Fluorine-free and silicon-free durable waterproof composition with low chemical footprint

Abstract

The invention relates to the treatment of fibrous substrates for obtaining durable waterproof effects. The described method is demonstrated to be environmentally friendly and allows the use of renewable starting materials. Specifically disclosed are impregnation dispersions, concentrate dispersions, corresponding kits, each comprising candelilla wax and an NF-polymer that is free of isocyanate-based extenders and fluorine, and preferably has a critical surface energy of from 20 mN / m to 28 mN / m and / or a water repellency index of at least Spray 70. Methods for preparing the concentrate dispersion, impregnating the dispersion, and treating a fabric are also provided. Fabrics treated with the impregnation dispersion of the present invention exhibit unexpected beneficial properties and include improved water repellency when compared to known treatments, even after multiple wash cycles and for a wide variety of fabrics. The fabrics thus obtained can be used in a wide variety of applications, including outdoor garments and protective garments.

Description

[0001] Overview

[0002] The present invention relates to a novel treatment for fiber substrates for achieving a durable water-repellent effect. The methods described herein are shown to be environmentally friendly and allow the use of renewable starting materials. Specifically, impregnation dispersions, concentrate dispersions, and corresponding kits are disclosed. The present invention also provides novel methods for preparing concentrate dispersions, impregnation dispersions, and treating fabrics. Fabrics treated with the impregnation dispersions of the present invention exhibit unexpectedly beneficial properties when compared to known treatments. These beneficial properties include improved water repellency and a low chemical footprint, even after multiple wash cycles and for a wide variety of fabrics. The resulting fabrics can be used in a wide variety of applications, including outdoor clothing, outdoor gear, and protective clothing. Background Art

[0003] Applying a durable water repellent (DWR) treatment to fabrics is a process widely used in the textile industry to produce high-performance outdoor clothing, outdoor gear, and protective apparel. Generally speaking, these treatments can be categorized into fluorocarbon (FC) DWR systems and non-fluorocarbon DWR systems. The most widely used application processes are padding and coating.

[0004] Fluorocarbon (FC) DWR Systems: Until recently, fluorocarbon (FC) systems were commonly used due to their effectiveness on a wide variety of fabrics. Such FC-DWR systems consist of an emulsion or dispersion of an FC polymer in water and typically have an active solids content of approximately 30% w / w. FC systems are typically applied via a padding or coating process, as outlined in more detail below. However, low-molecular-weight impurities associated with fluoropolymers have been recognized to have serious health effects. Consequently, many major commercial brands have discontinued the use of fluorocarbon-based products, and demand for alternatives has increased.

[0005] In the padding process, an open-width fabric is saturated with a dilute solution of FC polymer and 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) to squeeze excess liquid out of the fabric. The squeeze pressure is typically adjusted so that the fabric retains 60 to 100 grams of liquid per 100 grams of fabric. This is known as "pick-up" and is important when calculating the amount of product applied to the fabric, or the "treatment level." The fabric is passed through a tenter frame, where it is held open width between parallel chains as it passes through a series of drying zones, allowing water to be removed and the surfaces of the individual yarns, filaments, or fibers in the fabric to become coated with a very thin film of the hydrophobic fluorocarbon polymer.

[0006] An alternative method for applying fluorocarbon polymers to fabrics is to use a coating process, in which a continuous film of fluorocarbon polymer is formed on the surface of the fabric. A thickener is added to the fluorocarbon polymer to increase its viscosity and form a paste. There are many different types of coating processes, but the doctor blade system is the most common, in which the paste is applied in a thin layer to one surface of the fabric. The coated fabric is then passed through a tenter frame to dry the film on the fabric surface.

[0007] Additionally, crosslinkers can be added to fluorocarbon polymers to enhance the performance and durability of the system. Crosslinkers are typically based on blocked isocyanate chemistry, where a polyfunctional isocyanate reacts with a blocking agent to produce a product that is inert at room temperature, but whose isocyanate functionality can be reactivated by heat. This type of product is often referred to as an "extender." The temperature of a zone in the tenter frame can be elevated to induce this activation and subsequent crosslinking reactions within the polymer and between the polymer and the fiber surface.

[0008] Silicone-containing DWR system: a system containing a silicon group (-Si(R2)-[O-Si(R2)] n Silicone-based DWR systems are being developed to replace fluorinated DWR systems. However, silicones are also considered undesirable from both a consumer and environmental perspective. As a result, many major commercial brands have stopped using silicone-containing products, and demand for alternatives has increased.

[0009] Non-Fluorine DWR Systems: Currently, non-fluorine DWR (NF-DWR) systems are being developed that can be applied to textiles. An important requirement for NF-DWR treatments is that they can be applied using the exact same textile processing machinery and procedures used to apply fluorine-based DWR systems. This would simplify the introduction of new technologies into the industry with minimal cost, and the present invention meets these requirements.

[0010] Traditionally, water repellency has been achieved on textile products by using coating techniques to melt wax onto the fabric or by applying the wax from an aqueous dispersion. However, unlike FC-DWR systems, traditional wax-based systems are not very durable. Recently, in the development of NF-DWR systems, methods to improve the durability of wax-based systems have been investigated.

[0011] The wax dispersions used in these traditional DWR systems may be synthetic waxes, such as paraffin wax, or natural waxes. In the development of NF-DWR systems, natural waxes will be preferred because they increase the biochar content and thus improve the sustainability of the treatment. Beeswax and carnauba wax are examples of natural waxes that are used in industrial applications to create a water-repellent effect on hard surfaces, such as floor and car polishes. While paraffin wax is well known for creating a water-repellent effect on textiles, natural waxes are not commonly used because they provide low performance levels and lack durability in the manner in which they have been used previously.

[0012] The above-mentioned general aspects concerning systems for impregnating fibers / textiles are described in more detail in the documents indicated below:

[0013] For example, Sworen et al. (WO2015 / 191326) discloses an aqueous dispersion for treating fiber substrates comprising a wax and a polymer extender. Beeswax is suggested as a suitable wax. A specific fully reacted polyurethane polymer is disclosed as a suitable extender. While suitable, the results obtained and indicated in Table 4 of this document are considered insufficient for many applications. This document proposes a padding process using an aqueous dispersion. It should be noted that the polyurethane extender mentioned by Sworen et al. is completely different in chemical structure and behavior from the NF-polymer system according to the present invention.

[0014] In addition, Schmaunz-Hirsch et al. (EP3702522) discloses a resorcinol- and formaldehyde-free aqueous impregnation composition for coating textile reinforcement materials, which comprises rubber latex, blocked isocyanate, and at least one hydrocarbon wax. The impregnation compositions disclosed by Schmaunz-Hirsch et al. include non-fluorinated and fluorinated compositions, as well as silicon-containing and silicon-free compositions.

[0015] In addition, Bartley et al. (US2013 / 0281606) discloses an aqueous composition composed of a non-fluorinated polyurethane containing a wax, which is suitable for treating fibers such as carpets. According to this document, the non-fluorinated polyurethane has (a) a plurality of silicone polyol units and (b) a plurality of organic polyol units. Therefore, the composition disclosed in this document is fluorine-free but contains silicone.

[0016] In addition, H. Holmquist et al. (Environment International 91 (2016) 251-264 255) provide an overview of the characteristics, performance, and associated hazards of state-of-the-art durable water repellent (DWR) chemicals used for textile finishing. The authors recommend that DWR chemicals be selected on a case-by-case basis, always weighing the benefits associated with improved performance against the risks to the environment and human health until environmentally safe alternatives that provide the desired performance become available.

[0017] Clearly, there is a need to provide improved DWR systems. In particular, such systems should target the performance of FC-DWR systems, but avoid the health and / or environmental impacts. Furthermore, it would be beneficial if such systems could be used with already available machinery, facilitating the transition to such new systems.

[0018] One or more of the above objects are achieved by the impregnation dispersion described in claim 1. Further aspects of the invention are disclosed in the description and the independent claims, and preferred embodiments are disclosed in the description and the dependent claims. The invention thus provides:

[0019] ● In a first aspect, an impregnation dispersion suitable for obtaining a durable water repellent effect on textile and fiber substrates;

[0020] ● In a second aspect, a concentrate dispersion and kit for preparing the above impregnation dispersion;

[0021] ● In a third aspect, a textile product having durable water-repellent properties;

[0022] ● In a fourth aspect, a method for making the impregnation dispersion, concentrate dispersion, and kit;

[0023] ● In a fifth aspect, a method for making a textile product having a durable water repellent effect.

[0024] The present invention will be described in more detail below.It should be understood that multiple embodiments, preferred embodiments and scopes as provided / disclosed in this specification can be combined arbitrarily.Specifically, "preferred" scopes can be combined, and "particularly preferred scopes can be combined".In addition, depending on the specific embodiment, the selected definition, embodiment or scope may not be applicable.As used herein, unless otherwise indicated in this article or clearly contradictory with the context, the terms "one", "a kind of", "said" and similar terms used in the context of the present invention (especially in the context of the claims) should be understood to cover both the singular and the plural.The term "comprises / includes" should cover "comprises / includes", "essentially consisting of" and "consisting of". DETAILED DESCRIPTION

[0025] exist First aspect The present invention relates to impregnation dispersions for imparting a degree of water repellency to textile substrates. These dispersions comprise candelilla wax and a polymer that contains no fluorine and does not require an isocyanate-containing crosslinking agent, as further described below. Such polymers are subsequently referred to as NF-polymers. These impregnation dispersions are suitable for achieving a durable water repellency effect on fiber substrates and are proven to be environmentally friendly, compatible with existing equipment, and safe for users. In industry, such impregnation dispersions are also referred to as "treatment fluids" because they can be applied directly to suitable substrates. This aspect of the invention will be described in further detail below.

[0026] Advantageously, the impregnation 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, characterized in that the wax is candelilla wax; and the NF polymer is selected from NF polymers specifically designed to impart a certain level of water repellency to textile materials. The amount of water in the impregnation dispersion can vary within a wide range, but is typically in the range of 886 mL / L to 993 mL / L. Such impregnation dispersions are used in industry, for example, in padding or coating processes. Such dispersions are often described as "finishing baths" and may contain additional components, such as those described below. It was unexpectedly discovered that a high level of water repellency can be achieved using a candelilla wax dispersion if applied to a fabric in combination with a specific NF polymer as disclosed herein. This result was unexpected, as candelilla wax only produces a low level of repellency when applied without the NF polymer, and the NF polymer alone produces a lower repellency effect in the absence of the wax. A true synergistic effect was observed. Even more surprising is that other natural waxes such as carnauba wax do not show these significant effects.

[0027] Advantageously, the impregnation dispersion is fluorine-free, i.e., contains neither fluorine as anion (F-) nor fluorine as a covalently bound atom (-F). The presence / absence of fluorine can be determined by standard methods, such as by XPS, or combustion IC via pyrolysis and subsequent ion chromatography.

[0028] Advantageously, the impregnation dispersion is silicon-free, ie does not comprise structural units of formula (I) or (II) as shown below. The presence / absence of silicones can be determined by standard methods such as XPS and ED-XRF.

[0029] Candelilla wax: Candelilla wax is a known component identified by CAS 8006-44-8 and E 902. It includes natural products extracted from plants of the genus Euphorbia (e.g., Euphorbia antisyphilitica and Euphorbia bracteata) and its synthetic equivalents, known as, for example, Kahlwax 6605.

[0030] Crude candelilla wax is obtained by first boiling the dried stems of a suitable candelilla wax-containing plant in water acidified with sulfuric acid to release the wax. The molten wax is then skimmed off, allowed to solidify, and refined by further treatment with sulfuric acid and subsequently passing through a filter press.

[0031] Candelilla wax is primarily composed of odd-numbered n-alkanes (C29 to C33) and esters of acids and alcohols with even-numbered carbon chains (C28 to C34). Free acids, free alcohols, sterols, neutral resins, and minerals are also present. Thus, suitable candelilla wax may have a purity as determined by one or more of the following parameters: a melting range of 68.5°C to 72.5°C, an acid number of 12 to 22, and a saponification number of 43 to 65.

[0032] In an embodiment, the dispersion of the present invention comprises candelilla wax but does not comprise other waxes as hydrophobes. In this embodiment, other waxes may be present in the additives. In an embodiment, the dispersion of the present invention comprises candelilla wax but does not comprise other waxes as hydrophobes nor in the additives.

[0033] NF-Polymers: Fluorine-free polymers have been developed that impart a degree of water repellency and do not require the addition of blocked isocyanate crosslinkers to enhance performance and durability. The hydrophobic character of these polymers typically stems from the presence of pendant nonpolar chains of methylene or methyl groups, which can be linear or branched. These side chains are formed on a flexible backbone, typically polyurethane or polyacrylic in nature, and allow the polymer to form a continuous, durable film on the surface of the fiber. The density of the side chains allows them to form impermeable, hydrophobic crystalline regions, preventing water from penetrating the fiber or fabric structure. These nonpolar side chains have an affinity for the nonpolar components of candelilla wax, thereby contributing to the wax's durability on the textile surface.

[0034] Suitable NF-polymers can be characterized by physical parameters including critical surface energy and water repellency index.

[0035] The critical surface energy γ (gamma) is a parameter known in the art and describes the work dW required to increase the length dx of a surface. This value can be determined by plotting a Zisman plot. For example, H. Holmquist et al. (Environment International 91 (2016) 251–264 255) describe 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. Close packing of functional groups results in critical surface energy values ranging from 31 mN / m (for CH2 groups) to 6 mN / m (for -CF3 groups).

[0036] The water repellency test is a method known in the art and was 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 ISO 4920. Briefly, water is sprayed onto the taut surface of a test specimen under controlled conditions to produce a wetting pattern whose size depends on the relative repellency of the fabric. Evaluation is performed by comparing the wetting pattern to an image on a standard chart. Suitable NF-polymers have a water repellency index of at least Spray 70 when measured according to AATCC 22. Preferably, NF polymers have a Spray 80 or higher.

[0037] Products of this type are commercially available and examples include Zelan R3 (Chemours) which is based on a polyurethane backbone and Unidyne XF 5007 (Daikin) which is based on a polyacrylate backbone.

[0038] Thus, the NF polymer is selected from polyacrylates, poly(meth)acrylates, and polyurethanes, preferably polyacrylates or poly(meth)acrylates. Suitable NF-polymers are free of fluorine (ii) and free of blocked isocyanate crosslinkers. In an embodiment, the NF-polymer exhibits a critical surface energy of ≤28 mN / m or a water repellency index of at least Spray 70 when measured according to AATCC 22-2010. In an embodiment, the NF-polymer exhibits a critical surface energy of 20 mN / m to 28 mN / m and a water repellency index of at least Spray 80 when measured according to AATCC 22-2010.

[0039] Silicon-free polymers: Advantageously, the NF-polymers according to the present invention are silicon-free. Silicon-free NF-polymers are NF-polymers as described herein, which do not contain silicon groups of formula (I)

[0040]

[0041] where y is 1 to 100, and R 1 to R 4 independently represents alkyl, alkyl-O-, cycloalkyl, cycloalkyl-O-, aryl or aryl-O-, in each case optionally substituted.

[0042] Additional Components / Additives: As is known in the art, additional functional components such as pH adjusters (e.g., acids or buffers), emulsifiers (e.g., nonionic emulsifiers), biocides, softeners, or wetting agents may be included. These components are commercially available and can be selected based on the specific application and included in amounts conventional in the art. In one advantageous embodiment, a wetting agent is included or used during the impregnation. In another advantageous embodiment, one or more emulsifiers, one or more wetting agents, and one or more pH adjusters are included or used during the impregnation.

[0043] Advantageously, all further components are fluorine-free. Fluorine-free components do not contain elemental fluorine, neither covalently bound (-F) nor ionic (F - ).

[0044] Advantageously, all further components are silicon-free. The silicon-free components do not contain silicon groups of formula (II)

[0045]

[0046] wherein the substituents are as defined above in formula (I).

[0047] Concentration: The finishing bath contains the above components (wax + NF-polymer and optional additional components) in relatively low amounts (typically 8 wt% or less, preferably 5 wt% or less). The remainder is an aqueous system, preferably water. The skilled artisan can adjust the concentration depending on the fabric to be treated, the equipment used, and the treatment conditions applied. The wax:NF-polymer ratio is typically in the range of 10:1 to 1:10 (w / w), for example, 5:1 to 1:5 (w / w).

[0048] Suitably, the "wet pick-up" as previously described is 70%. If the wet pick-up value is higher or lower, the amount of components in the finishing bath will have to be increased or decreased accordingly.

[0049] The finishing bath is usually obtained by diluting the below-described concentrate (second aspect) at a dilution factor of 3 to 60.

[0050] Fluorine-Free Dispersions: As mentioned above, the dispersions of the present invention are fluorine-free. Thus, none of their components (wax, NF polymer, optional additives) contain fluorine. The dispersions of the present invention have been found to perform just as well as fluorinated dispersions and, therefore, can replace currently used dispersions. Generally, currently available manufacturing equipment can be used, optionally by adjusting process parameters.

[0051] Similarly, the absence of fluorine (i.e., covalently bound fluorine-F and fluoride ion F) as described herein - ) are referred to as "fluoride-free concentrates" and "fluoride-free kits."

[0052] Silicon-Free Dispersions: As mentioned above, the dispersions of the present invention are preferably silicon-free. Therefore, none of their components (wax, NF polymer, optional additives) contain the silicon groups (I) and (II) shown above. The dispersions of the present invention have been found to perform just as well as silicon-containing dispersions and can therefore replace currently used dispersions. Generally, currently available manufacturing equipment can be used, optionally by adjusting process parameters.

[0053] Similarly, concentrates and kits lacking silicon groups (I) and (II) as discussed herein are referred to as "silicon-free concentrates" and "silicon-free kits."

[0054] In a further preferred embodiment, the present invention relates to an impregnation 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 polyacrylates and poly(meth)acrylates; and is fluorine-free; and is free of blocked isocyanate crosslinkers; and exhibits a critical surface energy of 28 mN / m or less, for example from 21 mN / m to 23 mN / 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.

[0055] exist Second aspect The present invention relates to concentrate dispersions comprising candelilla wax and NF-polymer, as further described herein, and kits comprising candelilla wax and NF-polymer, as further described herein. These concentrate dispersions and kits are suitable for preparing the impregnation dispersions described herein and have proven to be valuable commercial products for use in the textile industry. This aspect of the invention is described in further detail below.

[0056] In one embodiment, the present invention provides a concentrate dispersion comprising candelilla wax, NF-polymer, and additional components (additives), all of which are as described in the first aspect of the invention (forming the dispersed phase), with the remainder being water (forming the continuous phase) in an amount of 450 mL / L to 990 mL / L. Thus, the concentrate as described herein differs from the impregnation dispersion primarily in terms of water content. While concentrates have a low water content, making them more efficient for transport and storage, impregnation dispersions are suitable for use in machines used in the textile industry. Typically, for efficiency reasons, the concentration is selected to be as high as possible, while ensuring stability and dispersibility.

[0057] In one embodiment, the concentration of candelilla wax in the concentrate dispersion is in the range of 1% (w / w) to 55% (w / w). In a preferred embodiment, the concentration of candelilla wax in the concentrate dispersion is in the range of 10% (w / w) to 40% (w / w). In an exemplary embodiment, the concentration of candelilla wax in the concentrate dispersion is 30%.

[0058] In one embodiment, the amount of water in the concentrate dispersion is in the range of 450 mL / L to 990 mL / L, preferably 600 mL / L to 900 mL / L. In an exemplary embodiment, the amount of water in the concentrate dispersion is 700 mL / L.

[0059] In view of the above, it is clear that the concentrate dispersion is fluorine-free, and preferably silicone-free.

[0060] In another embodiment, the present invention provides a kit comprising a first container and a second container (a first cartridge and a second cartridge).

[0061] The first container comprises a first composition comprising candelilla wax as defined herein, water, optionally a pH adjuster as defined herein, a biocide, a wetting agent and an emulsifier. The concentration of candelilla wax in the first container is typically within the same range as described above.

[0062] The second container comprises a second composition comprising a NF-polymer as defined herein, preferably in the form of an aqueous dispersion.

[0063] In view of the above, it is clear that the individual components of the kit are fluorine-free, and preferably silicone-free.

[0064] Rather than providing a single concentrate, a kit containing two concentrates may be provided. Separating the wax from the NF-polymer may be beneficial in the textile industry because it increases shelf life and provides a higher degree of flexibility. Typically, the kit is combined with an appropriate amount of water to obtain an impregnation dispersion.

[0065] In a preferred embodiment, the kit comprises a candelilla wax dispersion in a first container and a NF-polymer in a second container. This embodiment is believed to provide the ultimate in performance for the product.

[0066] In an alternative and preferred embodiment, the kit comprises candelilla wax in a first container and a biobased (i.e., containing at least 50% bio-based carbon content when applying ASTM D6866 Method B) NF-polymer in a second container. This embodiment is believed to provide a particularly environmentally friendly product.

[0067] The invention also relates to the corresponding uses as outlined below:

[0068] In an embodiment, the present invention relates to the use of the dispersion and kit as defined herein for impregnating / treating a fibrous substrate, including a fabric or textile product as disclosed herein.

[0069] In an embodiment, the present invention relates to the use of candelilla wax as described herein in combination with a NF-polymer as an impregnating material.

[0070] In an embodiment, the present invention relates to the use of candelilla wax as described herein in combination with a NF-polymer and in combination with a wetting agent or an emulsifier or a pH adjusting agent (typically an acid) as an impregnating material.

[0071] In an embodiment, the present invention relates to the use of a kit as described herein for preparing an impregnation dispersion as described herein.

[0072] exist The third aspect In the present invention, the present invention relates to textile products having durable water-repellent properties. These valuable properties are achieved due to the textile surface comprising candelilla wax and NF-polymer as described herein. This aspect of the invention will be described in further detail below.

[0073] As already discussed, the impregnation dispersions disclosed herein (first aspect, treatment fluids) are suitable for use in the textile industry. A variety of fiber substrates can be treated. Such substrates include fibers, yarns, fabrics (woven, nonwoven, and knitted), and finished products (e.g., garments, such as jeans, sportswear), collectively referred to as products of the textile industry or textile products.

[0074] Therefore, the present invention provides a textile product comprising a fibrous carrier material and a coating, wherein the coating comprises candelilla wax and a NF polymer as defined in the first aspect of the invention. Depending on the NF polymer and the manufacture, reaction products of the NF polymer and the candelilla wax may also be present. The coating may be present as a layer on the fibrous carrier. The total amount of candelilla wax and NF-polymer and optional additional components on the textile product may vary over a wide range. Typically, a total of 0.5 wt% to 8 wt% [candelilla wax + NF-polymer + optional additives (if present)] on the textile product produces suitable DWR properties. The skilled person can adjust the ratio of candelilla wax to NF-polymer. Preferably, 1 wt% to 5 wt% candelilla wax is present on the textile product to obtain beneficial DWR properties.

[0075] In an embodiment, the carrier material (base material) is selected from cellulose-based materials (eg cotton, viscose), wool, polyester and polyamide and yarns or fiber blends of these materials.

[0076] In an embodiment, the textile product is a finished product. Advantageously, such a textile product is selected from sportswear and outdoor clothing and outdoor equipment and protective clothing.

[0077] In an embodiment, the textile product is a fabric selected from the group consisting of knitted fabrics, nonwoven fabrics, and woven fabrics.

[0078] In an embodiment, the textile product is a spun yarn or filament. Such a product may be in the form of a skein or a bale or a continuous web.

[0079] exist The fourth aspect The present invention relates to methods for making the impregnation dispersions, concentrate dispersions, and kits described herein, particularly the first and second aspects of the invention. Such methods of manufacture rely on process steps that are known per se but have not been applied to the specific starting materials and components described herein. This aspect of the invention is described in further detail below.

[0080] In one embodiment, the present invention provides a method for making an impregnation dispersion as described herein, comprising: (i) combining a concentrate dispersion as described herein with water or an aqueous composition, or (ii) combining a first composition and a second composition of a kit as described herein with water or an aqueous composition. Essentially, the impregnation dispersion is obtained by diluting the appropriate starting materials with water, as is conventional in the art. The order in which the components are added can be determined by one skilled in the art. Typically, water is provided first, and the concentrate or the first and second compositions are added sequentially while stirring the entire mixture. The temperature can be controlled, but generally room temperature is sufficient.

[0081] In one embodiment, the present invention provides a method for making a concentrate dispersion as described herein, comprising: (x) providing a first composition and a second composition as described herein; (y) combining the first dispersion and the second dispersion, optionally by controlling the temperature at 3°C to 70°C, thereby obtaining a liquid composition; and optionally (z) diluting the liquid composition thus obtained with water or an aqueous solution containing an additive as described herein, thereby obtaining the concentrate dispersion.

[0082] In one embodiment, the present invention provides a method for making a dispersion of candelilla wax as described herein (the "first composition"). Candelilla wax is solid at room temperature, but as described below, an aqueous dispersion is formed by high shear mixing of candelilla wax in water heated to a temperature above the melting point of candelilla wax and containing an emulsifier to form a dispersion, and then rapidly cooling (quenching) the mixture. Those skilled in the art will appreciate that other techniques can be used to produce wax dispersions, which will produce the same results. Thus, one method for obtaining the first composition comprises the steps of: (i) dissolving the emulsifier in water and heating the aqueous composition to 70°C to 90°C; (ii) adding candelilla wax, about 10% by weight; (iv) emulsifying the composition thus obtained, for example by applying high shear forces; (v) quenching the emulsion thus obtained, thereby obtaining the first composition as disclosed herein.

[0083] exist The fifth aspect The present invention relates to a method for producing a textile product having a durable water-repellent effect, in particular the textile product described in the third aspect of the invention. It is believed to be particularly advantageous that such a production method relies on process steps known per se and machinery already used in industry. However, such process steps have not yet been applied to the specific starting materials described herein, in particular those of the first and second aspects above. This aspect of the invention will be described in further detail below.

[0084] The impregnation dispersions can be applied at all levels of the textile industry, ie the substrate is selected from (i) yarns or fibers or filaments; (ii) knitted, woven or nonwoven fabrics; (iii) finished products.

[0085] In one embodiment, the present invention provides a method for manufacturing a fabric, the method comprising the steps of: (a) providing a knitted, woven or nonwoven fabric to be coated; then (b) coating or padding with the impregnation dispersion described in the first aspect of the invention; then (c) drying and curing; and optionally followed by (d) further finishing steps as conventional in the art, thereby obtaining a coated fabric. These method steps are known per se, but have not been applied in the context of an impregnation dispersion as described herein (i.e., comprising candelilla wax and a specific blocked isocyanate). Suitably, the manufacture is a continuous process.

[0086] Step (a): The material to be coated is a fibrous substrate in its broadest sense. In embodiments, such a substrate includes an initial coating. In alternative embodiments, such a substrate does not have a coating. It is believed that the coating dispersions of the present invention can be applied to both coated and uncoated substrates. The term fibrous substrate includes filaments, fibers, yarns, nonwovens, and woven fabrics.

[0087] Step (b): This process step is already used in the textile industry, for example, in coating and padding. In one exemplary configuration, a dispersion concentrate as described in the second aspect contains 20% (w / w) candelilla wax. This concentrate is diluted to produce an impregnation dispersion ("treatment solution") containing 150 g / L of the concentrate. This treatment solution is applied to the material from step (a) at a 70% (w / w) pick-up rate.

[0088] Step (c): This step preferably includes squeezing to remove excess dispersion from the substrate. In one exemplary setup, the amount of candelilla wax is 2.1% as obtained.

[0089] Step (d): This drying step is preferably carried out at an elevated temperature, for example at least 120°, for at least 30 seconds, to remove excess water from the substrate, thereby leaving a thin coating of the concentrate on the substrate.

[0090] In one embodiment, the present invention provides a method for manufacturing a textile product, preferably by a garment impregnation process, comprising (a) providing a textile product to be treated; then (b) impregnating, spraying or washing the product by using the impregnation dispersion of the first aspect of the invention as described herein; then (c) drying and curing; and optionally followed by (d) a further finishing step; thereby obtaining a treated textile product.

[0091] Step (a): The product to be treated is a textile product in its broadest sense, for example an article of clothing, such as a pair of jeans. The product to be treated includes a product to be finished or coated. The product applied to step (a) may already include an initial coating.

[0092] Step (b): This process step utilizes treatment steps already used in the textile industry, such as impregnation or washing. In one exemplary configuration, the dispersion concentrate described in the second aspect contains 20% (weight / weight) candelilla wax. This concentrate is diluted to produce an impregnation dispersion ("treatment solution") containing 150 g / L of the concentrate. This treatment solution is applied to the textile product from step (a) to achieve a liquid pickup of 70% (weight / weight).

[0093] Step (c) is performed as described above. In one exemplary arrangement, the amount of candelilla wax is 2.1% with respect to the textile product obtained.

[0094] To further illustrate the present invention, the following Example These examples are not intended to limit the scope of the invention. A simple procedure has been designed for producing aqueous dispersions of natural waxes in the laboratory and is described in detail below:

[0095] Laboratory preparation of concentrate dispersions:

[0096] Using a magnetic stirrer with a hot plate, 5 g / l SPAN 20 and 5 g / l TWEEN 20 were heated in a glass beaker to approximately 10° C. above the melting point of the wax.

[0097] 100 g / l of candelilla wax were added and stirring was continued at approximately 250 rpm until the wax was completely melted.

[0098] The resulting composition was emulsified using an Ultraturrax (T25 disperser tool) at 11 000 rpm for 1 minute while continuing to heat.

[0099] As a quenching step, the emulsion thus obtained was poured into a pre-cooled glass bottle (refrigerator) and cooled in an ice bath or refrigerator.

[0100] After the above-mentioned quenching step, the blocked isocyanate used ("Extender TTL") was added to the dispersion. The aqueous dispersion of blocked isocyanate was slowly added to the wax dispersion using an Ultraturrax (T25 dispersing tool). The NF-polymer (Unidyne XF 5007) was added in a similar manner.

[0101] Preparation of impregnation dispersion:

[0102] The above concentrate is diluted with cold water to form a padding or treating solution.

[0103] Textile processing

[0104] A wide range of fabrics were studied, some of which are summarized in the table below:

[0105] Fabric A, 100% cotton, woven

[0106] Fabric B, 94% Polyamide; 6% Elastane, Woven

[0107] Fabric C, 100% cotton, knit

[0108] Fabric D, 100% PES, knit

[0109] The treatment of the fabrics described in the present invention was carried out using a Mathis laboratory padding machine (Model-Nr. HF1669) and a Mathis laboratory tenter frame (Model-Nr. DH 45888). Individual fabric samples measuring approximately 400 mm x 300 mm were prepared, saturated with the padding composition before passing through the padding machine to remove excess padding composition, and then dried in the tenter frame.

[0110] The samples were dried at 100°C for 1 minute and then at 160°C (fabric surface temperature) for 1 minute.

[0111] The samples were weighed dry before treatment and then after padding to enable calculation of wet pick-up and treatment level.

[0112] Padding composition

[0113]

[0114] Performance Testing

[0115] The DWR performance of the treatments was measured using AATCC test method 22-2010. The durability of the treatments was measured by washing samples in a Siemens IQ300 front-loading washer according to test method EN ISO 6330 (5A) using a 5A (40°C) wash cycle to wash a 2 Kg load.

[0116]

[0117]

[0118] When evaluating performance, it is important to note that the score ranges from "0" to "100." While "100" is the best score that cannot be exceeded, "90+ / -5" is considered an excellent result, "75+ / -5" is an acceptable result, and "50 or less" is considered a poor result. Typically, industrial users issue specifications requiring an initial score of at least "90" and at least "70" after 20 washes.

[0119] The main findings of the results can be summarized as follows:

[0120] The presence of the NF polymer allows the replacement of extender TTL without compromising performance. The industry considers that working methods without isocyanates (i.e. without extender TTL) have a lower chemical footprint and improved chemical sustainability (3.3 vs. 3.8 and 3.11).

[0121] - Candelilla wax dispersion itself does not provide any market relevant water resistance properties.

[0122] - By combining the two components, NF polymer and candelilla wax, synergistic effects in terms of performance and durability have been identified.

[0123] - All comparative and inventive examples are already fluorine-free and silicon-free. However, the chemical footprint is reduced (3.3 vs. 3.11).

Claims

1. A silicon-free impregnation 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 fluorine-free polymer ("NF-polymer") and optionally additives, characterized in that ● The wax is candelilla wax; ● The NF-polymer - selected from polyacrylates, poly(meth)acrylates and polyurethanes; and - does not contain blocked isocyanate crosslinkers; and - exhibits a critical surface energy of ≤ 28 mN / m (as determined by a Zisman plot) and / or a water resistance index of at least Spray 70 (when measured according to AATCC 22-2010); ● The additives are selected from pH adjusters, emulsifiers, biocides, wetting agents and softeners; and ● The amount of dispersed phase (wax + NF-polymer + optional further components) is 8% by weight or less.

2. The silicone-free impregnating dispersion of claim 1 , wherein the candelilla wax meets one or more of the following parameters: ● Melting point of 68.5℃ to 72.5℃, ● Acid value of 12 to 22, ● Saponification value of 43 to 65.

3. The silicon-free impregnation dispersion according to claim 1 or 2, wherein the NF-polymer is selected from polyacrylates and poly(meth)acrylates.

4. The silicon-free impregnation dispersion according to any one of claims 1 to 3, wherein the NF-polymer ● selected from polyacrylates or poly(meth)acrylates; and • Exhibits a critical surface energy of 20 to 28 mN / m and / or a water repellency index of at least Spray 80.

5. The silicon-free impregnation dispersion according to any one of claims 1 to 4, comprising one or more of the following additives: ● pH adjusting agent, preferably an acid or a buffer; and / or ● an emulsifier, preferably a nonionic emulsifier; and / or ● biocides; and / or ● Wetting agent; and / or ● Softener.

6. A silicon-free concentrate dispersion comprising a continuous phase and a dispersed phase, said dispersion comprising, preferably consisting of: ● Candelilla wax according to claim 1 or 2; and ● The NF-polymer according to claim 1, 3 or 4; and optionally ● One or more additives according to claim 5; and ● The remainder is water in an amount of 60% to 90% by weight.

7. A kit comprising a first container and a second container ● The first container comprises a first composition comprising candelilla wax as defined in any one of claims 1 or 2, water, optionally a pH adjuster as defined in claim 5, and optionally an emulsifier as defined in claim 5; and ● The second container comprises a second composition comprising a NF-polymer as defined in claim 1 , 3 or 4 , preferably in the form of an aqueous dispersion; It is characterized by The first composition and the second composition do not contain polyurethane having silicone polyol units.

8. The kit of claim 6, wherein ● The first container contains a candelilla wax dispersion and the second container contains a polyurethane or polyacrylate or polymethacrylate based NF-polymer; or ● The first container contains candelilla wax and the second container contains a NF-polymer which may be a polyurethane or polyacrylate and is bio-based; or ● The first container comprises candelilla wax in combination with a non-fluorinated durable water repellent (NF-DWR) polymer, and the second container comprises a petrochemical-based NF-polymer; or ● The first container contains a candelilla wax dispersion, and the second container contains a NF-polymer that is compatible with a natural fiber carrier; or ● The first container contains a candelilla wax dispersion, and the second container contains a NF-polymer that is compatible with a synthetic fiber carrier.

9. A method for producing the silicon-free concentrate dispersion according to claim 6, comprising the following steps: x. Providing a first composition as defined in claim 7 and a second composition as defined in claim 7; y. combining the first composition and the second composition, optionally by maintaining the temperature at 3°C to 70°C, preferably 20°C to 40°C, thereby obtaining a liquid composition; and optionally z dilute the liquid composition obtained in step y with water or an aqueous solution comprising an additive as defined in claim 5; Thereby, the silicon-free concentrate dispersion is obtained.

10. A method for producing a silicon-free impregnation dispersion according to any one of claims 1 to 5, comprising ● combining a concentrate dispersion as defined in claim 6 with water or an aqueous composition; or ● The first and second compositions of the kit as defined in claim 7 are combined with water or an aqueous composition.

11. A textile product comprising a base material and a coating, It is characterized by The coating comprises a wax according to claim 1 or 3 and a NF-polymer according to claim 1, 2 or 4 and optionally reaction products thereof; as well as The invention is characterized in that the coating is silicon-free.

12. The textile product according to claim 11, wherein the textile product is selected from the group consisting of finished products, fabrics, yarns and fibers.

13. The textile product according to claim 11 or 12, wherein the base material is selected from cellulose-based materials, wool, polyester, polyamide and blends thereof.

14. The textile product according to claims 11 to 13, wherein the textile product is ● Finished product, preferably selected from sportswear and outdoor equipment and outdoor clothing, or ● fabric, said fabric being selected from nonwoven fabrics, woven fabrics and knitted fabrics, or ● Yarn, said yarn being selected from natural or synthetic fibers or synthetic filaments.

15. A method for producing a coated fabric comprising the steps of a. providing a knitted or woven fabric to be coated; then b. coating or padding the fabric using the dispersion according to any one of claims 1 to 5; subsequently c. drying and curing; and optionally subsequently d. Further finishing steps; A coated fabric is thereby obtained.

16. The method according to claim 15, wherein ● The fabric of step (a) may or may not include an initial coating; and / or ● said step (c) being carried out at an elevated temperature, preferably at least 120°C, for at least 30 seconds; and / or ● Step (b) includes (b-1) coating or padding and (b-2) extrusion.

17. A method for producing a treated textile product, preferably by a garment dipping process, comprising a. Provide the textile products to be processed; then b. impregnating or washing the product by using a dispersion according to any one of claims 1 to 5; subsequently c. drying and curing; and optionally subsequently d. Further finishing steps Thereby a treated textile product is obtained.

18. Use of a silicone-free dispersion as defined in any one of claims 1 to 5 or a kit as defined in any one of claims 7 to 8 for impregnating / treating textiles or textile products.

19. Use of candelilla wax as defined in any one of claims 1 to 2 in combination with one or more silicon-free NF polymers as defined in claims 1, 3 or 4 and optionally in combination with one or more additives, preferably wetting agents, as impregnating material.

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