WO2012085653A1 - Traitement imperméabilisant - Google Patents

Traitement imperméabilisant Download PDF

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Publication number
WO2012085653A1
WO2012085653A1 PCT/IB2011/003147 IB2011003147W WO2012085653A1 WO 2012085653 A1 WO2012085653 A1 WO 2012085653A1 IB 2011003147 W IB2011003147 W IB 2011003147W WO 2012085653 A1 WO2012085653 A1 WO 2012085653A1
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WIPO (PCT)
Prior art keywords
fluorinated
substrate
comprised
paraffins
concentration
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PCT/IB2011/003147
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English (en)
Inventor
Alessio BENELLI
Simona BENELLI
Original Assignee
Benelli Alessio
Benelli Simona
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Publication of WO2012085653A1 publication Critical patent/WO2012085653A1/fr

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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
    • 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
    • D06M11/07—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/20—Halides of elements of Groups 4 or 14 of the Periodic System, e.g. zirconyl chloride
    • 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
    • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
    • 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
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/213—Perfluoroalkyl carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/33—Esters containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
    • D06M15/353—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes containing fluorine
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11—Halides

Definitions

  • the present invention relates to a composition and its use for imparting repellent properties to a substrate selected from fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof; the process to provide repellent properties to these substrates; and the treated substrates.
  • GB 2085491 describes a composition comprising a polyurethane foam and, optionally, a wax or a waxes mixture, metallic compounds, silicone compounds or fluorocarbons, which makes the treated substrate water resistant.
  • US 20020142162 describes a process to partially impregnate the hemp fibers and enhance their properties, by using a mixture of fluorinated monomers in organic solvents, or, alternatively, a mixture comprising paraffin, zirconium salts and acetic acid.
  • US 348691 1 describes a composition containing a C2-C4 perfluoro aliphatic compound, or a chromium co-ordination complex of perfluoro octanoic acid, a natural wax, Al or Zr salts in a liquid vehicle to impart repellency to fabrics, leather and paper.
  • This composition provides water and oil repellency to the treated material only after heating the fabric to elevated temperatures for a commensurate time period.
  • WO 2009088564 describes a treatment of a nanofiber surface having specific weight and sizes to obtain water repellent fabrics, such treatment preferably comprising calendering.
  • This treatment is carried out with DUPONT Zonyl® surfactants and resins, such as isocyanates, formaldehyde resins, paraffin mixtures and zirconium or aluminium salts, in ratio of 2:1 up to 4: 1, in water and/or other solvents, such as esters of acetic acid, chetones, diols and glycol ethers.
  • the repellency methods sofar known require a heating treatment at temperatures higher than 110-130°C, with deleterious effects on wool and silk fibers.
  • the treatment with fluorinated polymers may affect the fabric characteristics such as softness, colour,
  • An object of this invention is to provide a composition able to confer good water and oil repellent properties to the treated materials, as well as a simple, economic, eco-compatible, laundering resistant process, in order to impart repellency to the treated materials without altering their original characteristics.
  • the present invention relates to a process for imparting repellent properties to a substrate selected from fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof, comprising:
  • this invention relates to a process for providing repellency to a yarn, comprising:
  • aqueous dispersion of the repellent composition until a concentration of 5-35%, comprising fluorinated monomers, fluorinated polymers with a C6-C21 fluoroalkyl or fluoroalkenyl chain, paraffins with a melting point comprised between 0 and 80°C and zirconil compounds, diluted until a concentration of 20-25%, preferably 25-45%, more preferably 35%, during the finish;
  • the present invention relates to a substrate treated with the above mentioned repellent composition.
  • this invention relates to a repellent composition in form of an aqueous dispersion diluted until a concentration of 5-35%, comprising fluorinated monomers, fluorinated polymers with a C6-C21 fluoroalkyl or fluoroalkenyl chain, paraffins with melting point comprised between 0 and 80°C and zirconil compounds.
  • this invention relates to the use of the above mentioned composition and processes for treating substrates selected from fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof.
  • the repellent composition according to the present invention is able to confer water and oil repellency together with stains resistance to the treated substrate without using high temperatures.
  • This allows the treated substrate to maintain its original properties such as, for example, mechanical properties, such as elasticity, flexibility, colour, stability to light, soft feeling, breathability.
  • the repellent effect persists through repeated launderings and/or ⁇ dry cleanings. Any kind of substrate may acquire repellent properties both when treating raw material or finished products.
  • the repellent composition according to this invention is used in the form of an aqueous dispersion, thus avoiding using chemical solvents, with consequent problems for disposal, environmental toxicity, particular precautions for the operators or equipments, specific machinery.
  • - fig. 1 shows a process scheme according to the invention, applied to garments
  • - fig. 2 shows a process scheme according to the invention, applied to wool fabrics, e.g. berets;
  • - fig. 3 shows a process scheme according to the invention, applied to fabrics, e.g. raw material cones for hats manufacturing;
  • - fig. 4 shows a process scheme according to the invention, applied to textile fibers or yarns;
  • - fig. 5 shows the results of a water-repellency test on a fabric;
  • substrate refers both to raw material and finished products.
  • raw material refers, but is not limited, to yarns, fabrics, leather, hides, fur, paper, paperboard, blends thereof and the like.
  • any fibrous material, yarn, fabric known to the skilled in the art may be used in the present invention, e.g., natural fibers, cellulose fibers, synthetic fibers, semi-synthetic fibers, micro- fibers and combinations thereof.
  • fibers, yarns, fabrics include, but are not limited to, fine fabrics, resistant fabrics, cotton, wool, angora, cachemire, camel hair, mohair, alpaca, llama, vicuna, pashmina, silk, satin, linen, hemp, iuta, sisal, straw, acrylic, polyamide, nylon, aramid fiber, polyester, polypropylene, viscose, rayon, polyurethane, cellulose and the like.
  • finished products refers, but is not limited to, inside and outside clothing, garments, such as, for example, hats, berets, woolen caps, gloves, socks, vests, shirts, t-shirts, polo shirts, suits, woolen cloths, pullover, skirts, trousers, pyjamas, underwear, undervests, lingerie, bathing costumes, tracksuit, jackets, overcoats, mantles, raincoats; technical and sportswear, for example wind jackets, ski, jogging, football, bike, and golf wear; rain wear, for example mantles; working wear, for example white coat, overalls, shoes, boots; accessories such as belts, bags, umbrellas; military equipment; camping equipment, for example, sleeping bags, backpacks, tents, awning, tarpaulins, boat-covers, gazebo, upholstery, carpets, suitcases, trunks, and the like.
  • garments such as, for example, hats, berets, woolen caps, gloves, socks, vest
  • hat refers to “cones” and “bonnet”: hat raw material, before ironing, shaping and finishing touches.
  • the term "repellent” refers to the ability to impart water and oil repellency and stain resistance.
  • the water/oil repellency is the characteristic of a substrate to provide water and oil repellence, to be waterproof, to be resistant to water and oil penetration from outside to inside.
  • the water repellency is evaluated according to the substrate resistance to superficial dipping, assessing the wetting index through the Spray Test method, according to UNI EN 24920 (corresponding to AATCC Test Method 22-1996 and AATCC Test method 22-2005) and assessing the resistance to water penetration (test under hydrostatic pressure) by measuring the hydrostatic pressure born by the tested sample according to UNI EN 2081 1 : 1993 (corresponding to UNI 4818 Part 32 - May 1992 and AATCC Test Method 127-2003).
  • the oil repellency is evaluated according to the resistance to hydrocarbons (Hydrocarbon Resistance Test) in accordance with 1 18-2002 AATCC Test Method (C16-C7 Hydrocarbons) (corresponding to UNI EN ISO 14419-2010).
  • Aqueous Liquid Repellency Test Water/ Alcohol Solution Resistance Test according to AATCC Test Method 193-2005 Stain Repellency, described in the experimental part.
  • the term "breathability” relates to the ability of materials, such as fabrics, to transfer from inside to outside the greatest possible quantity of water vapor.
  • the assessment of the substrate water vapor transmission speed is carried out by measuring the tested sample mass by grams, before and after the test, according to UNI 4818-26:1992.
  • laundering relates to domestic and/or industrial washing, hand or machine washing, or dry cleaning of the substrate to a temperature between 30°C and 90°C.
  • dipping relates to the substrate treatment by immersion in a solution, emulsion, aqueous dispersion containing the composition according to the invention.
  • fluoralkyl or fluoralkenil chain C6-C21 refer to alkyl or alkenyl chains, with one or more double bonds, linear, branched, cyclic or blends thereof, having at least an H atom substituted by an F atom, containing from 6 to 21 atoms of carbon, preferably, and from 6 to 14 carbon atoms (C6-C14).
  • Examples include, but are not limited to, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoroundecane, perfluorododecane, perfluorohexene, perfluoroheptene, perfluoroctene, perfluorononene, perfluorodecene, perfluoro n-octhylethylene, perfluorooctyl acrylate and the like.
  • fluorinated monomers refer to monomers, omopolymers, copolymers, comprising for example, terpolymers, tetrapolymers and superior terms in which the most part of the present chemical bonds is of the C-F type and having a C6-C21 fluoralkyl or fluoralkenil chain, preferably C6-C14. It is evident that fluorinated monomers, fluorinated polymers may include non fluorinated parts.
  • the fluorinated monomers and fluorinated polymers according to the invention include perfluorinated monomers, perfluorinated polymers. Hydrogen, other halogens and other elements may be present in lower quantities. Fluorinated monomers and fluorinated polymers are well known to the skilled in the art, and include, but are not limited to, fluorinated compounds such as C6-C21 alcohols or acids which have reacted with appropriate chemical compounds to form esters, starches or polymers, vinyl polymers, such as acrylates, metacrylates and the like.
  • Examples include, without limitation, perfluorohexane, perfiuoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoroundecane, perfluorododecane, perfluorohexene, perfluoroheptene, perfluoroctene, perfluorononene, perfluorodecene, perfluoro n-octhylene, perfluorooctyl acrylate, and the like.
  • fluorinated monomers, fluorinated polymers are perfluorohexane, perfluorohexene, perfluoroctene, perfluorodecene, perfluoro n-octhylethylene, perfluoroocthyl acrylate.
  • the fluorinated monomers, fluorinated polymers according to this invention have a melting point comprised between 30 and 80°C, preferably 30-60°C, more preferably 40-50°C. They do not contain toxic compounds, such as nonylphenols (APEO), perfluorooctanoic acid (PFOA) and sulphonated perfluorooctane (PFOS).
  • APEO nonylphenols
  • PFOA perfluorooctanoic acid
  • PFOS sulphonated perfluorooctane
  • the fluorinated monomers and fluorinated polymers of the invention are dispersed in an aqueous solution (see in general Fluorine-Containing Polymers, Encyclopedia of Polymers Science & Technology, pp. 179-203, Interscience, 1967); preferably at dilutions of 5-35%, more preferably 20-30%, most preferably 30% by weight.
  • the fluorinated monomers, fluorinated polymers according to this invention provide to the aqueous solution in which they are dispersed a pH ranging between 1 and 6, preferably 2- r more preferably 2.5-4.5.
  • paraffin refers to any saturated hydrocarbon, comprising normal paraffins, branched paraffins, iso-paraffins, cyclic paraffins, micro-waxes and blends thereof.
  • the paraffins according to the invention have a melting point comprised between 0 and 80°C, preferably 20-60°C, more preferably 50-60°C.
  • Zirconil derivates comprise, for example, zirconium oxide, zirconium hydroxide, zirconium sulfate, zirconium silicate; zirconium salts, for example, zirconium nitrate, zirconium disulfate, zirconium phosphate, zirconium salts with fatty acids containing 2-21 carbon atoms chains, for example zirconium stearate; zirconium halides, for example zirconium chloride, zirconium fluoride, zirconium tetrafluoride; zirconium esters, for example zirconium acetate, zirconium tetraacetate, zirconium proprionate, zirconium butylate, zirconium valerate, zirconium hexanate, zirconium heptanate, zirconium octoate, zirconium
  • Zirconil derivates function is to fix paraffin. Any metal derivates known to the skilled in the art, which can fix paraffin, may be used according to the present invention.
  • paraffin and zirconil derivate/derivates are previously dispersed in an aqueous solution, properly diluted according to requirements, preferably at dilutions of 5-35%, more preferably 20-30%; most preferably 30% by weight.
  • the aqueous dispersion of paraffin and zirconil derivate/derivates has a pH comprised between 1 and 5, preferably 2-5, more preferably 2.5 - 4.
  • the total concentration of metallic zirconium in this dispersion is comprised between 0.01 - 3%, preferably 0.1-1%, more preferably 0.15-0.18%.
  • Such mixtures are commercially available, for example, under the trade name of Draig NSZ ® , Draig Z ® (Bozzetto Group), Contraqua PZ (Thor).
  • fatty acids refers to saturated or unsaturated monocarboxylic aliphatic acids, branched or linear, containing from 4 to 32 carbon atoms, preferably 4 - 22, more preferably 6-18 carbon atoms.
  • fatty acids include, without limitation, saturated aliphatic monocarboxylic acids, for example butyric, valerenic, caproic, enantic, caprylic, pelargonic, caprynic, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, margaric, iso- heptadecanoic, stearic, iso-stearic, nonadecanoic, arachidic, behenic, tricosanoic, lignoceric, cerotic, montanic, melissic, laceroic, and the like; unsaturated, monounsaturated aliphatic monocarboxylic acids, for example myristoleic, undecyle
  • substituted fatty acids include, without limitation, ricinoleic acid, hydroxystearic, mercaptoundecanoic, methyltetradecanoic, methylpentadecanoic, and the like.
  • the term "about” encompasses the range of experimental error that may typically occurs in a measurement.
  • the composition according to this invention includes fluorinated monomers, fluorinated polymers having a C6-C21 fluoralkyl or fluoralkenyl chain, paraffins with a melting point comprised between 0 and 80°C and zirconil derivates.
  • Other additives such as for example, resins, colorants, perfumes, preservatives, germicides, ... may be added to such a composition.
  • the composition according to this invention is used in the form of aqueous dispersion at a 5-35% concentration, mixing the fluorinated monomers, the fluorinated polymers optionally pre-dispersed in water and the paraffins and the zirconil derivate/derivates, optionally pre-dispersed in water.
  • composition according to this invention is properly diluted in water according to requirements and/or materials to be treated. If necessary, pH is adjusted to the desired values. Preferably the composition according to this invention is diluted in water so as to obtain a 10-15% concentration, preferably 13-14%. Such dispersion is stable, above all during the storing and working steps and has good fixing properties. It may be further diluted up to the desired level and may be applied to the substrate to be treated through any process known to the skilled in the art, for example, dipping, spraying , rolling and the like.
  • the substrate to be treated is dipped in the composition according to this invention, up to complete and uniform absorption, for about 1-5 minutes.
  • the removal of the excess dispersion is made through any process known to the skilled in the art, for example, by centrifugation.
  • the excess aqueous mixture is eliminated through a 4-5 minutes centrifugation.
  • the recovered dispersion may be completely re-used for further working cycles.
  • the so treated substrate becomes repellent after complete drying at room temperature, or sun drying or with a domestic or industrial dryer. Temperatures ranging from 40 to 70°C are enough to provide repellency to the treated substrate.
  • Ironing is one of the preferred heating treatment processes, but it is not always required to obtain repellency.
  • the invention relates to a process for providing repellency to a substrate selected from fibers, fabrics, leather, hides, fur, paper, paperboard and mixtures thereof, comprising:
  • the repellent composition is diluted up to obtain a 10-15% concentration, more preferably 13-14%;
  • the process for providing repellency may include further working steps.
  • the hats after the dipping process and after drying at room temperature for 12-24 hours according to the material, the hats are humidified through any method known to the skilled in the art, for example through spraying, then vaporized for about 5-10 minutes and finally, after arranging them on a shaping frame, they are ironed.
  • Ironing is made at different temperatures and times according to the substrate to be treated. For example, materials such as straw, paper, viscose, etc, are ironed at a temperature of 50°C for 2-5 minutes; materials such as angora, thermoplastic angora, woolen felt, lapin felt, etc. are ironed at a temperature of 80-100°C for about 2-5 minutes.
  • the treated hats can then be well finished as desired.
  • Dipping with the composition according to this invention may be carried out in any of the substrate working steps.
  • the berets and the woolen caps are dipped in a steel tub, during the "fulling" where the fabric and the fibers are pressed with the addition of sulfuric acid.
  • the berets and the woolen caps, properly arranged on an a shaping frame, are then dried preferably by ironing, at a temperature of about 40-45°C.
  • the process according to the present invention may be used at the beginning of a fabric production cycle.
  • the process and the repellent composition according to the present invention may be used directly on the yarns by dipping them during "finish" step. No procedure and no production time typical of the spinning operations must be modified.
  • the fibers are directed to the beater which carries out dust and impurities removal.
  • the yarns are opened, for example, with the aid of the opener.
  • Substrate division is induced with the aid of machines and the process goes on with the dipping with t1 ⁇ 4e composition according to the invention during the finish step.
  • the composition according to the invention is diluted up to a concentration of 20-50%, preferably 25-45%, more preferably 35%.
  • the fibers are then collected by means of a cutter and all of the yarn working steps, such as carding, ironing and the final spinning are carried out, thus obtaining the repellent yarn.
  • the start of the composition repelling process takes place during the finishing (in the case of fabrics) or during washing, drying and ironing (in the case of knitwear).
  • the process according to the invention provides repellent properties to a substrate in an uniform, homogeneous, extremely simple and quick way, under very mild conditions, without having to use high temperatures to dry the treated substrate.
  • the use of mild temperatures required to start the repelling process of the composition according to the invention allows the maintenance of the original characteristics of the treated substrate as well as costs reduction.
  • the fabrics susceptible to thermal treatments, such as silk, may undergo a repelling treatment with the composition of this invention.
  • the process according to this invention is carried out in an aqueous solution, with no use of solvents, toxic solvents, or envinronmentally dangerous solvents, which would always require waste disposal.
  • the process of the present invention does not require any equipment, any specific machinery, any closed machinery.
  • the used substances are not toxic, do not cause irritation and can easily be disposed of.
  • this invention relates to the substrates treated with the repellent composition according to this invention, such as fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof.
  • the process according to this invention allows to provide repellency to a substrate without altering its characteristics: colors do not change, remain light resistant, do not fade; white or light materials are prevented from being tinged yellow; soft feel, elasticity, flexibility, resistance, mechanical characteristics remain unchanged.
  • the repellent composition according to this invention coats homogeneously the treated substrate and may be applied, always with excellent repellency results, both to the raw material and the finished product.
  • the water repelling characteristic persists to repeated launderings and dry cleanings, even when a softener is used.
  • a natural drying or a simple ironing are sufficient to re-activate the repellent composition.
  • the treatment of the materials of interest with the composition according to this invention persists to at least seven washings. Resistance to washings is an index of the stability on the treated substrate surface of the composition according to this invention.
  • the treated substrate presents excellent water and oil repellent characteristics, as it can be seen from the data shown in Tables 1, 3, 4-7 and is stains resistant (Tables 4-7).
  • the treated substrate has a very good breathability (Table 2), allows evaporation of perspiration, which is an important characteristic for the sportswear and rainwear.
  • the repellency of the material of interest may be immediately restored simply through washing and subsequent ironing.
  • This advantage is very important in the case of garments, such as knitwear, t-shirts, shirts, trousers, which are frequently subjected to washings.
  • the present invention relates to the use of the composition for treating substrates selected from fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof.
  • a dispersion of fluorinated polymers (Draig 300 ® cone, Bozzetto Group) in water and a mixture of paraffins and zirconil derivates ((Draig NSZ ® , Bozzetto Group) are blended in ratio 1 :1 at room temperature and diluted in water (fluorinated polymers mixture, paraffins and zirconil derivates 13.40% / water 86.60%).
  • the resulting mixture may be stored.
  • the material to be treated is dipped in the mixture described in Example 1 until complete and uniform absorption (1-5 min.). The excess aqueous mixture is eliminated through centrifugation (about 5 min.). The treated material is then completely suA dried, or by domestic or industrial dryer. (40-70°C).
  • the treated material according to Example 2 is ironed through domestic ironing.
  • the hat to be treated is dipped in the mixture of Example 1 until complete and uniform absorption (1-5 min.). The excess aqueous solution is eliminated through centrifugation (5 min.). The hat is dried completely at room temperature for 12-24 hours according to the material used. It is then humidified by spraying for the time required to get superficially wet. It is finally vaporized for 5-10 minutes. After vaporization it is arranged on a shaping frame and ironed. Then it is taken off the shaping frame and well finished as desired.
  • Example 1 The mixture of Example 1 is added during "fulling".
  • the berets are soaked in a steel tub, where the fabric and the fibers are pressed with the addition of sulfuric acid.
  • the mixture according to Example 1 is added and the berets are left soaking for about 30 min. at a temperature of about 40°C.
  • the excess aqueous solution is eliminated through centrifugation (5 min.).
  • the material, arranged on appropriate shaping frames, is dried by ironing at a temperature of about 40-45°C.
  • the fibers of a cachemire mix material are directed to the beater which carries out the dust and impurities removal operations.
  • the fibers are opened by means of an opener. Material division is induced by means of machines.
  • the fibers are treated with the mixture of example 1 during "finishing".
  • the fibers are then collected by means of a cutter (possible second or third passing through the flock opening machine according to the product refinement and quality desired) carding, ironing and final spinning.
  • the grade of repellence to water is indicated according to UNI EN 24920: value ISO 1 (50) (min) - value ISO 5 (100) (max).
  • the indexes of ISO descriptive scale correspond to the values of AATCC scale, as follows:
  • the material water vapor transmission speed has been determined by measuring the tested sample mass by grams before and after the test, according to UNI 4818-26: 1992.
  • test under hydrostatic pressure The evaluation of resistance to water penetration (test under hydrostatic pressure) has been carried out by measuring the hydrostatic pressure born by the tested sample, according to UNI EN 20811 :1993 (corresponding to UNI 4818 Part 32 - May 1992 and AATCC Test Method
  • Composition 1 (A+B)
  • composition 4 (TG+B)
  • Impregnation method dipping
  • Oil Repellency carried out according to Hydrocarbon Resistance Test, according to AATCC Test Method 118-2002 (C16-C7 hydrocarbons) (corresponding to UNI EN ISO 14419:2010)
  • Aqueous Liquid Repellency carried out according to the Water/Alcohol Solution Resistance Test, according to AATCC Test Method 193:2005.
  • Stain Repellency repellency to aqueous solutions has been evaluated through the Aqueous/Liquid Repellency Test: Water/ Alcohol Solution Resistance Test according to AATCC Test Method 193-2005 Stain Repellency: resistance to stains has been tested by applying to the different water repelling substrates three 0.05 ml drops of a mixture of Vaseline oil and normal-heptane at different concentrations, according to what is reported in Table 3A. The shape and the wetting properties of the deposited drops are observed for 180 seconds and the repellency grade is assigned with reference to the mixture with the best grade which does not wet the treated substrate, with reference to Figure 5.
  • Table 3 The test liquids scale for stain resistance, and the corresponding value from 0 to 7 for fabrics assessment
  • Water repellency - Spray Test carried out according to AATCC Test Method 22-2005 (corresponding to UNI EN 24920:1993, AATCC Test Method 22-1996, Water Repellency: Spray).
  • the Spray Test on a jeans fabric has been repeated after 3, 15 and 25 washing and drying cycles so as to assess the extent of the water repellency decrease.
  • Hand washings with a conventional detergent and a softener have been made at a temperature of 30°C; subsequently the fabric was spin-dried at 1000 rpm for 5 minutes, and dried with an industrial dryer at a temperature of about 60-70°C for 5-7 minutes.
  • the results are shown in table 4.1. • Resistance to water penetration (test under hydrostatic pressure) carried out according to UNI 4818 Part 32 - May 1992 (corresponding to UNI EN 20811 : 1993 and AATCC Test Method 127-2003).
  • Fig. 1 shows an fl garments dipping step, in a tub 2 containing the composition according to this invention.
  • the garments are preferably treated in a spinning drier, 3 (f2 step) and then subjected to the ⁇ drying step, for example with a dryer 4, and/or sun drying, and/or ironing 5, so as to start the water repellent process of the treated garments.
  • Fig. 2 shows the treatment of wool berets 1 , laid in a tub 2, to carry out the fl dipping step.
  • additives are used in order to achieve the beret felting 1 (fulling treatment).
  • the beret 1 is preferably sent to a centrifuge'
  • Fig. 3 shows the treatment of cones or bonnet 1 that is the material used for hats manufacturing 13.
  • the fl dipping step includes the cones immersion 1 in a tub 2 containing the composition according to the invention.
  • an f4 humidification step through sprinkling and an f5 step for the absorption of the composition may be foreseen, for example, for a 12-24 hours time period.
  • the cone 1 is subjected to the G drying phase, preferably through ironing processes 7, at a preferred temperature depending on the treated material.
  • Fig. 4 shows the treatment of textile fibers, that is the material used for the production of yarns 1 1, fabrics and/or knitwear 12.
  • the dipping step fl is carried out during the fibers "finish” treatment, adding in tub 2 the composition of the invention and the other known additives required for the "finish" operations.
  • the fibers are treated by means of known equipments 9 to obtain yarns. 11
  • the yarns 1 1 used for fabrics production are subjected to the f3 drying step during "finishing" so as to start the repelling process.
  • the yarns are used for knitwear production 12 and the G drying step is carried out through garments 12 ironing.

Abstract

La présente invention concerne une composition et son utilisation, en vue de conférer un caractère hydrofuge à un substrat sélectionné parmi les fibres, les textiles, le cuir, les peaux, la fourrure, le papier, le carton et les mélanges de ceux-ci. L'invention porte en outre sur des procédés conférant un caractère hydrofuge à ces substrats, et sur lesdits substrats traités.
PCT/IB2011/003147 2010-12-23 2011-12-23 Traitement imperméabilisant WO2012085653A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
ITFI20120131A1 (it) * 2012-06-22 2013-12-23 Benelli S R L Composizione e trattamento impermeabilizzante
JP2021065267A (ja) * 2019-10-18 2021-04-30 テックワン株式会社 使用によって傘のシートの撥水性が低下したのを回復させる方法

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US3681266A (en) 1971-05-24 1972-08-01 Nalco Chemical Co Copolymers from a polyfluoro amido silane and a polyalcohol
GB2085491A (en) 1980-10-16 1982-04-28 Saxby W E Nottingham Ltd Waterproofing Products and Process
EP0537578A2 (fr) * 1991-10-17 1993-04-21 Bayer Ag Polyisocyanate bloqué dispersable dans l'eau, procédé pour sa préparation et son utilisation
US5308511A (en) * 1992-12-04 1994-05-03 Minnesota Mining And Manufacturing Company Solvent-based water- and oil-repellent treating agent
US20020142162A1 (en) 2001-03-29 2002-10-03 Davis J. Edward Method of treating hemp fibers and a treated hemp fiber
EP1493761A1 (fr) * 2003-07-02 2005-01-05 3M Innovative Properties Company Fluoropolymère basé sur les acrylates ou les méthacrylates avec des courtes chaínes fluorées, et leurs compositions du type imperméable à l'eau et à l'huile
WO2009088564A1 (fr) 2008-01-08 2009-07-16 E. I. Du Pont De Nemours And Company Vêtements résistants à l'eau et perméables à la vapeur d'eau comprenant un non-tissé hydrophobe traitée obtenu à partir de nanofibres

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US3486911A (en) 1967-08-21 1969-12-30 Sun Chemical Corp Textile treating compositions and textiles treated therewith
US3681266A (en) 1971-05-24 1972-08-01 Nalco Chemical Co Copolymers from a polyfluoro amido silane and a polyalcohol
GB2085491A (en) 1980-10-16 1982-04-28 Saxby W E Nottingham Ltd Waterproofing Products and Process
EP0537578A2 (fr) * 1991-10-17 1993-04-21 Bayer Ag Polyisocyanate bloqué dispersable dans l'eau, procédé pour sa préparation et son utilisation
US5308511A (en) * 1992-12-04 1994-05-03 Minnesota Mining And Manufacturing Company Solvent-based water- and oil-repellent treating agent
US20020142162A1 (en) 2001-03-29 2002-10-03 Davis J. Edward Method of treating hemp fibers and a treated hemp fiber
EP1493761A1 (fr) * 2003-07-02 2005-01-05 3M Innovative Properties Company Fluoropolymère basé sur les acrylates ou les méthacrylates avec des courtes chaínes fluorées, et leurs compositions du type imperméable à l'eau et à l'huile
WO2009088564A1 (fr) 2008-01-08 2009-07-16 E. I. Du Pont De Nemours And Company Vêtements résistants à l'eau et perméables à la vapeur d'eau comprenant un non-tissé hydrophobe traitée obtenu à partir de nanofibres

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITFI20120131A1 (it) * 2012-06-22 2013-12-23 Benelli S R L Composizione e trattamento impermeabilizzante
JP2021065267A (ja) * 2019-10-18 2021-04-30 テックワン株式会社 使用によって傘のシートの撥水性が低下したのを回復させる方法

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