EP4612358A1 - Compositions hydrofuges durables exemptes de fluor et exemptes de silicium à faible empreinte chimique - Google Patents

Compositions hydrofuges durables exemptes de fluor et exemptes de silicium à faible empreinte chimique

Info

Publication number
EP4612358A1
EP4612358A1 EP24824538.3A EP24824538A EP4612358A1 EP 4612358 A1 EP4612358 A1 EP 4612358A1 EP 24824538 A EP24824538 A EP 24824538A EP 4612358 A1 EP4612358 A1 EP 4612358A1
Authority
EP
European Patent Office
Prior art keywords
free
dispersion
polymer
silicon
wax
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24824538.3A
Other languages
German (de)
English (en)
Inventor
Mike Rushforth
Matthias Foessel
Mickael Mheidle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Swiss Performance Chemicals Ag
Original Assignee
Swiss Performance Chemicals Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swiss Performance Chemicals Ag filed Critical Swiss Performance Chemicals Ag
Publication of EP4612358A1 publication Critical patent/EP4612358A1/fr
Pending legal-status Critical Current

Links

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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/17—Natural resins, resinous alcohols, resinous acids, or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/06—Waxes
    • 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
    • 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
    • D06M15/564—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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to novel treatments of fibrous substrates for obtaining a durable water repellent effect .
  • the methods described herein prove to be environmentally friendly and allow the use of renewable starting materials .
  • impregnating dispersions , concentrate dispersions , corresponding kit of parts are disclosed .
  • the invention further provides for novel methods to prepare concentrate dispersions , impregnating dispersions and treatment of fabrics .
  • the fabrics treated with the inventive impregnating dispersions show unexpected beneficial properties , when compared to known treatments . These beneficial properties include improved water repellency, even after multiple washing cycles and for a wide variety of fabrics as well as a low chemical footprint .
  • the thus obtained fabrics are applicable in a wide variety of applications , including outdoor clothing , outdoor equipment and protective clothing .
  • DWR durable water repellent
  • FC DWR systems Fluorocarbon (FC) DWR systems : Until recently, fluorocarbon ( FC ) systems were commonly used because they were highly effective on a wide range of fabrics . Such FC-DWR systems consist of emulsions or dispersions of the FC-polymer in water and typically have an active solids content of approximately 30% w/w . FC systems are typically applied either by a padding or a coating process as outlined below in more detail . However , it has been recognized that low molecular weight impurities associated with the fluoropolymer have serious health implications . Consequently, many maj or commercial brands have stopped using fluorocarbon-based products and there has been an increased demand on alternatives .
  • the open width fabric is saturated with a dilute solution of the FC polymer and is then passed through a mangle , which consists of two synthetic rubber rollers with hydraulic pressure applied to one of the rollers , usually the upper roller , so that excess liquor is squeezed from the fabric .
  • the squeeze pressure is usually adj usted so that the fabric retains between 60- and 100-grams liquor per 100g fabric . This is referred to as the "pick-up" and is important in calculating the amount of product applied to the fabric , or the "treatment level” .
  • the fabric is passed through a stenter frame , where it is held at open width between parallel chains as it passes through a series of drying zones so that the water is removed and the surfaces of the individual yarns , filaments or fibers in the fabric become coated with a very thin film of the hydrophobic fluorocarbon polymer .
  • An alternative method of applying fluorocarbon polymers to fabrics is to use a coating process , in which a continuous film of the fluorocarbon polymer is formed on the surface of the fabric .
  • a thickening agent is added to the fluorocarbon polymer to increase its viscosity and form a paste .
  • knife coating systems are most commonly used in which the paste is applied as a thin layer to one surface of the fabric .
  • the coated fabric is then passed through a stenter frame to dry the film on the surface of the fabric .
  • a cross-linking agent may be added to the fluorocarbon polymer to increase the system' s performance and durability .
  • the cross-linking agent is usually based on blocked isocyanate chemistry, where a polyfunctional isocyanate has been reacted with a blocking agent to produce a product which is inert at room temperature but the isocyanate functionality can be re-activated by heat . Products of this type are commonly referred to as "extenders" .
  • the temperature of zones in the stenter frame can be increased to cause this activation and subsequent cross-linking reactions to occur both within the polymer and between the polymer and fiber surface .
  • Silicon-containing DWR systems DWR systems containing polymers with silicon groups ( -Si ( R2 ) - [O-Si ( R2 ) ] n - are developed for replacing fluorinated DWR systems .
  • silicon is also considered disadvantageous , both from a consumer perspective as well as from an environmental perspective . Consequently, many maj or commercial brands have stopped using silicon-containing products and there has been an increased demand on alternatives .
  • Non-fluorine DWR systems Currently, non-fluorine DWR (NF-DWR) systems which can be applied to textiles are being developed . An important requirement of a NF-DWR treatment is that it can be applied using exactly the same textile processing machinery and procedures used for applying the fluorine-based DWR systems . This will simplify the introduction of the new technology into the industry at minimum cost and this present invention meets these requirements .
  • the wax dispersion used in these traditional DWR systems might have been a synthetic wax , such as a paraffin wax, or a natural wax .
  • a natural wax would be preferred because it increases the biocarbon content and hence the degree of sustainability of the treatment .
  • Beeswax and Carnauba wax are examples of natural waxes which are used in industrial applications to produce water repellent effects on hard surfaces , for example floor and car polishes .
  • paraffin waxes can be used to produce water repellent effects on textiles
  • natural waxes are not commonly used because , in the ways they have been applied previously, they give low levels of performance and lack durability .
  • Sworen et al disclose aqueous dispersions for treating fibrous substrates , comprising a wax and a polymer extender .
  • suitable wax beeswax is proposed .
  • suitable extender specific polyurethane polymers are disclosed which are fully reacted .
  • Schmaunz-Hirsch et al disclose a resorcinol- and formaldehyde-free aqueous dipping composition for coating a textile reinforcing material comprising rubber latex , blocked isocyanate and at least one hydrocarbon wax .
  • the dipping compositions disclosed in Schmaunz-Hirsch et al include non-f luorinated and fluorinated compositions as well as silicon-containing and silicon free compositions .
  • Bartley et al disclose aqueous compositions composed of non-f luorinated Polyurethanes with wax , suitable for the treatment of fibers , such as carpets .
  • the nonfluorinated Polyurethanes according to this document have ( a ) plurality of silicon polyol units and (b ) a plurality of organic polyol units . Accordingly, the compositions disclosed in this document are fluorine-free but silicon-containing .
  • H . Holmquist et al . ( Environment International 91 ( 2016 ) 251-264 255 ) provide an overview on properties , performance and associated hazards of state-of-the-art durable water repellent ( DWR) chemistry for textile finishing .
  • the authors recommend, to choose DWR chemistry on a case-by-case basis , always weighing the benefits connected to increased performance against the ris ks to the environment and human health, until environmentally safe alternatives , which provide the required performance , are available .
  • the present invention relates to impregnating dispersions comprising Candelilla wax and a polymer which does not contain fluorine and does not require an isocyanate containing crosslinking agent to produce a degree of water repellency on a textile substrate as further specified below .
  • Such polymers are subsequently referred to as NF-Polymers .
  • These impregnating dispersions are suitable to obtain a durable water repellent effect on fibrous substrates , they prove to be environmentally friendly, compatible with existing equipment and safe to the user .
  • such impregnating dispersions are also referred to as "treatment liquors" , as they may be directly applied to a suitable substrate . This aspect of the invention shall be explained in further detail below .
  • the impregnating dispersion comprises a continuous phase and a dispersed phase , wherein the continuous phase is an aqueous system and the dispersed phase comprises a wax and a NF Polymer in that the wax is candelilla wax; and the NF Polymer is selected from the group consisting of NF polymers specifically designed to impart some level of water repellency to textile materials .
  • the amount of water in the impregnating dispersion may vary over a broad range , but typically is in the range of 886 - 993 mL/L .
  • Such impregnating dispersions are used in industry, for example in padding processes or coating processes. Such dispersions are often described as "finishing bath" and may contain further components, such as those described below.
  • the impregnating dispersion is fluorine-free, i.e. does not contain fluorine, neither as anion (F-) , nor as covalently bound atom (-F) .
  • the presence / absence of fluorine may be determined by standard methods, such as XPS or combustion IC with pyrohydrolysis and subsequent ion chromatographic determination.
  • the impregnating dispersion is silicon-free i.e. does not contain structural units of formula (I) or of formula (IT) as shown below.
  • the presence / absence of silicone may be determined by standard methods, such as XPS and ED-XRF.
  • Candelilla Wax is a known component identified by CAS 8006-44-8 and E902. It includes the natural product, extracted from plants of the Genus Euphorbia (E.g. Euphorbia antisyphilitica and Euphorbia bracteata) and its synthetic equivalent, known e.g. as Kahlwax 6605.
  • Crude Candelilla wax is obtained by first boiling the dried stalks of a suitable candelilla containing plant in water acidified with sulfuric acid to release the wax. The molten wax is then skimmed off and allowed to solidify and refined by further treatment with sulfuric acid and subsequent passage through filter-presses.
  • Candelilla wax consists primarily of odd-numbered n-alkanes (C29 to C33) , together with esters of acids and alcohols with even-numbered carbon chains (C28 to C34) . Free acids, free alcohols, sterols, neutral resins, and mineral matter are also present. Accordingly, suitable candelilla wax may have a purity as determined by one or more of the following parameters: melting range 68.5 - 72.5 °C, acid value 12 - 22 and saponification value 43 - 65.
  • the inventive dispersion comprises candelilla wax but no other wax as hydrophobe . In this embodiment , other waxes may be present in the additives . In embodiments , the inventive dispersion comprises candelilla wax but no other wax , neither as hydrophobe nor in the additives .
  • Fluorine-free polymers have been developed which produce a degree of water repellency and do not require a blocked isocyanate cross-linking agent to be added to increase their performance and durability .
  • the hydrophobic character of these polymers usually arises from the presence of pendant , non-polar chains of methylene or methyl groups and which may be linear or branched . These side chains are formed on a flexible backbone , which is commonly polyurethane or polyacrylic in nature and the polymer permits a continuous , durable film to be formed on the surface of the fibre .
  • the density of the side chains is such that they can form hydrophobic , crystalline regions which are impervious to water, thereby preventing water from penetrating the structure of either the fibre or the fabric .
  • These non-polar side chains will have an affinity for the non-polar components in the Candelilla wax , thereby helping to increase the permanence of the wax on a textile surface .
  • Suitable NF-Polymers may be characterized by physical parameters , including critical surface energy and water repellency index .
  • the critical surface energy y ( gamma ) is a parameter known in the field and describes the work dW involved in increasing the surface by a length dx . This value may be determined by drawing a Zisman plot .
  • H . Holmquist et al . ( Environment International 91 ( 2016 ) 251-264 255 ) have described the relationship between the chemical composition of DWR treatments , the surface energy associated with the functional groups in the polymer and the degree of repellency . Closepacking of the functional groups gives critical surface energy values ranging from 31mN/m for CH2 groups to 6mN/m for -CF3 groups .
  • the Water Repellency test is a method known in the field, developed by the American Association of Textile Chemists and Colorists (AATCC ) , and described in detail in Test Method 22-2010 , which is technically equivalent to ISO4920 . Briefly, water sprayed against the taut surface of a test specimen under controlled conditions produces a wetted pattern whose size depends on the relative repellency of the fabric . Evaluation is accomplished by comparing the wetted pattern with pictures on a standard chart . Suitable NF-Polymers have a water repellency index of at least Spray 70 when measured according to AATCC 22 standard. Preferably, NF polymers have a Spray 80 or higher.
  • NF polymers are selected from the group of polyacrylates, poly (meth) acrylates and polyurethanes, preferably polyacrylates or poly (meth) acrylates .
  • Suitable NF-polymers are free of fluorine (ii) free of blocked isocyanate cross-linkers.
  • NF-polymers show a critical surface energy of X28mN/m or a water repellency index of at least Spray 70 when measured according to AATCC 22 standard.
  • NF-polymers show a critical surface energy of 20-28mN/m and a water repellency index of at least Spray 80 when measured according to AATCC 22-2010 standard.
  • the NF-polymer according to this invention is silicon-free.
  • a silicon-free NF-Polymer is a NF- polymer as described herein, not containing silicon groups of formula (I)
  • R 1 to R 4 independently represent alkyl, alkyl- O- , cycloalkyl, cycloalkyl-O- , aryl, or aryl-O-, in each case optionally substituted.
  • Further Components / additives As known in the field, further functional components may be included, such as pH adjusting agents (e.g. acid or buffer) , emulsifiers (e.g .non-ionic emulsifier) , biocides, softeners or wetting agents. These components are commercial items and may be selected in compliance with the specific application and included in amount conventional in the field.
  • wetting agent is included or used during impregnation.
  • one or more emulsifiers and one or more wetting agents and one or more pH adjusting agents are included or used during impregnation.
  • all further components are fluorine-free. Fluorine- free components do not contain the element fluorine, neither covalently bound (-F) nor ionic (F-) .
  • all further components are silicon-free. free components do not contain silicon groups of formula (II)
  • the finishing bath contains the above components (wax + NF-Polymer and optional further components) in comparatively low amounts, typically 8 wt % or less, preferably 5 wt% or less.
  • the remainder being the aqueous system, preferably water.
  • the concentration can be adjusted by the skilled person, depending on the fabrics to be treated, the equipment used and the treatment conditions applied.
  • the ratio of wax : NF-Polymer is typically in the range of 10:1 to 1:10 (w/w) , such as 5:1 to 1:5 (w/w) .
  • the "pick-up" as described previously is 70%. If the pickup value is higher or lower then the amounts of the components in the finishing bath will have to be increased or decreased accordingly.
  • the finishing bath is typically obtained by diluting the concentrate described below (2 nd aspect) with a dilution factor of 3 - 60.
  • the inventive dispersion is fluorine-free. Thus, none of its components, the wax, the NF- Polymer, the optional additives contain fluor. It was found that the inventive dispersions are as performant as fluorinated dispersions and may thus replace currently used dispersions. Typically, the manufacturing equipment currently in place may be used, optionally by adapting process parameters.
  • concentrates and kits of part as discussed herein, lacking fluor are referred to as "fluorine free concentrates" and "fluroine free kits of part”.
  • the inventive dispersion is preferably silicon-free.
  • the wax, the NF-Polymer, the optional additives contain silicon groups (I) and (II) shown above. It was found that the inventive dispersions are as performant as silicon-containing dispersions and may thus replace currently used dispersions. Typically, the manufacturing equipment currently in place may be used, optionally by adapting process parameters .
  • the invention relates to an impregnating dispersion comprising a continuous phase and a dispersed phase , wherein the continuous phase is an aqueous system and the dispersed phase comprises a wax and a NF-Polymer, characterized in that the wax is Candelilla wax ; the NF-Polymer is selected from the group of polyacrylates , and poly (meth) acrylates ; and is free of fluorine ; and is free of blocked isocyanate cross-linkers ; and shows a critical surface energy of 28mN/m or less , for example 21-23mN/m, (when determined by a Zisman plot ) and a water repellency index of at least Spray 80 (when measured according to AATCC 22 standard) ; and the amount of dispersed phase (wax + NF-Polymer + optional further components ) is 8 wt% or less .
  • the wax is Candelilla wax
  • the NF-Polymer is selected from the group of polyacryl
  • the present invention relates to concentrate dispersions comprising Candelilla wax and NF-Polymer as further specified herein and a kit of parts comprising Candelilla wax and NF- Polymer as further specified herein .
  • concentrate dispersions and kit of parts are suited to prepare the impregnating dispersions described herein and prove to be valuable commercial items , ready for use in textile industry . This aspect of the invention shall be explained in further detail below .
  • the invention provides for a concentrate dispersion comprising Candelilla wax , NF-Polymer and further components ( additives ) , all of which are as described in the 1 st aspect of the invention (forming a dispersed phase ) , the remaining part being water ( forming a continuous phase ) in an amount of 450 - 990 mL/L .
  • the concentrates as described herein distinguish from the impregnating dispersions essentially in the water content . While the concentrates have a low water content , making them more efficient for transportation and storage , the impregnating dispersions are adapted to the machinery used in textile industry .
  • concentration is chosen as high as possible for efficiency reasons , but at the same time to ensure stability and dispersibility .
  • the concentration of candelilla wax in the concentrate dispersion is in the range of 1 - 55% (w/w) .
  • the concentration of candelilla wax in the concentrate dispersion is in the range of 10 - 40% (w/w ) .
  • the concentration of candelilla wax in the concentrate dispersion is 30% .
  • the amount of water in the concentrate dispersion is in the range of 450-990 mL/L, preferably 600- 900 mL/L . In an exemplary embodiment , the amount of water in said concentrate dispersion is 700 mL/L .
  • the concentrate dispersion is free of fluorine and preferably free of silicone .
  • the invention provides for a kit of parts comprising a first and a second container (first and second drum) .
  • Said first container comprising a 1 st composition, said 1 st composition comprising a Candelilla wax as defined herein, water , optionally pH adj usting agents , biocides , wetting agents and emulsifiers as defined herein .
  • Concentrations of candelilla wax in said first container are typically in the same range as discussed above .
  • Said second container comprising a 2 nd composition, the 2 nd composition comprising an NF-Polymer as defined herein, preferably in the form of an aqueous dispersion .
  • kit of parts comprising two concentrates may be provided . Separating the wax from the NF-Polymer may be beneficial in the textile industry, as shelf life is increased and a higher degree of flexibility is provided .
  • the kit of parts is combined with water in appropriate amounts to obtain an impregnating dispersion .
  • the kit of part comprises in a first container Candelilla wax dispersion and in a second container a NF- Polymer . It is believed this embodiment provides for product of ultimate performance .
  • the kit of part comprises in a first container Candelilla wax and in a second container a NF- Polymer which is bio-based ( i . e . contains a bio-based carbon content of at least 50% when applying ASTM D6866 method B ) . It is believed this embodiment provides for a particularly environmentally friendly product .
  • the invention also pertains to corresponding uses as outlined below :
  • the invention relates to the use of a dispersions and kit of parts as defined herein, for impregnating / treating fibrous substrates , including fabrics or textile products as disclosed herein .
  • the invention relates to the use of Candelilla wax in combination with a NF-Polymer as described herein as an impregnating material .
  • the invention relates to the use of Candelilla wax in combination with a NF-Polymer as described herein and in combination with a wetting agent or an emulsifier or a pH adj usting agent ( typically an acid ) , as an impregnating material .
  • the invention relates to the use of a kit of parts as described herein for preparing an impregnating dispersion as described herein .
  • the present invention relates to textile products having a durable water repellent properties . These valuable properties are obtained, as the textile surface contains Candelilla wax and NF- Polymer as described herein . This aspect of the invention shall be explained in further detail below .
  • the impregnating dispersions disclosed herein are suitable for use in textile industry .
  • a large variety of fibrous substrates may be treated .
  • Such substrates include fibers , yarns , fabrics (woven, non-woven and knitted) and finished products (such as clothing, e . g . j eans , sportswear ) , collectively products of textile industry or textile products .
  • the invention provides for a textile product , comprising a fibrous support material and a coating, wherein the coating comprises candelilla wax and NF Polymer as defined in the 1 st aspect of the invention .
  • the coating may be present as a layer on the fibrous support .
  • the total amount of Candelilla wax and NF-Polymer and optional further components on said textile product may vary over a broad range .
  • 0.5 - 8 wt% total of [Candelilla wax + NF-Polymer + optional additives, if present] on said textile product result in suitable DWR properties.
  • the ratio of Candelilla to NF-Polymer can be adjusted by the skilled person.
  • 1 - 5 wt% Candelilla wax are present on said textile product to thereby obtain beneficial DWR properties.
  • the support material is selected from cellulose-based materials (e.g. cotton, viscose) , wool, polyesters and polyamides and yarn or fibre blends of these materials.
  • the textile product is a finished product.
  • such textile product is selected from sportswear garments and outdoor garments and outdoor equipment and protective clothing .
  • the textile product is a fabric selected from knits, non-woven fabrics and woven fabrics .
  • the textile product is a spun yarn or filament.
  • Such products may be present in the form of a hank or a package or a continuous web.
  • the present invention relates to methods for manufacturing impregnating dispersions, concentrate dispersions, and kit of parts as described herein, particularly 1 st and 2 nd aspect of the invention.
  • Such manufacturing methods rely on process steps known per se, but not yet applied to the specific starting materials and components described herein. This aspect of the invention shall be explained in further detail below.
  • the invention provides for a method to manufacture an impregnating dispersion as described herein, the method comprising, either (i) combining a concentrate dispersion as described herein with water or an aqueous composition or (ii) combining a 1 st and 2 nd composition of a kit of parts as described herein with water or an aqueous composition.
  • the impregnating dispersion is obtained by dilution of a suitable starting material with water as it is conventional in the field.
  • the sequence of adding the components may be determined by a person skilled in the art. Often, the water is provided first, and concentrate or 1 st and 2 nd composition are subsequently added while stirring the whole mixture. Temperature may be controlled, but typically room temperature is sufficient.
  • the invention provides for a method to manufacture a concentrate dispersion as described herein, the method comprising , ( x ) providing a 1 st composition and a 2 nd composition as described herein; ( y) combining said 1 st and 2 nd dispersion, optionally by controlling temperature between 3 and 70 ° C to thereby obtain a liquid composition; and optionally ( z ) diluting the thus obtained liquid composition with water, or an aqueous solution comprising additives as described herein, to thereby obtain said concentrate dispersion .
  • the invention provides for a method to manufacture a Candelilla wax dispersion (" 1 st composition" ) as described herein .
  • Candelilla wax is solid at room temperature , but as detailed below, aqueous dispersions are formed by high shear mixing Candelilla wax in water heated to a temperature above the melting point of the candelilla wax and containing emulsifying agents to form a dispersion and then flash chilling ( quenching ) the mixture .
  • flash chilling quenching
  • one method for obtaining the 1 st composition comprises the steps of ( i ) dissolving emulsifier ( s ) in water and heating the aqueous composition to 70 - 90 ° C; ( ii ) adding candelilla wax, approx . 10 wt% ; ( iv) emulsifying the thus obtained composition, e . g . by applying high sheer forces ; (v) quenching the thus obtained emulsion to thereby obtain the 1 st composition as disclosed herein .
  • the present invention relates to methods for manufacturing textile products having a durable water repellent effect , particularly to the textile products described in the 3 rd aspect of this invention . It is considered particularly beneficial that such manufacturing methods rely on process steps known per se and machinery already used in industry . However , such method steps have not yet been applied to the specific starting materials described herein, particularly 1 st and 2 nd aspect above . This aspect of the invention shall be explained in further detail below .
  • the impregnating dispersion may be applied on all levels of textile industry, ie . substrates selected from ( i ) yarns or fibers or filaments ; ( ii ) knitted, woven or non-woven fabrics ; ( iii ) finished products .
  • the invention provides for a method for manufacturing a fabric , the method comprising the steps of ( a ) providing knitted, woven or non-woven fabric to be coated; followed by (b) coating or padding using the impregnating dispersion described in the first aspect of the invention; followed by (c) drying and curing; and optionally followed by (d) further finishing steps as conventional in the field to thereby obtain a coated fabric.
  • These method steps are known per se, but not yet applied in the context of an impregnating dispersion as described herein (i.e. comprising Candelilla wax and one of the specific blocked isocyanates) .
  • the manufacturing is continuous process .
  • Step (a) The material to be coated is, in its broadest sense, a fibrous substrate.
  • a fibrous substrate contains an initial coating.
  • such substrate is free of a coating. It is considered beneficial that the inventive coating dispersion may be applied to both, coated and non-coated substrates.
  • fibrous substrate includes filaments, fibers, yarns, nonwoven fabrics, and woven fabrics.
  • Step (b) This step process steps already applied in textile industry, such as coating and padding.
  • a dispersion concentrate as described in the 2 nd aspect contains 20 % (w/w) Candelilla wax. This concentrate is diluted to obtain the impregnating dispersion ("treatment liquor") containing 150 g/L of said concentrate. This treatment liquor is applied to the material of step (a) using a pick - up of 70% (w/w) .
  • Step (c) This step preferably includes squeezing to remove excess dispersion from the substrate.
  • an amount of Candelilla wax is 2.1% owf obtained.
  • Step (d) This drying step is preferably performed at increased temperatures, e.g. least 120° for at least 30 sec. to remove excess water from the substrate, leaving a thin coating of the concentrate on the substrate .
  • the invention provides for a method of manufacturing a textile product, preferably by garment dip process, the process comprises (a) providing a textile product to be treated; followed by (b) dipping, spraying or washing the product by using the impregnating dispersion described herein, 1 st aspect of the invention; followed by (c) drying and curing; and optionally followed by (d) further finishing steps; to thereby obtain a treated textile product.
  • Step (a) The product to be treated is, in its broadest sense, a textile product, such as a piece of clothing, e.g. a pair of jeans.
  • a product to be treated includes a product to be finished or to be coated .
  • the product supplied to step ( a ) may already contain an initial coating .
  • Step (b) This process step uses treatment steps already applied in the textile industry, such as dipping or washing .
  • a dispersion concentrate as described in the 2 nd aspect contains 20 % (w/w ) Candelilla wax .
  • This concentrate is diluted to obtain the impregnating dispersion ("treatment liquor" ) containing 150 g/L of said concentrate .
  • treatment liquor is applied to the textile product of step ( a ) to obtain a pick - up of 70% (w/w) .
  • Step (c) is performed as discussed above .
  • an amount of candelilla wax is 2 . 1% of on said textile product obtained .
  • the resulting composition was emulsified with Ultraturrax (T25 disperser tool ) at 11 ' 000 rpm for 1 minute , while heating continued .
  • Ultraturrax T25 disperser tool
  • the thus obtained emulsion was poured in a precooled glass bottle ( refrigerator ) and cooled down in ice-bath or refrigerator .
  • the blocked isocyanate used ( "Extender TTL” ) was added to the dispersion after the quenching step referred to above .
  • the aqueous dispersion of the blocked isocyanate was added slowly to the wax dispersion using the Ultraturrax (T25 disperser tool ) .
  • the NF-Polymer (Unidyne XF 5007 ) was added in a similar way .
  • the samples were dried for 1 minute at 100°C and then for 1 minute at 160°C ( fabric surface temperature ) .
  • the samples were weighed dry before treatment and then after padding, in order to be able to calculate the pick-up and treatment level .
  • the DWR performance of the treatments was measured using the AATCC Test Method 22-2010 .
  • the durability of the treatment was measured by wash-testing the samples in a front-loading washing machine , Siemens IQ300 according to Test Method EN ISO 6330 ( 5A) in which a 2Kg load is washed using a 5A ( 40°C ) wash cycle .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention se rapporte à des traitements de substrats fibreux permettant d'obtenir un effet hydrofuge durable. Les procédés décrits s'avèrent être respectueux de l'environnement et permettent l'utilisation de matières premières renouvelables. Plus particulièrement, l'invention concerne des dispersions d'imprégnation, des dispersions de concentré, un kit de pièces correspondant, comprenant chacune de la cire de candelilla et un polymère NF qui est exempt d'un allongeur à base d'isocyanate, et exempt de fluor, et a de préférence une énergie de surface critique de 20 à 28 mN/m et/ou un indice d'hydrophobie d'au moins Spray 70. L'invention concerne en outre des procédés de préparation de dispersions de concentré, d'imprégnation de dispersions et de traitement de tissus. Les tissus traités avec les dispersions d'imprégnation selon l'invention présentent des propriétés bénéfiques inattendues, par comparaison avec des traitements connus et comprennent un caractère hydrofuge amélioré, même après de multiples cycles de lavage et pour une grande variété de tissus. Les tissus ainsi obtenus sont applicables dans une grande variété d'applications, y compris des vêtements d'extérieur et des vêtements de protection.
EP24824538.3A 2023-12-13 2024-12-11 Compositions hydrofuges durables exemptes de fluor et exemptes de silicium à faible empreinte chimique Pending EP4612358A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23216463.2A EP4570984A1 (fr) 2023-12-13 2023-12-13 Compositions hydrofuges durables sans fluor à faible empreinte chimique
PCT/EP2024/085723 WO2025125350A1 (fr) 2023-12-13 2024-12-11 Compositions hydrofuges durables exemptes de fluor et exemptes de silicium à faible empreinte chimique

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EP4612358A1 true EP4612358A1 (fr) 2025-09-10

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EP24824538.3A Pending EP4612358A1 (fr) 2023-12-13 2024-12-11 Compositions hydrofuges durables exemptes de fluor et exemptes de silicium à faible empreinte chimique

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US8716392B2 (en) * 2012-04-19 2014-05-06 Arrowstar Llc Nonfluorinated polyurethanes and methods of making and using thereof
KR20250044797A (ko) 2014-06-12 2025-04-01 더 케무어스 컴퍼니 에프씨, 엘엘씨 표면 효과 조성물을 위한 왁스 및 우레탄계 증량제 블렌드
TWI686439B (zh) * 2014-07-04 2020-03-01 瑞士商亞克羅瑪智財公司 不含氟之拒水性組成物
US10308898B2 (en) * 2014-09-26 2019-06-04 The Chemours Company Fc, Llc Method of imparting water repellency with non-fluorinated laundry treatment compositions
WO2017218527A1 (fr) * 2016-06-14 2017-12-21 Carbtex Technology, Inc. Fibres de coton résistant à l'inflammation
KR102410074B1 (ko) * 2016-09-23 2022-06-20 훈츠만 텍스틸레 에펙츠 (게르마니) 게엠베하 텍스타일 직물의 마감가공용 불소-비함유 수성 분산액
EP3702522A1 (fr) 2019-03-01 2020-09-02 Continental Reifen Deutschland GmbH Composition aqueuse de trempage

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WO2025125350A1 (fr) 2025-06-19
EP4570984A1 (fr) 2025-06-18

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