WO2025062043A1 - Revêtement hydrophobe de fibres, de fils et de textiles - Google Patents

Revêtement hydrophobe de fibres, de fils et de textiles Download PDF

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Publication number
WO2025062043A1
WO2025062043A1 PCT/EP2024/076685 EP2024076685W WO2025062043A1 WO 2025062043 A1 WO2025062043 A1 WO 2025062043A1 EP 2024076685 W EP2024076685 W EP 2024076685W WO 2025062043 A1 WO2025062043 A1 WO 2025062043A1
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WIPO (PCT)
Prior art keywords
blended yarn
fibre
elastic fibre
elastic
covalently coated
Prior art date
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PCT/EP2024/076685
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English (en)
Inventor
Dirk Hegemann
Martin Amberg
Patrick RUPPER
Dominik PREGGER
Bernd Schäfer
Philipp KOSNIK
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Baeumlin & Ernst Ag
Lothos Klg
Eidgenoessische Materialpruefungs und Forschungsanstalt
Original Assignee
Baeumlin & Ernst Ag
Lothos Klg
Eidgenoessische Materialpruefungs und Forschungsanstalt
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Publication of WO2025062043A1 publication Critical patent/WO2025062043A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, e.g. by ultrasonic waves, corona discharge, irradiation, electric currents or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Sonic or ultrasonic waves; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin

Definitions

  • Elastic fibres made of an elastomer typically containing a high amount of polyurethane, silicon or polymultiester, have a complex structure comprising soft elastomer and rigid polymer segments. Elastic fibres can be stretched to a multiple of their length providing a large surface for water to accumulate, resulting in long drying processes.
  • Hydrophobic treatment of textiles is usually conducted using conventional wet chemical methods, wherein surface active compounds or crosslinking agents adhere to the textile fibre surfaces.
  • such conventionally treated textiles have several disadvantages, wherein the hydrophobic coating does not sufficiently adhere to the elastic fibres within the textile and are thus only hydrophobic right after the hydrophobic treatment, but the hydrophobic effect decreases through wearing the textile and laundry processes.
  • the patent RU 2043438 C1 describes the principle of plasma treatment of fibres on one bobbin during rewinding onto a second bobbin.
  • the patent EP 0695384 B1 discloses plasma coating of fibres and textile structures, e.g. for water repellence by means of chemical bonding of the plasma layer to the fibre surface.
  • the patent EP 3697958 B1 discloses a method for preparing a textile with hydrophobically coated surface through plasma and wet chemical treatment.
  • the objective of the present invention is to provide means and methods to prepare hydrophobically coated elastic fibres or yarns with improved hydrophobic properties, textiles made thereof as well as an apparatus for conducting hydrophobic treatment of elastic fibres or yarns.
  • a first aspect of the invention relates to a method for coating of elastic fibre or blended yarn comprising the coating of elastic fibre or blended yarn with an activated coating compound, yielding a covalently coated elastic fibre or covalently coated blended yarn, wherein the covalently coated elastic fibre or covalently coated blended yarn is characterised in that the coating has a thickness of 5 to 200 nm.
  • a second aspect of the invention relates to a covalently coated elastic fibre or covalently coated blended yarn, wherein the coating has a thickness of 5 to 200 nm.
  • a third aspect of the invention relates to a hydrophobic elastic textile comprising covalently coated elastic fibre or covalently coated blended yarn according to the second aspect of the invention, wherein the coating has a thickness of 5 to 200 nm.
  • a fourth aspect of the invention relates to an apparatus for covalent coating of elastic fibre or blended yarn comprising a. a plasma chamber with at least one plasma zone, b. at least one inner bobbin containing the elastic fibre or blended yarn, c. an outer bobbin to wind up the elastic fibre or blended yarn, wherein the at least one inner bobbin is localised inside the at least one plasma zone and the outer bobbin is localised outside the plasma chamber.
  • a fifth aspect of the invention relates to a covalently coated elastic fibre or covalently coated blended yarn, according to the first aspect of the invention, characterised in that the covalently coated elastic fibre or covalently coated blended yarn has hydrophobic properties.
  • references to “about” a value or parameter herein includes (and describes) variations that are directed to that value or parameter per se. For example, description referring to “about X” includes description of “X.”
  • elastic fibre in the context of the present specification relates to a fibre containing elastomer segments, a class of polymer fibre with a high elasticity and which can be stretched to a multiple of its length and return into its original state when the stretching force is omitted.
  • Elastic fibre is commonly classified according to the elastic elongation, that is, high elastic fibre with elongation of 400 to 800 %, medium elastic fibre with elongation of 150 to 390 % and low elastic fibre with elongation of 20 to 150 %.
  • Examples for elastic fibres are elastanes, based on polyurethane, silicones or polymultiester.
  • Elastic fibre has a high elasticity, is shaperetaining, firm, tear-resistant and light.
  • blended yarn in the context of the present specification relates to yarn containing elastic fibres and non-elastic fibres, wherein elastic fibres are as defined herein and non-elastic fibres relate to polymer synthetic fibres which do not contain elastomer segments, including but not limited to polyethyleneterephthalate, polyamide, polypropylene, polyacryl and polylactid.
  • activated coating compound in the context of the present specification relates to a compound with hydrophobic properties, wherein a volatile precursor reacts and/or decomposes with or on a substrate, particularly the surface of the elastic fibre, yielding an activated coating compound by firmly (covalently) binding on the substrate.
  • adjacent areas in the context of the present specification relates to areas built when a covalently coated elastic fibre is stretched.
  • the coating on the fibre surface is pulled apart when stretched and maintains contiguous areas, when the coiled elastomer segments of the elastic fibre are increasingly straightened.
  • fluorocarbon in the context of the present specification relates to chemical compounds with carbon-fluorine bonds, such as perfluorinated compounds containing further chemical elements and compounds consisting purely of fluorine and carbon atoms such as tetrafluoromethane, hexafluoropropene, octafluorocyclobutane.
  • hydro fluorocarbon in the context of the present specification relates to organic compounds that contain carbon, fluorine and hydrogen atoms, such as trifluoromethane, pentafluoropentane, tetrafluoroethane, and hexafluoropropane.
  • covalently coated in the context of the present specification relates to a strong chemical bond between the fibre surface and the activated coating compound, wherein the electrons participating in the covalent bond are distributed between the bonding partners, resulting in a stable bond. Covalently coated fibres are thus more stable against acting outer forces such as through abrasion or stretching.
  • a first aspect of the invention relates to a method for coating of elastic fibre or blended yarn comprising the coating of elastic fibre or blended yarn with an activated coating compound, yielding a covalently coated elastic fibre or covalently coated blended yarn, wherein the covalently coated elastic fibre or covalently coated blended yarn is characterised in that the coating has a thickness of 5 to 200 nm.
  • the elastomer segments of the elastic fibres can be straightened out resulting in the elastic properties of the fibres, while the rigid segments provide the fibre structure yielding solid strands.
  • prepolymers are drawn out to produce the solid strands that are bundled together to achieve long elastic fibres. Due to the natural stickiness of the elastic strands that adhere to one another, the elastic fibre has properties similar to a monofilament fibre.
  • the sticky surface of the elastic fibre further requires the application of a finishing agent after the drawing process, typically a silicone oil.
  • the finishing material is loosely applied and non-covalently bond to the elastic fibres. However, while the finishing material is hydrophobic, it gets easily spread or washed out, so that the elastic fibres lose their hydrophobicity over time.
  • the herein claimed method is a method for directly coating the elastic fibre or a yarn comprising an elastic fibre, prior to incorporating them into a textile, wherein the coating is applied as a hydrophobic coating, the activated coating compound, which covalently binds onto the fibre or yarn yielding an adjustable coating of 5 to 200 nm thickness.
  • the adjusted film thickness allows high adhesion of the activated coating compound at least on portions of the elastic fibre surface.
  • the hydrophobic coating is more durable and less prone to be reduced in its effect due to wearing and washing and still allows further textile processing.
  • the method for coating of elastic fibre or blended yarn comprises the coating of elastic fibre or blended yarn with an activated coating compound, yielding a covalently coated elastic fibre or covalently coated blended yarn, wherein the covalently coated elastic fibre or covalently coated blended yarn is characterised in that the coating has a thickness of 10 to 100 nm.
  • the method for coating of elastic fibre or blended yarn comprises the coating of elastic fibre or blended yarn with an activated coating compound, yielding a covalently coated elastic fibre or covalently coated blended yarn, wherein the covalently coated elastic fibre or covalently coated blended yarn is characterised in that the coating has a thickness of 25 to 40 nm.
  • the film thickness of 25 to 40 nm is both, sufficiently thick to guarantee a highly hydrophobic surface, yet thin enough to allow unrestricted stretching and recoiling of the elastic fibres to avoid film failure under tensile and compressive stress.
  • the elastic fibre or blended yarn is washed prior to being coated with the activated coating compound, enabling covalent coating on the surface of the elastic fibre or blended yarn.
  • washing of the elastic fibre or blended yarn prior to being coated at least partly removes the finishing agent applied to the elastic fibre, which is typically a silicon oil.
  • the finishing agent applied for handling the elastic fibres due to the natural stickiness of the elastic strands that adhere to one another is removed to an extent to uncover the fibre surface, while keeping the fibre structure, i.e. the sticking of the bundles, intact.
  • Application of a coating can thus directly interact with the sticky fibre surface.
  • the method further comprises pre-stretching of the elastic fibre or blended yarn.
  • the elastic fibres are pre-stretched while applying the activated coating compound.
  • the elastic fibre or blended yarn is pre-stretched by at least 10%.
  • Pre-stretching of the elastic fibre or blended yarn by at least 10% allows for at least 50% surface coverage through the coating maintained during stretching and relaxing which provides a coated fibre or coated blended yarn with improved hydrophobic properties.
  • the elastic fibre or blended yarn is pre-stretched between 10% to
  • the elastic fibre or blended yarn is pre-stretched between 10% to
  • the elastic fibre or blended yarn is pre-stretched between 30% to
  • the method comprises winding the pre-stretched elastic fibre or prestretched blended yarn onto a bobbin, yielding winded elastic fibre or winded blended yarn.
  • the method comprises introducing the winded elastic fibre or winded blended yarn into a vacuum chamber.
  • the activated coating compound is applied onto washed elastic fibre or washed blended yarn using chemical vapor deposition.
  • the method comprises introducing the winded elastic fibre or winded blended yarn into a plasma chamber in such way that the outer fibres on the bobbin are facing the coating zone of the plasma.
  • the activated coating compound is applied onto washed elastic fibre or washed blended yarn using plasma polymerisation.
  • the activated coating compound is applied as a gaseous substance which is activated by the plasma to form a coating species at low temperatures.
  • the coating species become adhesive and are covalently bound onto the elastic fibre without altering the fibre bulk properties.
  • the coating species show an improved infiltration through diffusion into the textile structure of the fibres coiled onto the bobbin, so that the fibres are coated not just in parts facing the plasma, but on the whole surface as well as partly on the inlying fibres.
  • the activated coating compound is applied to the elastic fibre or blended yarn by unwinding it from a bobbin at an unwinding speed of 10 to 1000 m/min.
  • the inlying fibres are gradually exposed and coated.
  • the activated coating compound can be applied to the elastic fibres or blended yarn on several bobbins placed in the plasma chamber simultaneously.
  • the thickness of the coating can be adjusted by the deposition rate of the activated coating compound and the residence time of the elastic fibre in a coating zone.
  • the activated coating compound is applied to the elastic fibre or blended yarn by unwinding it from a bobbin at an unwinding speed of 50 to 600 m/min.
  • the activated coating compound is applied to the elastic fibre or blended yarn by unwinding it from a bobbin at an unwinding speed of 100 to 600 m/min.
  • An unwinding speed of higher than 100 m/min increases the processual speed.
  • the activated coating compound is selected from the group consisting of organic silicon compounds, hydrofluorocarbons, fluorocarbons and hydrocarbons.
  • the activated coating compound is selected from the group consisting of organic silicon compounds and fluorocarbons.
  • the activated coating compound is selected from the group consisting of organic silicon compounds.
  • Organic silicon compounds are ecologically compatible.
  • the organic silicon compound is selected from a siloxane or silicone.
  • the organic silicon compound is a siloxane.
  • the organic silicon compound is a siloxane selected from the group consisting of hexamethyldisiloxane, tetramethyldisiloxane, 1 , 1 ,1 , 3, 3, 5,5,5- octamethyltrisiloxane, octamethylcyclotetrasiloxane.
  • the organic silicon compound is a siloxane selected from the group consisting of hexamethyldisiloxane and octamethylcyclotetrasiloxane.
  • the activated coating compound is hexamethyldisiloxane.
  • the activated coating compound is gaseous.
  • the activated coating compound is mixed with argon gas.
  • coated elastic fibre or coated blended yarn is further spun to a textile.
  • the coated elastic fibre is spun to a textile.
  • the hydrophobically coated elastic fibre is incorporated into a textile using textile methods known to any skilled person, forming a yarn or a piece of textile.
  • the coated elastic fibre is spun to a textile and further coated with a hydrophobic compound.
  • the textile can undergo further wet chemical methods for further treatment with hydrophobic compounds.
  • Textiles containing already hydrophobically coated elastic fibres according to the invention have the advantage of being hydrophobically coated even on the inlying fibres and are thus, after additional wet chemical hydrophobic coating, coated throughout the entire textile having a long lasting hydrophobic effect. Insufficient adherence or a decreasing hydrophobic effect through appropriate washing and wearing the textile is avoided.
  • the textile has additionally better drying properties after storage in water and an improved wash resistance.
  • the elastic fibre is an elastane.
  • the elastic fibre is an elastane comprising polyurethane.
  • Elastane based on polyurethane has an increased colour fastness. This applies to elastic fibre used as such and blended yarn comprising elastic fibre.
  • a second aspect of the invention relates to a covalently coated elastic fibre or covalently coated blended yarn, wherein the coating has a thickness of 5 to 200 nm.
  • the adjusted film thickness allows high adhesion of the activated coating compound at least on portions of the elastic fibre surface during stretching and recoiling.
  • the hydrophobic coating is more durable and less prone to be reduced in its effect due to wearing and washing and still allows further textile processing.
  • the covalently coated elastic fibre or covalently coated blended yarn has a coating with a thickness of 10 to 100 nm. In certain embodiments, the covalently coated elastic fibre or covalently coated blended yarn has a coating with a thickness of 25 to 40 nm.
  • the covalently coated elastic fibre is an elastane.
  • the covalently coated elastic fibre is an elastane comprising polyurethane.
  • Elastane based on polyurethane has an increased colour fastness.
  • the covalently coated elastic fibre or covalently coated blended yarn is covalently coated in adjacent areas covering at least 50% of the fibre surface, when the covalently coated elastic fibre or covalently coated blended yarn is stretched to 300%, providing hydrophobic properties of the covalently coated elastic fibre.
  • the covalently coated elastic fibre or covalently coated blended yarn is covalently coated in adjacent areas covering at least 70% of the fibre surface, when the covalently coated elastic fibre or covalently coated blended yarn is stretched to 300%, providing hydrophobic properties of the covalently coated elastic fibre.
  • covalently bound coating portions When stretching the elastic fibre, covalently bound coating portions maintain contiguous areas that are pulled apart when the coiled amorphous segments are increasingly straightened. These coated portions forming adjacent areas are sufficient to provide hydrophobic properties of the elastic fibres.
  • a third aspect of the invention relates to a hydrophobic elastic textile comprising covalently coated elastic fibre or covalently coated blended yarn according to the second aspect of the invention, wherein the coating has a thickness of 5 to 200 nm.
  • the hydrophobic elastic textile comprises covalently coated elastic fibre or covalently coated blended yarn according to the second aspect of the invention, wherein the coating has a thickness of 10 to 100 nm.
  • the hydrophobically elastic textile comprises covalently coated elastic fibre or covalently coated blended yarn according to the second aspect of the invention, wherein the coating has a thickness of 25 to 40 nm.
  • the hydrophobic elastic textile is further coated with a hydrophobic compound.
  • the textile can undergo further wet chemical methods for further treatment with hydrophobic compounds.
  • Textiles containing already hydrophobically coated elastic fibres have the advantage of being hydrophobically coated even on the inlying fibres and thus, after additional wet chemical hydrophobic coating coated throughout the entire textile, have a long lasting hydrophobic effect. Insufficient adherence or a decreasing hydrophobic effect through washing and wearing the textile is avoided.
  • the textile has additionally better drying properties after storage in water and an improved wash resistance.
  • the hydrophobic elastic textile comprises covalently coated elastic fibre according to the second aspect of the invention and non-elastic fibres.
  • the non-elastic fibres are hydrophobically, covalently coated prior to being spun into the textile.
  • the non-elastic fibres are covalently coated according to the method of the first aspect of the invention.
  • the textile comprising covalently coated elastic fibres and covalently coated non-elastic fibres has improved hydrophobic properties.
  • the hydrophobic elastic textile comprises covalently coated elastic fibre according to the second aspect of the invention and non-elastic fibres, wherein the non- elastic fibres are hydrophobically, covalently coated prior to being spun into the textile and wherein the hydrophobic elastic textile is further coated with a hydrophobic compound.
  • Additional hydrophobic treatment of the hydrophobic elastic textile using wet chemical methods can improve the grip or the permeability of the textile.
  • the hydrophobic elastic textile comprises covalently coated blended yarn comprising elastic fibre.
  • a fourth aspect of the invention relates to an apparatus for covalent coating of elastic fibre or blended yarn
  • a plasma chamber with at least one plasma zone e. at least one inner bobbin containing the elastic fibre or blended yarn, f. at least one outer bobbin to wind up the elastic fibre or blended yarn, wherein the at least one inner bobbin is localised inside the at least one plasma zone and the outer bobbin is localised outside the plasma chamber.
  • the apparatus allows for an increased processual rate as an increased amount of fibre or yarn can be introduced into a plasma zone by winding on at least one inner bobbin.
  • the plasma chamber with at least one plasma zone is a plasma chamber with at least one inductively coupled plasma zone.
  • the apparatus comprises a source for a coating compound to be uniformly introduced into the plasma zone.
  • the apparatus comprises an argon source used as carrier gas for the coating compound.
  • the apparatus for covalent coating of elastic fibre or blended yarn comprising a. a plasma chamber with one plasma zone, b. one inner bobbin containing the elastic fibre or blended yarn, c. an outer bobbin to wind up the elastic fibre or blended yarn, wherein the inner bobbin is localised inside the plasma zone and the outer bobbin is localised outside the plasma chamber.
  • the apparatus for covalent coating of elastic fibre or blended yarn comprising a. a plasma chamber with two plasma zones, b. six inner bobbins containing the elastic fibre or blended yarn, c. up to six outer bobbins to wind up the elastic fibre or blended yarn, wherein the six inner bobbins are localised inside the plasma zone and the up to six outer bobbins are localised outside the plasma chamber.
  • the throughput using an apparatus comprising six inner bobbins is increased six times compared to an apparatus comprising one inner bobbin.
  • the two plasma zones are located at opposite ends of the plasma chamber.
  • three of the six bobbins are located in one of the two plasma zones and three of the six bobbins are located in the other of the two plasma zones on the opposite side of the plasma chamber.
  • the apparatus has two sources of the coating compound in case the apparatus comprises two plasma zones.
  • a fifth aspect of the invention relates to a covalently coated elastic fibre or covalently coated blended yarn, according to the first aspect of the invention, characterised in that the covalently coated elastic fibre or covalently coated blended yarn has hydrophobic properties.
  • a covalently coated elastic fibre or blended yarn has increased hydrophobic properties and faster drying properties than non-covalently coated elastic fibre or non-covalently coated blended yarn.
  • Fig. 1 shows a covalently coated elastic fibre which was coated in a 10% pre-stretched state in a) its relaxed state showing no adjacent areas and a continuous coating layer; b) its stressed state at 300% stretch showing adjacent areas of on average 2 pm wide portions of the hydrophobic coating transverse to the fibre direction covering around 50% of the fibre surface. SEM images are 60 pm wide.
  • Fig. 2 shows a covalently coated elastic fibre which was coated in a 30% pre-stretched state in a) its relaxed state showing a slight corrugation and 100% coverage of the fibre surface with the hydrophobic coating; b) its stressed state at 300% stretch showing adjacent areas of on average 2 pm wide portions of the hydrophobic coating transverse to the fibre direction covering around 60% of the fibre surface.
  • SEM pictures are a) 120 pm and b) 60 pm wide.
  • Fig. 3 shows a covalently coated elastic fibre which was coated in a 100% prestretched state in a) its relaxed state showing slightly corrugated adjacent areas of the hydrophobic coating interrupted along the fibre direction covering still almost 100% of the fibre surface; b) its pre-stretched state of 100% during the coating process showing a continuous layer of hydrophobic coating; c) its stressed state at 300% stretch showing adjacent areas of on average 5 pm wide portions of the hydrophobic coating transverse to the fibre direction covering around 70% of the fibre surface. SEM pictures are a) 50 pm, b) 60 pm and c) 120 pm wide.
  • Fig. 5 shows a plot of the deposition rate normalized to the gas flow rate of the precursor hexamethyldisiloxane (HMDSO) vs. the energy input, given by power input per HMDSO flow rate for an inductively coupled plasma (ICP) at a pressure of 3 Pa with argon as carrier gas.
  • the optimum deposition rate and hydrophobic properties are observed at the highest point of the linearly increasing deposition rate according to an apparent threshold energy, Eth, here 60 nm/min and 103° water contact angle on a flat reference sample.
  • Eth apparent threshold energy
  • Fig. 6 shows the covalently coated fibre of a textile made of such fibres which were further wrapped with polyamide fibres into a blended covered yarn. The covered yarn was used to produce the textile and said textile was further hydrophobically coated using wet chemical methods. Fig. 6 shows that the covalent coating of the covalently coated elastic fibres is maintained throughout the textile fabrication resulting in a textile with equally hydrophobic properties as the covalently coated elastic fibres. SEM image is 30 pm wide.
  • Fig. 7 shows the covalently coated elastic fibre of a covered yarn, wherein the covered yarn is a blended yarn consisting of covalently hydrophobic coated elastic fibre and covalently hydrophobic coated polyethylene terephthalate (PET) fibre.
  • Fig. 7 shows that the covalent coating of the covalently coated elastic fibres is maintained throughout the textile fabrication resulting in a textile with equally hydrophobic properties as the covalently coated elastic fibres, a) shows the elastic fibres and PET fibres at low resolution; b) shows the elastic fibres at higher resolution. SEM images are a) 1.2 mm and b) 20 pm wide.
  • Fig. 8 shows the drying properties of different hydrophobically treated textiles after 20 min immersion in water.
  • a dendrimer (siloxane-containing) finish and a fluorocarbon (C6) finish applied to a PA/EL (15%) fabric ('orig') is compared to the same fabric containing covalently coated ('CC') elastic fibre with subsequent hydrophobic finish and covalently coated blended covered yarn (PET/EL (15%)) without further hydrophobic finish according to the invention.
  • An elastic fibre made of elastane (EL 78 dtex) is first cleaned in a roll-to-roll process to partly remove the finishing agent and to uncover the fibre surface.
  • the slightly pre-stretched fibres provided on a bobbin are winded through an ultrasonic cleaning bath with following parameters:
  • the fibre is immediately dried with an air dryer at 100°C before winding up on a second bobbin.
  • the fibres Upon winding, the fibres are stretched to 100%.
  • the fibre is re-winded to reach a defined prestretching of 50%, using 60 m/min for the winder and 30 m/min for the take-up reel.
  • the inner bobbin is provided containing the fibre for the coating process.
  • the bobbin carrying the pre-stretched, cleaned and uncoated fibre is centered in front of an inductively-coupled plasma (ICP) source with 80 mm distance.
  • ICP inductively-coupled plasma
  • Plasma excitation frequency of ICP source RF (13. 56 MHz)
  • Fibre length exposed to plasma zone 140 m According to these settings, a nominal coating thickness of 35 nm is observed on the prestretched elastic fibre. Such covalently coated hydrophobic elastic fibres are then used for further textile processes.
  • An elastic fibre made of elastane (EL 78 dtex) is covalently coated according to Example 1.
  • a second, non-elastic uncoated yarn made of polyamide 6.6 (PA 78 dtex x2) is used to cover the covalently coated hydrophobic elastic fibre made of elastane (EL 78 dtex) to produce a blended yarn (PA/EL (15%)).
  • a blended yarn (PET/EL (15%)) is produced similar to Example 2 by using an uncoated elastic fibre made of elastane (EL 78 dtex) and an uncoated non-elastic yarn made of polyethylene terephthalate (PET 78 dtex x2).
  • the blended yarn is first cleaned in a roll-to-roll process according to Example 1.
  • the blended yarn is winded on a bobbin applying a pre-stretching of 200% with respect to the elastic fibre.
  • the bobbin is centered in front of an inductively-coupled plasma (ICP) source with 80 mm distance for the low pressure plasma coating process.
  • ICP inductively-coupled plasma
  • Plasma excitation frequency of ICP source RF (13. 56 MHz)
  • a nominal coating thickness of 40 nm of a hydrophobic coating is observed on the blended yarn.
  • An elastic fibre made of elastane (EL 78 dtex) is covalently coated according to example 1.
  • a second, non-elastic yarn made of polyethylene terephthalate (PET 78 dtex x2) is covalently coated. The yarn is provided as a pre-cleaned yarn, thus not further cleaning is applied.
  • the non-elastic, uncoated yarn is winded without pre-stretching on the inner bobbin for the low pressure plasma coating process, centered in front of an inductively-coupled plasma (ICP) source with 80 mm distance.
  • ICP inductively-coupled plasma
  • Plasma excitation frequency of ICP source RF (13. 56 MHz)
  • the deposition rate is determined on the turning bobbin by placing a masked silicon wafer sample at the position of the fibre and measuring the film thickness after deposition along the edge of the unmasked sample by profilometry. The film thickness on the fiber is then calculated regarding the fibre length exposed to the plasma zone and the velocity of winding.
  • the mass of the deposited coating can be obtained.
  • the film thickness can then be calculated.
  • SEM Scanning Electron Microscopy
  • Washing trials were performed for a duration of 45 minutes at a temperature of 50 degree Celsius using 150 ml of water and 0.25 g of detergent (ECE-98). To simulate five typical washing cycles, steel balls with a diameter of 4 mm were applied to the washing container.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne un procédé de revêtement de fibre élastique ou de fil mélangé comprenant le revêtement de fibre élastique ou de fil mélangé avec un composé de revêtement activé, produisant une fibre élastique revêtue de manière covalente ou un fil mélangé revêtu de manière covalente, la fibre élastique revêtue de manière covalente ou le fil mélangé revêtu de manière covalente étant caractérisé en ce que le revêtement présente une épaisseur de 5 à 200 nm. L'invention concerne en outre une fibre élastique revêtue de manière covalente ou un fil mélangé revêtu de manière covalente, un textile élastique revêtu de manière hydrophobe comprenant une fibre élastique revêtue de manière covalente ou un fil mélangé revêtu de manière covalente. L'invention concerne en outre un appareil de revêtement covalent de fibre élastique ou de fil mélangé.
PCT/EP2024/076685 2023-09-21 2024-09-23 Revêtement hydrophobe de fibres, de fils et de textiles Pending WO2025062043A1 (fr)

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EP23198840.3A EP4528019A1 (fr) 2023-09-21 2023-09-21 Revêtement hydrophobe de fibres, fils et textiles
EP23198840.3 2023-09-21

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WO2025062043A1 true WO2025062043A1 (fr) 2025-03-27

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Citations (6)

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RU2043438C1 (ru) 1992-12-02 1995-09-10 Ивановский научно-исследовательский экспериментально-конструкторский машиностроительный институт Способ обработки длинномерного материала низкотемпературной плазмой и устройство для его осуществления
EP0695384B1 (fr) 1993-04-21 2002-04-03 Maass, Ruth Procede d'enrobage de fils et de fibres dans des objets textiles
US20100035119A1 (en) * 2006-12-20 2010-02-11 Carl Freudenberg Kg Stable temperature plasma treated formation, and method for the production thereof
US20160250831A1 (en) * 2013-10-21 2016-09-01 The North Face Apparel Corp. Functional biomaterial coatings for textiles and other substrates
EP3697958B1 (fr) 2017-10-16 2021-03-10 Werner & Mertz GmbH Procédé de fabrication d'un article textile ayant une surface textile hydrophobisée par traitement plasma et un traitement chimique au mouillé
US20210214887A1 (en) * 2018-05-31 2021-07-15 Xefco Pty Ltd Improved water repellent substrate and application method therefor

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RU2043438C1 (ru) 1992-12-02 1995-09-10 Ивановский научно-исследовательский экспериментально-конструкторский машиностроительный институт Способ обработки длинномерного материала низкотемпературной плазмой и устройство для его осуществления
EP0695384B1 (fr) 1993-04-21 2002-04-03 Maass, Ruth Procede d'enrobage de fils et de fibres dans des objets textiles
US20100035119A1 (en) * 2006-12-20 2010-02-11 Carl Freudenberg Kg Stable temperature plasma treated formation, and method for the production thereof
US20160250831A1 (en) * 2013-10-21 2016-09-01 The North Face Apparel Corp. Functional biomaterial coatings for textiles and other substrates
EP3697958B1 (fr) 2017-10-16 2021-03-10 Werner & Mertz GmbH Procédé de fabrication d'un article textile ayant une surface textile hydrophobisée par traitement plasma et un traitement chimique au mouillé
US20210214887A1 (en) * 2018-05-31 2021-07-15 Xefco Pty Ltd Improved water repellent substrate and application method therefor

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WATERPROOF: "Water Repellent Textiles and Clothing", 2018, ELSEVIER LTD

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