the composition for forming the barrier film or the coating layer or the composition used for imparting a desired characteristic or functionality to the textile material
  • the finishing composition can be applied to the textile material in accordance with any of the conventional techniques known in the art.
  • the contacting of the textile material with the composition can be, but is not limited to, spraying, painting, rinsing, washing, dipping in the composition, and the like.
  • the treatment composition can be applied to the textile material by saturating the textile material in a trough and squeezing the saturated textile material through pressure rollers to achieve a uniform application (padding process).
  • wet pick-up refers to the amount of treatment composition applied to and/or absorbed into the textile material based on the original weight of the textile material.
  • “Original weight of the textile material” or simply “weight of the textile material” refers to the weight of the textile material prior to its contact with the treatment composition. For example, 50% pick-up means that the textile material picks up an amount of treatment solution equal to about 50% of the textile material's original weight.
  • the wet pick-up is at least about 20%, preferably from about 50% to 100%, more preferably from about 65% to about 80%, by weight of the textile material for many applications. It is noted that, for fluorocarbon treatments of materials to be labeled “organic,” 3-7% pick-up is preferred to maintain the label.
  • Other application techniques that can be employed include kiss roll application, engraved roll application, printing, foam finishing, vacuum extraction, spray application or any process known in the art. Generally, these techniques provide lower wet pick-up than the padding process. The concentration of the components in the solution can be adjusted to provide the desired amount of barrier film or the coating layer on the original weight of the textile material.
  • the composition is applied in an amount to insure a moisture content of more than about 10% by weight, preferably more than about 30% by weight, on the textile material.
  • the textile material can be pretreated with a textile pre-treatment preparation technique known in the art. Suitable preparation techniques include brushing, singeing, de-sizing, scouring, mercerizing, and bleaching.
  • a textile pre-treatment preparation technique known in the art. Suitable preparation techniques include brushing, singeing, de-sizing, scouring, mercerizing, and bleaching.
  • the textile material can be treated by brushing which refers to the use of mechanical means for raising surface fibers that will be removed during singeing.
  • the textile material then be singed using a flame to burn away fibers and fuzz protruding from the fabric surface.
  • the textile material can be de-sized, which refers to the removal of sizing chemicals such as starch and/or polyvinyl alcohol, which are put on yarns prior to weaving to protect individual yarns.
  • the textile material can be scoured, which refers to the process of removing natural impurities such as oils, fats and waxes and synthetic impurities such as mill grease from the textile material.
  • Mercerization refers to the application of high concentrations of sodium hydroxide (or optionally liquid ammonia) and optionally high temperatures, steam, and tension to a fabric to alter the morphology of fibers, particularly cotton fibers.
  • Fabrics may be mercerized to improve fabric stability, moisture retention and uptake, chemical reactivity, tensile strength, dye affinity, smoothness, and luster. Fabrics may also be compressively stabilized (e.g., SANFORIZED®) by manipulation/compaction of the fabric in the presence of heat and steam.
  • bleaching refers to the process of destroying any natural color bodies within the natural fiber.
  • a typical bleaching agent is hydrogen peroxide.
  • the textile material can optionally be washed to remove residual materials or to apply additional technologies/treatments to the textile material.
  • Post-washing of the textile material can occur before or after construction of the end-product. Washing can occur via continuous or batch processes.
  • the finish composition can comprise, in addition to the material for forming the barrier film or the coating layer or the material for imparting a desired characteristic or functionality to the textile material, additional ingredients to enhance the characteristics of the final finished textile material.
  • additional ingredients include, but are not limited to, wetting agents, brighteners, softening agents, stain repellant agents, color enhancing agents, anti-abrasion additives, water repellency agents, UV absorbing agents and fire retarding agents.
  • the invention also provides the textile material treated with the methods disclosed herein.
  • the textile material is in the form of a wearable, i.e., an article of clothing.
  • the textile material e.g., the article of clothing is worn against the skin.
  • the treatment process can further comprise contacting the substrate with a composition comprising a formaldehyde scavenger.
  • exemplary formaldehyde scavengers include, but are not limited to, urea, ethylene urea 4,5-dihydroxyl ethylene urea, ammonium phosphate monobasic and ammonium phosphate dibasic, FREETEX® HFSE, and tannin.
  • Additional formaldehyde scavengers amenable to the present invention include those described, for example, in U.S. Pat. No. 5,194,674 and US Patent Publication No. 2009/0014034, the contents of which are incorporated herein by reference in their entirety.
  • the treatment process can further comprise one or more wash steps.
  • the susbtrate undergoes a washing step before contacting with the composition that is free of formaldehyde or formaldehydic compounds.
  • the substrate undergoes a washing step before contacting with the composition that s free of formaldehyde or formaldehydic compounds.
  • the treatment process can be at any appropriate temperature, e.g., room-temperature (e.g., about 16° C. to about 30° C.), a cold temperature (e.g. about 0° C. to about 16° C.), or an elevated temperature (e.g., about 30° C. to about 95° C.). Further, different steps of the treatment process can be carried out at different temperatures.
  • room-temperature e.g., about 16° C. to about 30° C.
  • a cold temperature e.g. about 0° C. to about 16° C.
  • an elevated temperature e.g., about 30° C. to about 95° C.
  • contacting of the composition with the substrate is for sufficient duration to impart a desired level of oleophobic, hydrophobic, hydrophilic, superoleophobic, superhydrophobic, superhydrophilic and/or omniphobic characteristics to the substrate. Accordingly, the contacting can be from anywhere from few seconds to minutes, hours, days, weeks or months.
  • compositions that can impart superoleophobic, superhydrophobic and/or omniphobic characteristics to a surface include those described, for example, in U.S. Pat. No. 8,580,027, the contents of which are incorporated herein by reference in their entirety.
  • the first method is based on the extraction of a weighed amount of sample material (approx. 1.0 g) with water at 40° C. for one hour (an oscillating water bath was used). The extract is then filtered and treated with acetylacetone (Nash reactive), with which formaldehyde reacts to give a yellow compound (3,5-diacetyl-1,4-dihydrolutidine). The color development is obtained in half an hour at 40° C. The absorbance of the reaction product is measured at 412 nm and the quantification of formaldehyde is performed with the use of external standards.
  • the second method (EN ISO 14184-2) is based on the absorption in water of formaldehyde vapour released by a weighed amount of sample material (approx. 1.0 g) suspended over water in a sealed jar. The jar is placed in an oven at 49° C. for 20 hours. The quantification of formaldehyde in the aqueous solution is performed, as in the previous method, by a colorimetric reaction with Nash reagent.
  • the wax on the lotus leaf surface is weakly hydrophilic, even though the lotus leaf is known to be superhydrophobic.
  • Conventional understanding suggests that a surface of such a waxy composition should not be able to support superhydrophobicity and high contact angles between a liquid and the surface.
  • the unexpected superhydrophobicity is related to the presence of “reentrant texture” (that is, a multivalued surface topography) on the surface of the lotus leaf.
  • the inventors used their understanding of this multivalued surface topology to enable the development of superoleophobic surfaces (i.e., surfaces that repel soil and water at extremely low-surface-tension liquids, such as various fluoroalkanes), where essentially no naturally oleophobic materials exist.
  • the invention further provides general design parameters for “breathability,” that enable the evaluation of the robustness of the composite interface on textile surface depending on the usage and amount of “waterproofness and breathability.” Based on design parameters of a textile's “weave,” airflow can be regulated. For example, the more open weave a fabric has, the more “breathable” it will be in transporting water away from the body, although axiomatically that also means less waterproofness as there is a direct tradeoff between airflow and not letting water in.
  • liquid-repellent surfaces typically involves the manipulation of two key surface parameters: surface energy and physical roughness.
  • the overall free energy of the system determines whether a given liquid fully wets or creates a composite interface with a particular textured surface.
  • the composite interface typically leads to high contact angles and low roll-off angles (corresponding to low contact-angle hysteresis).
  • Studies show that a series of rough or textured substrates within the fabric, with progressively decreasing surface energy, or increasing equilibrium contact angles ( ⁇ ), exhibit a transition from a fully wetted state to a composite interface, equating the critical value of the equilibrium contact angle ( ⁇ c) this transition.
  • the contact angle ⁇ is one way to characterize wetting of surfaces.
  • the contact angle ⁇ is affected both by the chemical nature of the surface and by its roughness. Affinity of a flat surface towards a certain liquid is defined in terms of the “flat” (or intrinsic, or Young's) contact angle:
  • ⁇ is the surface energy (or surface tension)
  • subscript S stands for solid
  • L for liquid
  • A for air.
  • the solid-liquid surface energy can be estimated via the other two as follows:
  • the surface is called (hydro-, oleo-, etc.) -phobic if the contact angle is greater than 90°, and -philic otherwise.
  • surface energy ⁇ LA 73 mJ m ⁇ 2
  • the best non-wetting situation on a flat surface is achieved if it is terminated with —CF 3 groups, which brings its surface energy down to SA ⁇ 6 mJ m ⁇ 2 .
  • the value of intrinsic (Young's) contact angle for water on such a surface is ⁇ flat ⁇ 120°.
  • the term “oleophobic” comprises surfaces having a contact angle for an organic liquid of greater than 90°.
  • the term “superoleophobic” comprises surfaces having a contact angle for an organic liquid of greater than 150°.
  • Such organic liquids may comprise hydrocarbon liquids having a surface energy ⁇ LA ⁇ 30 mJ m ⁇ 2 .
  • Such liquid hydrocarbons may he characterized as hydrophobic and may be liquid at ambient temperature and pressure.
  • Such liquids may comprise aliphatic hydrocarbons having from 6 to 14 carbon atoms, for example octane, decane or hexadecane.
  • a preferred organic liquid for the purposes of defining superoleophobicity herein is hexadecane.
  • hydrophobic comprises surfaces having a contact angle for water of greater than 90°.
  • superhydrophobic as used herein comprises surfaces having a contact angle for water of greater than 150°.
  • the area fraction, f, of the surface can be important for providing desirable superoleophobic properties. It can be desirable to provide the textile fabric surface with an area fraction in the range of from 0.01 to 0.20, or from 0.01 to 0.15, or from 0.01 to 0.10, or from 0.05 to 0.10, or from 0.02 to 0.09, or from 0.03 to 0.08, or from 0.04 to 0.07, or from 0.05 to 0.06.
  • hydrophilic comprises surfaces havinf a contact angle for water of less than 90°.
  • superhydrophilic comprises surfaces having a contact angle for water of less than 10°.
  • anti-icing refers to the process of preventing ice from bonding to or forming on a surface. It will be understood that the term “anti-icing” refers to the prevention of the formation of ice in the first place whereas the term “de-icing” refers to the reduction, or elimination, of ice after it has begun to form.
  • reentrant as used herein comprises a surface feature that has a first portion with a first width and a second portion with a second width, the first width greater than the second width.
  • a re-entrant surface feature is provided by a plurality of nanoparticles aggregated atop a micropillar such that a composite top is formed having a diameter larger than that of the pillar.
  • Re-entrant features preferably have a convex upper surface.
  • Re-entrant surface features may resemble “mushroom caps”, “bean sprouts”, “hoodoos”, or a variety of other similar commonly known shapes when seen in side view.
  • the terms “reentrant” and “multivalued” as they refer to a surface topology are used interchangeably herein.
  • the textile process treatment disclosed herein imparts a reentrant texture to the textile fabric surface feature that has a first portion with a first width and a second portion with a second width, the first width greater than the second width.
  • a re-entrant surface feature is provided by a plurality of nanoparticles aggregated atop a micropillar such that a composite top is formed having a diameter larger than that of the pillar.
  • Re- entrant features preferably have a convex upper surface.
  • Re-entrant surface features may resemble “mushroom caps”, “bean sprouts”, “hoodoos”, or a variety of other similar commonly known shapes when seen in side view.
  • the terms “reentrant” and “multivalued” as they refer to a surface topology are used interchangeably herein.
  • the reentrant texture comprises microscale features or nanoscale scale features. In some embodiments, the reentrant texture comprises a combination of microscale and nanoscale features, i.e., the reentrant texture is a multiscale surface. In some embodiments, the reentrant texture comprises features that appear to be pillars. In some embodiments, the reentrant texture comprises features that are multiscale pillars and/or hierarchical features.
  • the reentrant texture comprises features or shape formed from a plurality of co-deposited generally spherical particles, such as nanoparticles.

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WO (1) WO2016131012A1 (fr)

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US11771769B2 (en) 2017-11-10 2023-10-03 Cocoon Biotech Inc. Ocular applications of silk-based products
US11332830B2 (en) 2017-11-15 2022-05-17 Global Graphene Group, Inc. Functionalized graphene-mediated metallization of polymer article
US20190292720A1 (en) * 2018-03-20 2019-09-26 Nanotek Instruments, Inc. Graphene-Mediated Metallization of Fibers, Yarns, and Fabrics
US11401436B2 (en) 2019-04-04 2022-08-02 King Fahd University Of Petroleum And Minerals Method of making UHMWPE hybrid nanocomposite coating reinforced with nanoclay and carbon nanotubes
WO2023193378A1 (fr) * 2022-04-07 2023-10-12 苏州大学 Tissu hydrophobe à grandes stabilité mécanique et durabilité et son procédé de préparation

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