EP3697958A1

EP3697958A1 - Process for producing a textile article having a water-repellent textile surface by plasma treatment and wet-chemical treatment

Info

Publication number: EP3697958A1
Application number: EP18783048.4A
Authority: EP
Inventors: Vera Gratzl; Andreas Brakemeier; Volker STEIDEL; Gaffar HOSSAIN; Günter GRABHER
Original assignee: Plasmabionic GmbH; Werner and Mertz GmbH
Current assignee: Plasmabionic GmbH; Werner and Mertz GmbH
Priority date: 2017-10-16
Filing date: 2018-10-15
Publication date: 2020-08-26
Anticipated expiration: 2038-10-15
Also published as: EP3697958B1; DK3697958T3; SI3697958T1; LT3697958T; PL3697958T3; EP3470573A1; HRP20210558T1; CY1124169T1; RS61750B1; ES2868050T3; WO2019076823A1; HUE054827T2; PT3697958T

Abstract

A process for producing a textile article having a water-repellent textile surface is described, comprising the following steps: plasma-treatment of a textile surface such that a plasma-treated textile surface results, and subsequently wet-chemical treatment of the plasma-treaded textile surface, or of a textile surface produced therefrom in further steps, with a water repellent, such that a plasma-treated water-repellent textile surface results. Moreover, a textile article that is producible with the process according to the invention is described. Furthermore, the use of a low-pressure plasma process for the preparatory treatment of a textile surface of an article before the textile surface is made water-repellent by wet-chemical means is described.

Description

Process for producing a textile article having a hydrophobicized textile surface by plasma treatment and wet-chemical treatment

The present invention relates to a method for producing a textile article having a hydrophobicized textile surface, comprising the steps of: plasma-treating a textile surface, resulting in a plasma-treated textile surface and subsequently wet-chemically treating the plasma-treated textile surface or a textile surface produced therefrom in further steps a hydrophobing agent, so that a plasma-treated hydrophobicized textile surface results. Furthermore, the invention also relates to a producible by the process according to the invention textile article. Moreover, the invention also relates to the use of a low-pressure plasma process for the preliminary treatment of a textile surface of an article before the wet-chemical hydrophobing of the textile surface.

Textile articles having a hydrophobized surface, such as a water-repellent or waterproof surface, such as outdoor clothing articles, are currently manufactured predominantly by incorporation with fluorochemicals. Frequently, perfluorinated or polyfluorinated organic compounds, also known as "fluorocarbons", are used for this purpose, however, since such fluorocarbons are very long-lived and can be used in the conversion process. far and can accumulate in the human body - a hazard to the environment and the health of living organisms can not be excluded - are sought in the art alternatives, which have similar advantageous surface properties, but avoid the aforementioned disadvantages. Contributions to this discussion can be found, for example, in the publication "Perfluorinated and Polyfluorinated Chemicals - Preventing Pollution - Protecting the Environment" published by the Federal Environment Agency in July 2009 and the Press Release No. 32 of the Federal Environment Agency in October 2016.

In addition, as part of the so-called "Detox Campaign", since 2011 many manufacturers and distributors in Germany have committed themselves to remove perfluorinated and polyfluorinated chemicals from their supply chains by 2020 as potentially dangerous.

Already known alternatives for finishing textiles with fluorocarbons include, for example, the use of low-fluorinated hydrophobic and oleophobic application agents, fluorine-free hydrophobic application agents, including in particular silicones and conventional and modified polyurethanes, or also plastic membranes or products based on nanoparticles or nanofibers (ie fibers with at least one dimension in the size range of nanometers). An overview of such well-known alternatives can be found in the publication "Investigation of alternatives to fluorocarbon finishing in textiles" by M. Schöttner, master thesis at the University of Applied Sciences, Berlin 2012.

For the modification of textile surfaces and the plasma treatment is known per se. A plasma is a partially ionized gas, which is often referred to as the "fourth state of aggregation of matter." Phenomena such as lightning or northern lights (aurora borealis) are naturally occurring plasmas, which can be technically created by applying electric fields Because of their physical and chemical properties, plasmas are interesting in that they generate highly excited particles and radicals, which can trigger chemical reactions that are not possible under normal conditions, and the temperature of the workpieces to be treated with a plasma can be kept very low Document DE 101 1 1 427 A1 teaches a method and a device for cleaning and treating textiles in low-pressure plasma. The document EP 695 622 A2 describes a method and a device for the plasma modification of porous objects, for example textiles.

The document WO 2016/193486 A1 specifies a method for applying a halogen-free, water-repellent nano-coating to textiles by means of a low-pressure plasma polymerization method.

The document WO 2010/139466 A1 discloses impregnating active ingredients which contain non-fluorinated silicones and at least one cationic polymer.

The document JP S62 104975 A describes a method for producing a water-repellent fabric, which comprises the application of a liquid containing organopolysiloxanes and / or fluorine compounds to a fabric, a low-temperature plasma treatment and a repeated application of the liquid.

The document JP S60 194183 A describes a permanently coated synthetic or natural fabric comprising a silicone rubber film formed on a base fabric.

However, in view of the state of the art, there is still a need for a simple, effective and environmentally friendly process for the hydrophobicization of textile articles, which enables the production of durable, at least water-repellent, ideally waterproof, textile surfaces and thereby contribute to the use of more durable in the environment, at best only slowly degradable, to reduce or at least largely and ideally completely avoid chemicals such as fluorocarbons or alkylphenol ethoxylates. Likewise, there is also a need for a process for producing textiles suitable for numerous purposes (and also for such textiles themselves), which are at least partially and ideally fully biodegradable or compostable and, for example, the criteria for certification according to the Cradle Cradle-to-Cradle "product standards of the" Cradle-to-Cradle Products Innovation Institute ", Oakland, USA (" Cradle-to-Cradle Certified ™ ").

It was therefore a primary object of the present invention to provide a process for producing a textile article having a hydrophobicized textile surface provide, which allows an effective, durable and robust water repellency or impregnation of the textile surface and leads to a durable and resistant, at least water-repellent, ideally waterproof, textile surface.

The textile articles produced by said process should retain the hydrophobic, in particular water-repellent or waterproof, surface properties preferably also after demanding use - such as professional or industrial use, for example as workwear - with increased demands on abrasion resistance and surface finish resistance.

Another specific object of the present invention was to provide an environmentally friendly process which reduces or at least largely largely and ideally avoids the use of long-lived, in the best case only slowly degradable, chemicals such as fluorocarbons or alkylphenol ethoxylates. An important aspect of this specific task was also to produce, by said environmentally friendly method, textile articles which are at least partially and ideally fully biodegradable (ie by biological mechanisms such as the action of microorganisms) and thus at least partially or ideally fully compostable are and are therefore suitable for biological recycling.

It has now surprisingly been found that the primary object and other objects and / or subtasks of the present invention are achieved by a process according to the invention for producing a textile article having a hydrophobicized textile surface, comprising the following steps:

(a) making or providing an article having a textile surface,

(b) plasma-treating the textile surface produced or provided in step (a) to give a plasma-treated textile surface, (c) wet-chemically treating the plasma-treated textile surface resulting from step (b) or a textile surface produced therefrom in further steps Hydrophobizing agent, so that a plasma-treated hydrophobierte textile surface results. With the method according to the invention can be textile products with robust, durable water-repellent or waterproof properties produced in an environmentally friendly manner, even with reduced use or extensive or complete avoidance of long-lived, in the environment at best only slowly degradable chemicals such as fluorocarbons or Alkylphenolethoxylate.

Textile articles produced by the process according to the invention are suitable for demanding use such as professional or industrial use with its increased demands on abrasion resistance and resistance of the surface finish, for example for use as workwear and / or for industrial washing processes, since the textile Products retain their advantageous properties for a long time even under these demanding conditions.

In many cases, the textile articles produced by the process according to the invention have further advantageous surface properties, for example, they may additionally be dirt-repellent, weatherproof, easy to clean and / or difficult or hardly adhesive (bead-off effect).

Another advantage of the textile articles produced by the process according to the invention is their suitability for a refreshment of the hydrophobization or impregnation or a post-hydrophobicization or post-impregnation, if, for example, after prolonged use of the textile article its water-repellent or waterproof property should subside For this purpose, a textile article produced by the process according to the invention can again be given improved hydrophobic or water-repellent or water-tight properties by renewed wet-chemical treatment according to step (c) described above, for example by washing in the washing machine. The invention as well as preferred combinations of preferred parameters, properties and / or constituents of the present invention are defined in the appended claims. Preferred aspects of the present invention are also set forth and defined in the following description and examples.

In the context of the present invention, the term plasma treatment generally refers to all plasma processes which can be used for the surface treatment, in particular for the surface treatment of textile articles, especially plasma cleaning, plasma activation, plasma etching and plasma coating. The plasma treatment may include one or more of the aforementioned plasma processes, which will be explained in more detail below.

Plasma cleaning is often preceded by subsequent plasma treatment steps and is usually carried out in low-pressure plasma. A universally applicable low-pressure plasma system is therefore often equipped so that the essential cleaning processes, in particular a cleaning in oxygen plasma, can be performed. Such a low pressure plasma system used for cleaning processes is also referred to as a "plasma cleaner." Plasma activation (or plasma activation) is most commonly used to increase the surface tension of nonpolar substrates (ie, materials to be processed by plasma activation) For this purpose oxygen radicals are usually generated in the oxygen plasma (ie using oxygen or oxygen-forming compounds, usually gases), which can form bonds to the surface structures of a substrate due to their high reactivity, as a result of which the surface tension and / or the wettability of the substrate surface In plasma activation, no polymerizable monomers are used since direct targeting of the substrate surface with polymer films is not the objective, and plasma activation is typically performed for shorter periods, such as less than 10 minutes. The quality of plasma activation can be e.g. be assessed or tested by known contact angle measurement. In this method, the contact angle of a drop of a test liquid to the activated surface is measured. The better the activation, the flatter the drop is on the surface.

Plasma etching is understood to mean material-removing plasma-assisted etching processes on solids. In plasma etching, parts of the surface of a substrate are removed by chemical reaction with a process gas. The high reactivity of the excited atoms and molecules and in particular of the radicals is used. The most important criterion in the selection of the etching gas is its ability to form a readily volatile reaction product with the solid to be etched. The etching rate is very different (selective) on different substrates. Suitable organic etching gases are, for example, perfluorocarbons (perfluorocarbons, PFCs) such as tetrafluoromethane (CF4), hexafluoroethane (C2F6), perfluoropropane (C3F8), perfluorobutadiene (C4F6), unsaturated PFCs, perfluorinated aromatics and perfluorinated heteroaromatics. Suitable inorganic etching gases for example, sulfur hexafluoride, nitrogen (III) fluoride, boron trichloride, chlorine, hydrogen chloride or hydrogen bromide. Oxygen is usually not used as an etching gas, if a high material removal with significant change of physical or mechanical surface properties is to be achieved (usually at high energy input). Mixtures of different etching-active gases are common. Plasma etching is usually carried out for longer periods, for example in the range of 15 to 120 minutes.

In plasma coating, usually in low-pressure plasma, polymerizable monomers are introduced into a plasma chamber, which then polymerize under the influence of the plasma. The achieved with plasma polymerization layer thicknesses are usually in the range of micrometers. The process technology for plasma coating is considerably more complex than, for example, for plasma activation.

In the method according to the invention, the plasma treatment preferably comprises a plasma cleaning and / or a plasma activation, particularly preferably the plasma activation.

A process according to the invention is preferably where the plasma-treated (preferably plasma-cleaned and / or plasma-activated) resulting from step (c) is a hydrophobicized textile surface

- is comparatively more hydrophobic than the textile surface

the article manufactured or provided in step (a) and / or

the plasma-treated (preferably plasma-cleaned and / or plasma-activated) textile surface resulting in step (b), and / or

the article produced or provided in step (a) after only wet-chemical treatment as in step (c) but without prior plasma treatment in step (b), and / or - Has a comparatively more durable hydrophobic than the corresponding textile surface of the article produced or provided in step (a) after only wet-chemical treatment as in step (c), but without prior plasma treatment in step (b).

"Comparatively hydrophobic" means preferably that after step (c) resulting plasma-treated hydrophobic textile surface has a higher value (in cm) for the according to the standard ISO 81 1-1981 / DIN EN 2081 1: 1992-08 (water column above the textile surface, ie above / facing the plasma-treated textile surface or above / facing the plasma-treated, hydrophobized surface) measured water column, as the corresponding textile surface of or in step (a) manufactured or provided article, which no corresponding treatment according to has undergone steps (b) and (c) and / or of an article produced in step (b) which has not undergone any corresponding treatment according to step (c) and / or of one in step (a) produced or provided article after only wet-chemical treatment as in step (c), but without previous plasma treatment in Schr itt (b).

The textile surface of an article produced or provided in step (a) can be treated wet-chemically, in particular for the purpose of comparison with a process according to the invention and the textile surfaces resulting from a process according to the invention, directly, that is without prior plasma treatment. If the wet-chemical treatment of an article produced or provided in a step (a) for the purpose of a comparison is the same as in a step (c) according to the invention, a textile surface is obtained which can be assessed directly for its hydrophobicity. A comparative study is given below in Example 6 (see Table 3, Values "A: Moisture Repellency Initial"). "Comparatively more durable hydrophobicized" means preferably that the plasma-treated hydrophobicized textile surface resulting after step (c) has a higher value (in standard values according to the standard specification) determined according to the spray test of the AATCC TM22-2014 standard than that under the same conditions treated corresponding textile surface of the article produced or provided in step (a) after only wet-chemical treatment as in step (c), but without prior plasma treatment in step (b) (c) the resulting plasma-treated hydrophobicized textile surface, even after five washing and drying cycles (preferably carried out in accordance with standard ISO 6330: 2000 (E), conditions: washing machine type A / front loader, washing program 5A "normal" at 40 ± 3 ° C; drying in the tumble dryer) even higher, according to the standard AATCC TM22 -2014 has a value corresponding to the textile surface of the article produced or provided in step (a) after treatment under the same conditions (ie also present after five washing and drying cycles) after only wet-chemical treatment as in step (c), however, without prior plasma treatment in step (b).

The wet-chemical treatment in step (c) of the process according to the invention is preferably an aqueous wet-chemical treatment, i. a wet-chemical treatment, wherein the plasma-treated textile surface is contacted both with the hydrophobizing agent and with water, preferably simultaneously.

Also preferred is a process according to the invention or one described above or below, wherein the textile surface of the article produced or provided in step (a)

comprises one or more materials selected from the group consisting of

a first material (here and hereinafter meant in the sense of a "first group of materials"), preferably a natural material, preferably selected from the group consisting of cotton, wool, silk, cellulose and cellulose regenerate and mixtures thereof, particularly preferably selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof; a second material (here and hereinafter meant in the sense of a "second material group"), preferably a synthetic material, preferably selected from the group consisting of polyesters, polyamides, polyamideimides, polypropylene, polyacrylonitrile and polyacrylic thacrylate and mixtures thereof; selected from the group of synthetic polymers, preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof;

mixtures thereof (with regard to the number of components and their proportions, any desired mixtures of one or more first, preferably natural, materials and / or one or more second, preferably synthetic, materials) and / or

- is selected from the group consisting of woven, knitted, crocheted, braided, stitchbonded, felted, nonwoven, nonwovens, textile hoses, ropes, fibers, threads, yarns, rovings and mixtures thereof; preferably selected from the group consisting of woven fabrics, knitted fabrics, knitted fabrics, nonwoven fabrics, nonwoven fabrics and mixtures thereof.

The one or more materials comprised of the textile surface of the article made or provided in step (a) of the method of the invention may be used singly or in combination. For this purpose, one or more materials may be employed from a first material (ie, selected from the material group of a first material or group as defined above), or one or more materials may be selected from a second material (ie, selected from the material group a second material or a second material group as defined above) or a mixture or combination of one or more materials of a first material (ie selected from the material group of a first material or a first material group as defined above) with one or more materials from a second material (ie selected from the material group of a second material or a second material group as defined above) can be used. Combinations of preferred materials again result in preferred materials or combinations of materials.

In a preferred variant of the method according to the invention, the textile surface of the article produced or provided in step (a) comprises at least one second material selected from the group (preferably a second material group) consisting of polyesters, polyamides, polyamide-imides, polypropylene, polyacrylonitrile and polyacrylmethacrylate and their mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably the biodegradable synthetic see polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof.

In a further preferred variant of the method according to the invention, the textile surface of the article produced or provided in step (a) comprises only a second material selected from the group (ie one or more materials selected from a second material group) consisting of polyesters, polyamides, polyamide-imides, Polypropylene, polyacrylonitrile and polyacrylmethacrylate and mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof. In this preferred variant of the method according to the invention, the textile surface of the article manufactured or provided in step (a) does not comprise a first material (preferably natural material), i. no material which is preferably selected from the group (preferably a first material group) consisting of cotton, wool, silk, cellulose and cellulose regenerate and their mixtures.

If the textile surface of the article produced or provided in step (a) comprises one or more materials which - as indicated above - are selected from the group consisting of at least one first material (as defined above), preferably a natural one (and therefore biologically degradable) material, preferably selected from the group (preferably a first material group) consisting of cotton, wool, silk, cellulose and cellulose regenerate; and at least one second material (as defined above), preferably a synthetic material, which is selected from the group (preferably a second material material). group) of the synthetic polymers, preferably of the biodegradable synthetic polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, and mixtures of the aforementioned materials, the textile articles produced by the process according to the invention are advantageously at least partially and in the ideal case completely biodegradable (ie by biological mechanisms such as the action of microorganisms) and thus at least partially and ideally fully compostable and thus suitable for biological circulation , This variant of the method according to the invention is therefore preferred.

"Biodegradable" in the context of the present invention means that a textile article, a material, or a substance with this property is compostable and preferably within a period in the range of 12 to 36 months, particularly preferably in the range of 18 to 30 months, and preferably at a temperature in the range of 40 ° C to 80 ° C, more preferably in the range of 50 ° C to 75 ° C, at least predominantly (ie> 90 wt .-%, preferably> 95 wt .-%, of the starting material are biodegraded under the conditions specified herein) and, ideally, are degraded substantially completely biologically (ie by biological mechanisms such as the action of microorganisms), provided that the textile surface of the article produced or provided in step (a) comprises one or more materials which are selected from the group consisting of at least a first material (as defined above), preferably a natural (and therefore biodegradable) material selected from the group (preferably a first group of materials) consisting of cellulose and cellulose regenerate; and at least one second material (as defined above), preferably a synthetic material selected from the group (preferably a second material group) of the synthetic polymers, preferably the biodegradable synthetic polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides , As well as mixtures of the aforementioned materials, the products prepared by the process according to the invention are not only advantageously at least partially and ideally almost completely biodegradable and thus at least partially and ideally completely compostable, but they are also suitable, particularly high demands their mechanical strength and the longevity or durability of hydrophobic or water-repellent or waterproof properties. This variant of the method according to the invention is therefore particularly preferred.

Accordingly, a preferred process according to the invention or one described above or below is preferred, wherein the textile surface of the article produced or provided in step (a) comprises one or more materials which are selected from the group consisting of

- A first material selected from the group (preferably a first group of materials) consisting of cellulose and cellulose regenerate and mixtures thereof;

a second material selected from the group (preferably a second material group) consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; preferably the second material is selected from the group (preferably a second material group) of the copolyesters which contain as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1, 3-propanediol and 1, 4-butanediol, particularly preferably ethanediol) and which preferably comprise at least one further monomer; such as

- their mixtures; wherein preferably the textile surface comprises one or more materials, at least one of which is selected from the group consisting of a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein the second material is preferably selected from the group of copolyesters which contain as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1,3-propanediol and 1,4-butanediol, more preferably etanethiol) and which preferably comprise at least one further monomer which is different from the abovementioned monomers (terephthalic acid or one or more alkanediols);

In step (a) of the process according to the invention as the first, preferably natural, material to be used cellulose is preferably obtained from the wood of trees and / or plant fibers, preferably hemp, flax, bamboo, banana and / or ramie.

In the context of the present invention, the term "cellulose regenerate" preferably comprises regenerated fibers Regenerated fibers are fibers which are produced from naturally occurring, renewable raw materials via chemical processes, in particular cellulose derivatives of wood.

In the context of the present invention, cellulose (cellulose) or cellulose regenerates which can be used in step (a) of the process according to the invention preferably comprise the materials (or the fibers from the materials) viscose, modal, lyocell and cupro, particularly preferably lyocell.

Viscose fibers are chemical fibers (regenerated fibers) which are produced industrially by means of the known viscose process, a widespread wet spinning process. The starting material of the viscose process is cellulose, predominantly in the form of wood, in which the high-purity cellulose is extracted by various methods.

Modal fibers, like viscose fibers, are also 100 percent cellulose but, unlike other regenerated fibers, are made primarily from beech wood. The starting material is debarked and then crushed to separate from lignin into pieces beech wood. By modifying the manufacturing process can be achieved at Modal fibers have higher fiber strength and improved fiber properties than other pulp fibers. In addition, the modal fiber has a higher moisture absorption and dries quickly.

Lyocell is a per se known, cellulose-made, industrially produced cellulose regenerated fiber, which is produced according to the per se known direct solvent process. It is used in particular for the production of textiles and non-wovens Lyocell fibers have high dry and wet strength, are soft and absorb moisture very well, and textiles made from them regularly have a smooth and cool feel fluently, have a low tendency to crack, and can be washed and chemically cleaned.

Cupro, also referred to as copper silk or copper fiber, is a textile fiber composed of regenerated cellulose. The properties of Cupro are comparable to viscose. Cuprofibers are mainly processed into textile lining materials because they are breathable, hygroscopic and do not accumulate static. In addition, the fabrics have a silky soft feel and are smooth and shiny. Cupro can be washed and ironed, but is not iron free. Cupro is usually prepared by the copper oxide-ammonia process (cuoxam process).

In step (a) of the method according to the invention usable second, preferably synthetic, material also comprises elastomers, preferably biodegradable elastomers.

Particularly preferred synthetic polymers to be used as second material in step (a) of the process according to the invention, preferably biodegradable synthetic polymers, include substituted and / or unsubstituted polyesters and particularly preferably comprise copolyesters of aromatic and aliphatic monomers. These particularly preferred copolyesters of aromatic and aliphatic monomers preferably comprise as monomers terephthalic acid and one or more alkanediols, preferably selected from the group consisting of ethanediol, 1,3-propanediol and 1,4-butanediol. In a particularly preferred variant of the process according to the invention in step (a) as a second, preferably synthetic material to be used polyester as monomers terephthalic acid and one or more alkanediols (preferably an alkanediol, ie an alkanediol of a variety) selected from the group consisting of ethanediol, 1,3-propanediol and 1,4-butanediol (preferably ethanediol), and preferably comprise at least one other monomer. Examples of inventive particularly Preferred biodegradable substituted or unsubstituted polyesters or fibers of such biodegradable substituted or unsubstituted polyesters are polybutylene adipate terephthalate ("PBAT"), Ecoflex® (BASF) and infinito® (Lauffenmühle GmbH & Co. KG) (a) Polyamides useful in the process of the invention are polyamideimides and aramides (the latter are also referred to as "aromatic polyamides"), preferably as defined by the US Federal Trade Commission, according to which aramids are those polyamides having aromatic groups in the backbone in which at least 85% of the amide groups are bonded directly to two aromatic rings.

A particularly preferred biodegradable polyamide to be used in step (a) of the process according to the invention is polyamide 6 which is known per se. An example of a particularly preferred biodegradable polyamide according to the invention is Amni Soul Eco® (Rhodia / Solvay). The above-mentioned variants of the textile surface of the article produced or provided in step (a) can be used individually or in combination (together). For example, filaments, fibers or yarns of one or more of the above materials may be used singly or in combination. Thus, for example, threads of at least one synthetic material and / or threads of at least one natural material can be spun individually or together into yarns, or such different threads can each be processed individually or together to form a nonwoven, fabric or fabric, for example, joined, woven or knitted , become.

Preference is given to using textile articles produced or provided in step (a) of the process according to the invention whose textile surface is selected from the group consisting of woven and knitted fabrics. The plasma treatment of woven and knitted fabrics in step (b) of the process according to the invention can be carried out particularly efficiently and effectively. Textile fabrics or knitted fabrics produced by the process according to the invention can be further processed directly into ready-made textile articles, for example into textile articles for everyday use, such as outdoor clothing. The aforesaid materials (for example cellulose or cellulose regenerate and / or one or more synthetic polymers as defined above) and the types of textile surfaces (eg woven or knitted fabrics) mentioned above may preferably be combined and such combinations, in particular combinations of preferred Materials with preferred types of textile surfaces yield preferred variants of the method of the invention.

Also preferred is a process according to the invention or one described above or below as being preferred, wherein the textile surface of the article produced or provided in step (a) comprises a woven knitted fabric, knitted fabric, braided knit, felt, nonwoven fabric and / or a woven fabric textile hose, preferably a woven fabric and / or a knitted fabric, particularly preferably comprises a fabric, which or which

- Has a basis weight in the range of 20 g / m ² to 500 g / m ² , preferably in the range of 100 g / m ² to 200 g / m ² , and / or

- Has a thread density in the range of 80 to 120 warp / cm and 40 to 80 wefts / cm.

It has been shown in own experiments that these aforementioned preferred textile surfaces, in particular fabrics and / or knitted fabrics, are particularly well suited for plasma treatment in step (b) of the process according to the invention and thus a particularly good plasma activation and a particularly good subsequent Hydrophobization of a textile surface allow.

Also preferred is a process according to the invention or one described above or below as being preferred, wherein the water repellent used in step (c)

an aqueous hydrophobing agent, which preferably comprises modified polydimethylsiloxane, and / or does not comprise fluorine-containing organic compounds.

An aqueous hydrophobing agent allows the process to be carried out as an aqueous (i.e., at least in the presence of water) process, ideally without the presence of organic solvents. In this way, a few organic see or no organic solvents into the environment, without elaborate filter or retention measures would be required or there are few organic or no organic solvent residues that could affect the environment or would have to be disposed of consuming. Polydimethylsiloxanes are known to be at most slightly toxic and chemically at least largely inert, so that their use in the process according to the invention can at least largely and ideally exclude completely damage to living organisms.

The at least extensive and ideally complete abandonment of fluorine-containing organic compounds such as perfluorinated or polyfluorinated organic compounds (fluorocarboxylic) in the process according to the invention avoids the typical environmental disadvantages of these classes of substance, thus making an additional contribution to the high environmental compatibility of the process according to the invention is done.

In the process according to the invention or an inventive process described above or below as being preferred, the water repellent is preferably an aqueous hydrophobing agent which - modified polydimethylsiloxane, preferably modified polydimethylsiloxane, wherein one or more methyl groups are replaced by substituents with basic functional groups, alkyl groups and / or polyether groups , comprises; and additionally - comprising one or more cationic polymers selected from

Group consisting of

Polyacrylates, preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, me- thacrylic acid, methacrylic acid esters and optionally further monomers copolymerizable with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters, preferably styrene;

Polyurethanes, preferably polyurethanes of the polyester type and / or of the polycarbonate type, which are preferably formed by polycondensation of dialcohols or polyalcohols with diisocyanates and / or polyisocyanates;

Polyesters which are preferably formed by polycondensation of dialcohols or polyalcohols with dicarboxylic acids and / or polycarboxylic acids;

Polypeptides, which are preferably formed by polycondensation of amino acids,

Polyamides, which are preferably formed by polycondensation of amino acids,

preferably synthetic biopolymers, preferably polypeptides or polyamides, which are each preferably formed by polycondensation of amino acids; and

Polysaccharides, preferably selected from the group consisting of chitin and chitosan (for modifications and the like see below).

The polyacrylates which can be used in step (c) of the process according to the invention, which are preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, methacrylic acid and methacrylic acid esters, may optionally be combined with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters. in this context, the homopolymers and copolymers are formed from monomers of acrylic acid, acrylic esters, methacrylic acid and methacrylic acid esters, wherein (depending on the requirements of the individual case) further monomers co-polymerizable with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic esters are integrated or are not integrated. Preferably, the modified polydimethylsiloxane in the aqueous hydrophobing agent in step (c) of the process according to the invention in a weight ratio in the range of 1:20 to 20: 1, preferably in the range of 1:10 to 10: 1, particularly preferably in the range of 7: 1 to 1: 7, relative to the one or more cationic polymers used. The aqueous hydrophobing agent in step (c) of the process according to the invention preferably contains the modified polydimethylsiloxane in a total amount in the range from 0.1% by weight to 20% by weight, particularly preferably in the range from 0.2% by weight to 15 Wt .-% and particularly preferably in the range of 0.3 wt .-% to 10 wt .-%, based on the total weight of the aqueous hydrophobing agent. The aqueous hydrophobing agent in step (c) of the process according to the invention preferably contains the one or more cationic polymers in a total amount in the range from 0.05% by weight to 15% by weight, particularly preferably in the range from 0.1% by weight. % to 10 wt .-% and particularly preferably in the range of 0.15 wt .-% to 5 wt .-%, based on the total weight of the aqueous hydrophobing agent. Preferably, the modified polydimethylsiloxane usable in step (c) of the process according to the invention comprises one or more polydimethylsiloxanes which are selected from the group consisting of aminoalkyl-polydimethylsiloxane, amidoaminoalkyl-polydimethylsiloxane, alkylaminoalkyl-polydimethylsiloxane, alkylamidoaminoalkylpolydimethylsiloxane , Polyoxyalkylene-polydimethylsiloxane and alkyl-polyoxyalkylene-polydimethylsiloxane. Examples of such modified polydimethylsiloxanes which are preferably also used in step (c) of the process according to the invention are disclosed in particular in document WO 2010/139466.

The aforementioned modified polydimethylsiloxanes can be used individually or in combination with one another. The cationic polymers which can be used in step (c) of the process according to the invention are preferably homopolymers or copolymers comprising, as constituents of the side chains of the corresponding monomers, uncharged basic groups, preferably primary, secondary or tertiary amino groups, which contain cationic groups by uptake of H ⁺ ions can form. Examples of such cationic polymers which are preferably used in step (c) of the process according to the invention are disclosed in particular in document WO 2010/139466.

The aforementioned cationic polymers can be used individually or in combination with one another. In the context of the present invention, the term "polysaccharide" comprises modified and unmodified polysaccharides, preferably modified chitin and modified and unmodified chitosan, wherein differences may be present in terms of molecular weights, degrees of deacetylation and polysaccharide derivatives suitable according to the invention, preferably chitosan derivatives Preferable chitosan derivatives include chitosan succinate (N-succinyl chitosan), chitosan propionate (N-propionyl chitosan) and chitosan adipate (N-adipyl chitosan).

Cationic polymers which are preferably used in the process according to the invention specified above are the biopolymers chitin and / or chitosan and their derivatives, preferably chitosan and its derivatives. If more deacetylated than acetylated 2-amino-2-deoxy-.beta.-D-glucopyranose units are present in the total biopolymer molecule (> 50% deacetylated units), this is described in the present text, in accordance with the usual understanding in the art, referred to as chitosan. If there are more acetylated than deacetylated 2-amino-2-deoxy-β-D-glucopyranose units in the total biopolymer molecule (<50% deacetylated units), this will be understood in the present text, in accordance with the usual understanding in the art, referred to as chitin. The degree of the resulting deacetylation in chitin or chitosan may vary. To improve the solubility in aqueous solutions and / or to reduce the viscosity, the chain length and / or the degree of deacetylation of the polysaccharide (chitin or chitosan) can be changed. Due to the free amino groups formed by the deacetylation, chitosan in acidic solution is a polycation with a high charge density. For use in step (c) of the process according to the invention, preference is given to a chitosan having a degree of deacetylation of> 75%, particularly preferably having a degree of deacetylation of> 85% and very particularly preferably having a degree of deacetylation of> 90%. The molecular weight of the chitosan used in step (c) of the process according to the invention is preferably in the range of 10,000 daltons to 5,000,000 daltons, more preferably in the range of 100,000 daltons to 2,000,000 daltons, and most preferably in the range of 150,000 daltons to 1,000,000 daltons. Examples of chitosan types which can be used or preferably used in step (c) of the process according to the invention are disclosed in particular in document WO 2010/139466.

Accordingly, preference is also given to a preferred process according to the invention or one described above or below, wherein

the modified polydimethylsiloxane is a modified polydimethylsiloxane,

wherein one or more methyl groups are each replaced by a substituent with a basic functional group, preferably in each case by an aminoalkyl group or an amido-aminoalkyl group, and which preferably comprises terminal methoxy groups; and / or (preferably "and")

- wherein the one or more cationic polymers are selected from the

Group consisting of

Polyacrylates which are functionalized by cationic groups or basic groups, preferably by amino groups, wherein the functionalization is preferably effected by appropriately substituted or functionalized (meth) acrylic acid esters; preferably styrene-acrylate copolymers which are functionalized by basic groups, preferably by amino groups;

Polyurethanes functionalized by cationic groups or basic groups, preferably by amino groups; Polyesters which are functionalized by cationic groups or basic groups, preferably by amino groups;

Polypeptides comprising one or more basic amino acids, preferably selected from the group consisting of lysine, arginine, histidine, citrulline and ornithine, and

Chitosan, preferably with a degree of deacetylation> 75%; wherein preferably at least one of the one or more cationic polymers is selected from the group consisting of - polyacrylates, preferably styrene-acrylate copolymers, which are functionalized by cationic groups or basic groups, preferably by basic groups, more preferably by amino groups, and

Chitosan, preferably with a degree of deacetylation> 75%. In the context of the present text, a substitution, for example a side chain of a molecule, with a functional group (which may also be specified in detail in individual cases) is generally referred to as "functionalization." Accordingly, the terms "substituted" and "functionalized" are also used herein ( For the purposes of the present invention, the terms "polyamides" and "polypeptides" (ie in each case a natural or synthetic polymer linked by peptide bonds between amino acids) are used interchangeably and differ only depending on the material context Usually the term "polypeptide" is used in connection with corresponding natural polymers. Examples of aqueous, fluorine-free hydrophobing agents which are preferably used in step (c) of the process according to the invention are disclosed in particular in document WO 2010/139466. Also preferred is a process according to the invention or one described above or below as being preferred, wherein the plasma treatment in step (b) is a low-pressure plasma treatment, preferably a low-pressure plasma activation, or

a low pressure plasma treatment, preferably a low pressure plasma activation, and at least one further plasma treatment step.

A low-pressure plasma is usually generated between two or more electrodes by electromagnetic high-frequency fields, at a pressure which is considerably lower than the atmospheric pressure. Due to the large (mean) free path length of excited particles generated in this way, the expansion of the plasma can go beyond the effective range of the high-frequency field and also capture the entire volume of a plasma chamber. In the above-indicated preferred variant of the process according to the invention, the at least one further plasma treatment step preferably comprises a plasma cleaning, particularly preferably a plasma cleaning of the textile surface produced or provided in step (a), before a plasma activation of said textile surface is carried out. The plasma activation is thus followed by the plasma activation, preferably the low-pressure plasma activation.

Preference is given to a process according to the invention or one described above or below as being preferred, the low-pressure plasma treatment being carried out at a pressure in the range from 1 Pa (0.01 mbar) to 20 kPa (200 mbar), preferably at a pressure in the region of 1 Pa (0.01 mbar) to 0.5 kPa (5 mbar), more preferably at a pressure in the range of 10 Pa to 50 Pa (0.1 mbar to 0.5 mbar).

It has been found in own experiments that good or even the best result is achieved in the pressure ranges given hereinbefore as preferred or particularly preferred with regard to, on the one hand, the penetration of the textile surface by means of the low pressure plasma treatment, which is sufficient for the long-term stability of the treatment. On the other hand, the speed of the process, which is important for the economic implementation of the process. A higher gas pressure usually leads to a faster plasma activation, whose long-term stability is limited. In contrast, the use of a lower gas pressure (for example <10 Pa) generally leads to an advantageous penetration of the textile surface by means of the low-pressure plasma treatment, but requires longer treatment periods. Too high a gas pressure can in the worst case even lead to a significant decrease in the treatment success (reduction of the wettability of the treated tissue).

A process according to the invention or a preferred process according to the invention is therefore preferred, the pressure ranges specified above for step (b) being preferred or particularly preferred for the low-pressure plasma treatment, preferably the low-pressure plasma activation, being combined with those described below for step (b). as preferred or as particularly preferred for the low-pressure plasma treatment, preferably the low-pressure plasma activation, specified ranges of the time duration.

Preference is given to a method according to the invention or one described above or below as being preferred, wherein the low-pressure plasma treatment (step (b)) is carried out at a temperature in the range from 10 ° C to 50 ° C, preferably from 15 ° C to 40 ° C , When carrying out a plasma method, in particular a low-pressure plasma method or low-pressure plasma activation method, in the specified temperature range and under the conditions and preferred conditions given above and below, a "low-temperature plasma process", If step (b) of the process according to the invention is carried out at temperatures below the specified temperature range or preferred temperature range, for example, undesirable side reactions may occur, if step (b) of the process according to the invention occurs at temperatures above the specified temperature range or above If, for example, the deposition rate of components of the gas or gas mixture forming the plasma is undesirably reduced, the desired effect of the plasma treatment may be undesirably reduced can be compromised.

The plasma treatment, preferably the low-pressure plasma treatment, particularly preferably the low-pressure plasma activation, in step (b) of the method according to the invention The inert gas is preferably used in the presence of a reactive gas and / or (preferably "and") an inert gas. The inert gases used are preferably noble gases or mixtures thereof.

The reactive gas used is preferably one or more oxygen-containing compounds which at least temporarily release molecular oxygen (at least under the conditions of low-pressure plasma activation, for example precursors or precursors of oxygen) or make it available.

Therefore, a preferred process according to the invention or one described above or below is preferred, wherein the low-pressure plasma treatment is carried out with at least one oxygen-containing compound selected from the group consisting of O, O 2, O 3, NO, N 2 O and CO 2 such that Preferably, oxygen-containing functional groups (preferably -OH, -CO, -CHO or -COOH) are formed on the textile surface which are preferably covalently bonded to the textile surface. The detection of the production of such oxygen-containing functional groups on or the detection of their covalent bonding to the textile surface can be performed by suitable physical or physico-chemical methods, for example by Fourier transform infrared spectroscopy (FT-IR spectroscopy) or by X-ray photoelectron spectroscopy for chemical analysis (ESCA). Accordingly, a preferred process according to the invention or one described above or below, according to the invention, wherein the at least one oxygen-containing compound is particularly preferred

- O2 (molecular oxygen), and / or (preferably "and") - is present in admixture with at least one inert gas, preferably selected from the group consisting of He, Ar, Ne and Xe, and / or is present in a mixture, preferably a gas mixture, which comprises O 2 and at least one inert gas selected from the group consisting of He and Ar, wherein preferably the mixture (preferably said gas mixture, which is O 2 and at least one inert gas selected from the group consisting of He and Ar) comprises at least 99% by volume of O 2 and at least one inert gas selected from the group consisting of He and Ar, and more preferably contains at least 99% by volume of O 2 and Ar.

Preferably, the plasma treatment, preferably the low-pressure plasma treatment, particularly preferably the low-pressure plasma activation, in step (b) of the inventive method with a gas or gas mixture is performed, which (before the transition to the plasma state) in addition to the or the oxygen-containing gases not more than 1% by volume of other gaseous constituents. By such a small proportion of other ingredients, in particular unwanted side reactions can be largely avoided or even prevented by otherwise present other components of the gas mixture.

Also preferred is a process according to the invention or one described above or below as being preferred, wherein the aforementioned mixture (preferably said gas mixture comprising O 2 and at least one inert gas selected from the group consisting of He and Ar) (before the transition into the plasma state) contains a proportion of O 2 in the range of 70% by volume to 90% by volume and a proportion of inert gas, preferably of He and / or Ar, in the range from 10% by volume to 30% by volume , In our own experiments, it has been found that a gas mixture of this preferred composition gives very good or even best results in terms of preparatory plasma activation of a textile surface by the method according to the invention, so that also very good or even the best results with respect to the moisture-repellent properties of the inventive Process produced plasma-treated hydrophobized textile surface and the durability of these moisture-repellent properties result (see, for example, below the results of Example 6, Table 3 or Example 7, Table 4).

Likewise preferred is a process according to the invention or a process described above or below as being preferred, wherein the textile surface of the article produced or provided in step (a) comprises one or more materials selected from the group consisting of

a first material, preferably a natural material, selected from the group consisting of cotton, wool, silk, cellulose and cellulose regenerate and mixtures thereof; particularly preferably selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof;

- A second material, preferably a synthetic material selected from the group consisting of polyesters, polyamides, polyamide-imides, polypropylene, polyacrylonitrile and polyacrylmethacrylate and mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; such as

- their mixtures; wherein preferably the textile surface comprises one or more materials, at least one of which is selected from the group consisting of a second material preferably a synthetic material, preferably selected from the group consisting of polyesters, polyamides, polyamide-imides, polypropylene, polyacrylonitrile and polyacrylic methacrylate and their mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; the plasma treatment in step (b) a low-pressure plasma treatment, preferably a low-pressure plasma activation, wherein the low-pressure plasma treatment is carried out with at least one oxygen-containing compound selected from the group consisting of O, O 2, O 3, NO, N 2 O and CO 2, so that preferably oxygen-containing functional groups are produced on the textile surface, which are preferably covalently bonded to the textile surface, and the hydrophobizing agent used in step (c) is an aqueous hydrophobing agent comprising modified polydimethylsiloxane, preferably modified polydimethylsiloxane, in which one or more methyl groups are substituted by substituents basic functional groups, alkyl groups and / or polyether groups are replaced; and additionally comprises one or more cationic polymers selected from the group consisting of

Polyacrylates, preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters and optionally further monomers co-polymerizable with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters, preferably styrene;

Polyurethanes, preferably polyester-type and / or polycarbonate-type polyurethanes;

Polyester,

polypeptides

polyamides and

Polysaccharides, preferably selected from the group consisting of chitin and chitosan.

Particular preference is given to a method according to the invention or one described above or below as being preferred, wherein the textile surface of the article produced or provided in step (a) comprises one or more materials which are selected from the group consisting of

a first material selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof;

a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein preferably the second material is selected from the group of Copoly lyester which as monomers terephthalic acid and one or more alkanediols

(Preferably selected from the group consisting of ethanediol, 1, 3-propanediol and 1, 4-butanediol, more preferably ethanediol) and which preferably comprise at least one other monomer which of the aforementioned monomers (terephthalic acid or a several alkanediols) is different; such as

- their mixtures; wherein preferably the textile surface comprises one or more materials, at least one of which is selected from the group consisting of a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein the second material is preferably selected from the group of copolyesters which contain as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1,3-propanediol and 1,4-butanediol, more preferably etanethiol) and which preferably comprise at least one further monomer which is different from the abovementioned monomers (terephthalic acid or one or more alkanediols); the plasma treatment in step (b)

a low-pressure plasma treatment, preferably a low-pressure plasma activation, which is carried out in the presence of a gas mixture comprising O 2 and at least one inert gas selected from the group consisting of He and Ar, preferably wherein said gas mixture is at least 99% by volume at O2 and at least one inert gas selected from the group consisting of He and Ar, and particularly preferably said gas mixture contains at least 99 vol .-% of O2 and Ar, and the hydrophobizing agent used in step (c) is an aqueous hydrophobing agent comprising modified polydimethylsiloxane, preferably modified polydimethylsiloxane wherein one or more methyl groups are replaced by substituents having basic functional groups, alkyl groups and / or polyether groups; and additionally comprises one or more cationic polymers selected from the group consisting of

Polyacrylates, preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters and optionally further, with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic esters co-polymerizable monomers, preferably styrene;

Polyester,

polypeptides

polyamides

Also preferred is a process according to the invention or a process described above or below as being preferred, wherein in step (b)

the low-pressure plasma treatment is carried out for a duration in the range from 10 seconds to 10 minutes, preferably in the range from 30 seconds to 5 minutes, particularly preferably in the range from 1 minute to 3 minutes; and or

the low-pressure plasma is generated at a frequency in the range of 10 MHz to 18 MHz, preferably in the range of 1 1 MHz to 15 MHz, and or

- The low-pressure plasma is generated with electrodes, wherein the electrode density preferably in the range of 1 to 10 electrodes / m ² , more preferably in the range of 2 to 5 electrodes / m ² , most preferably in the range of 2.5 to 4 electrodes / m ² , based on the textile surface produced or provided in step (a); and or

- The low-pressure plasma treatment with a plasma generating source at a power in the range of 0.05 kW to 100 kW, preferably in the range of 1 kW to 25 kW, more preferably in the range of 2 kW to 15 kW, most preferably in the range of 5 kW to 10 kW is performed, and / or

- The low-pressure plasma treatment in a plasma treatment chamber at a power in the range of 0.25 kW / m ³ to 2.0 kW / m ³ , preferably in the range of 0.5 kW / m ³ to 1, 5 kW / m ³ , is performed ,

The parameters of the low-pressure plasma treatment in step (b) of the process according to the invention given above as being preferred or particularly preferred may preferably be combined and in combination give particularly preferred process conditions for carrying out step (b). In particular, variants of the method according to the invention are preferred, wherein in step (b) a low pressure plasma treatment, preferably a low pressure plasma activation, at a pressure in the range of 1 Pa (0.01 mbar) to 0.5 kPa (5 mbar) and for a duration in the range of 30 sec to 5 min. In addition, variants of the process according to the invention are particularly preferred, wherein in step (b) a low-pressure plasma treatment, preferably a low-pressure plasma activation, at a pressure in the range of 10 Pa to 50 Pa (0.1 mbar to 0.5 mbar) and a duration in the range of 1 min to 3 min is performed. As already stated above, the best effect or the best compromise of the process according to the invention for penetrating the textile surface by means of low-pressure plasma treatment, longevity of the activation achieved and subsequent hydrophobing of the textile surface, as well as cost-effective performance under these preferred conditions of pressure and time periods given the method.

If the low-pressure plasma is produced with electrodes in step (b) of the process according to the invention, the electrode density preferably being in the above-mentioned range, a particularly effective and uniform (homogeneous) activation and subsequent hydrophobicization of the textile surface is achieved.

If, in step (b) of the method according to the invention, the low-pressure plasma treatment is carried out in a plasma treatment chamber at a power in the above-mentioned range or with a plasma generation source at a power in the above-mentioned range, particularly good results with respect to the activation of the textile surface the subsequent hydrophobing and their longevity achieved.

It has been shown that particularly good or even the best results with regard to the preliminary plasma activation of a textile surface by the process according to the invention and thus also very good or even the best results in terms of moisture-repellent properties of the plasma-treated hydrophobierten tex- tilen surface and the durability of the moisture repellent Properties result when the inventive method (in step (b)) is carried out as a low-pressure plasma treatment with a plasma generation source at a power in the above range or in the preferred range specified above. Thus, at lower than the above values of the power of the plasma generation source, e.g. Inadequate plasma activation of the textile surface occurs, which ultimately leads to unsatisfactory moisture-repellent properties of the treated textile surface and / or to unsatisfactory durability of these moisture-repellent properties. In contrast, at higher than the above values of the power of the plasma generation source even damage to the textile surface used can occur.

Preference is given to a process according to the invention or one described above or below as being preferred, wherein the wet-chemical treatment in step (c) comprises one or more or all of the following measures: Impregnating, preferably full bath impregnating, particularly preferably by means of padding, the plasma-treated textile surface resulting in step (b) or a textile surface produced therefrom in further steps,

Drying of absorbed hydrophobizing agent on the textile surface,

Fixing absorbed hydrophobing agent on the textile surface, wherein the wet-chemical treatment preferably comprises a full bath impregnation, particularly preferably a full bath impregnation by padding, in step (b) resulting plasma-treated textile surface or a textile surface produced therefrom in further steps, preferably thereafter drying and / or fixing absorbed hydrophobing agent on the textile surface takes place.

In the context of the present invention, the impregnation in the course of the abovementioned wet-chemical treatment in step (c) of the process according to the invention can be carried out by any suitable method for this purpose, for example by spraying, dipping, pressure impregnation, kiss-and-roll, Wash-in impregnation, for example in the washing machine, full bath impregnation (preferred) or by a combination of several of the aforementioned methods.

The impregnation is preferably carried out according to the invention by full bath impregnation, particularly preferably by padding, preferably when the wet chemical treatment is an aqueous wet chemical treatment. In this way, the plasma-treated hydrophobicized textile surface obtained in step (c) of the process according to the invention is most effectively brought into contact with the hydrophobizing agent, resulting in a particularly completely and permanently hydrophobicized textile surface.

Also preferred is a preferred process according to the invention or one described above or below, wherein the wet-chemical treatment in step (c)

an aqueous wet-chemical treatment (as explained above), which comprises impregnating (as explained above), preferably full bath impregnation, in particular preferably by means of padding, comprising the plasma-treated textile surface or a textile surface produced therefrom in step (b) with an aqueous hydrophobing agent comprising modified polydimethylsiloxane, the modified polydimethylsiloxane being present in a concentration in the range of 200 g / L to 400 g / L, preferably in the range of 250 g / L to 350 g / L, based on the total amount of aqueous liquid used in the wet-chemical treatment in step (c) is used.

If the above-defined wet-chemical treatment with a modified polydimethylsiloxane (as described above or with such modified polydimethylsiloxane described as preferred) in a concentration in the range of 200 g / L to 400 g / L, preferably in the range of 250 g / L to 350 g / L, based on the total amount of aqueous liquid used in the wet-chemical treatment in step (c) (in particular on a textile surface of an article prepared or provided in step (a) as described above, which comprises one or more materials which are selected from the group consisting of a first material selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof), the best results according to the method according to the invention with respect to moisture-repellent properties of the resulting impregnated fabric and durability of the impregnation achieved. As a result, lower than the concentrations of modified polydimethylsiloxane indicated above may result in unsatisfactory moisture repellency properties of the treated textile surface. In contrast, higher than the concentrations of modified polydimethylsiloxane indicated above may even result in a decreased durability of the moisture-repellent properties of the treated textile surface.

Particular preference is given to a process according to the invention or one described above or below as being preferred, wherein the wet-chemical treatment in step (c) is an aqueous wet-chemical treatment and a full bath impregnation, preferably by means of padding, of the plasma-treated textile surface resulting in step (b) or the textile surface produced therefrom in further steps, wherein the full bath impregnation, preferably the padding, is carried out at a pressure in the range from 100 kPa to 500 kPa, preferably in the range from 200 kPa to 400 kPa and / or at a speed of passage of the textile surface (length dimension of the textile surface) through the full bath serving for the impregnation in the range of 0.5 m / min to 5 m / min, preferably in the range of 1 m / min to 3 m / min, and / or (preferably "and") at a temperature in the range of 15 ° C to 35 ° C, preferably in the range of 18 ° C to 25 ° C, is performed.

Preference is also given to a process according to the invention or a process described above or below as being preferred, wherein the wet-chemical

Treating in step (c) is an aqueous wet-chemical treatment and comprises drying absorbed hydrophobing agent on the textile surface, wherein the drying is carried out at a temperature in the range of 100 ° C to 140 ° C, preferably in the range of 1 10 ° C up to 130 ° C, and / or (preferably "and")

for a period in the range of 30 seconds to 5 minutes, preferably in the range of 1 minute to 4 minutes, and / or (preferably "and") in a tenter.

Preference is given to a method according to the invention or one described above or below as being preferred, wherein the wet-chemical treatment in step (c) is an aqueous wet-chemical treatment and comprises fixing absorbed hydrophobizing agent on the textile surface, wherein the fixing is carried out at a temperature in the range of 120 ° C to 190 ° C, preferably in the range of 140 ° C to 180 ° C, more preferably in the range of 150 ° C to 170 ° C, and / or (preferably "and")

for a period in the range of 20 seconds to 4 minutes, preferably in the range of 30 seconds to 3 minutes, more preferably in the range of 1 minute to 3 minutes, and / or (preferably "and") in a tenter.

The measures specified above for the wet-chemical treatment in step (c) of the process according to the invention or as (particularly) preferred, including drying and fixing, are preferably combined with one another, which results in particularly preferred variants of the process according to the invention which are particularly effective and / or permanently hydrophobicized textile surfaces. Such particularly permanently hydrophobicized textile surfaces retain their advantageous, in particular water-repellent or watertight, properties particularly long and are particularly resistant to mechanical stress, for example by abrasion or washing or drying operations.

The present invention also relates to a textile article comprising a hydrophobicized textile surface, producible by a method according to the invention, preferably preparable by a method according to the invention described above as being preferred.

The textile article according to the invention is preferably selected from the group consisting of weatherproof clothing; Outdoor clothing, functional clothing; Work clothing, preferably for outdoor use; Ponchos; ponchos; Tarpaulins for motor vehicles or construction; awnings; Sunroofs; Umbrellas; Umbrellas; Tarpaulins; Tents and transport containers, preferably suitcases, carrier bags, sports bags, rucksacks and panniers. With regard to preferred embodiments of a textile article according to the invention, the explanations given above for the process according to the invention apply correspondingly, and vice versa.

The present invention also relates to the use of a low-pressure plasma process for the preliminary treatment of a textile surface of an article, before the wet-chemical hydrophobing of the textile surface.

With regard to preferred embodiments of the use according to the invention, the explanations given above for the process according to the invention and / or for the textile article according to the invention apply correspondingly, and vice versa. Preference is given to a use according to the invention or one described above or below as preferred of a low-pressure plasma process which is carried out with a gas mixture which comprises O 2 and at least one inert gas selected from the group consisting of He and Ar for the preparatory treatment of a textile surface of a Article, wherein the textile surface comprises one or more materials selected from the group consisting of

a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein the second material is preferably selected from the group of copolyesters which as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1, 3-propanediol and 1, 4-butanediol, particularly preferred Ethanediol) and which preferably comprise at least one other monomer other than the aforementioned monomers (terephthalic acid or one or more alkanediols); such as

- their mixtures; wherein preferably the textile surface comprises one or more materials, of which at least one is selected from the group consisting of

a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein preferably the second material is selected from the group of copolyesters which comprise as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1, 3-propanediol and 1, 4-butanediol, more preferably ethanediol) and which preferably comprise at least one other monomer which is one of the abovementioned monomers

(Terephthalic acid or one or more alkanediols) is different; before the wet-chemical hydrophobing of the textile surface. EXAMPLES The examples below are intended to describe and explain the invention in more detail without restricting its scope.

Example 1: Providing an article with a textile surface

As the article having a textile surface, in each of the examples given below, a fabric was used (provided) consisting of 100% individual filaments of a biodegradable synthetic polymer (a copolyester comprising Monomeric terephthalic acid and ethanediol and at least one other monomer). The weight per unit area of the fabric was about 150 g / m ² and the thread density was about 100 warp threads / cm and about 50 weft threads / cm.

The tissue thus provided was designated "G-to".

Similarly convincing results as described below, in particular with regard to the improvement of the water-repellent properties achievable by the process according to the invention, are also obtained when using other textile surfaces, for example when using one of the textile surfaces specified above or preferably usable according to the invention. By way of example, mention may be made here of a fabric based on lyocell (cellulose) (for example Tencel®) or laminated polyester.

Example 2: Plasma treatment of a textile surface 2.1 Plasma treatment with a gas mixture

A sample of the tissue provided above (see Example 1) was subjected to low pressure plasma activation in a Nano Plasmacoater BAG with plasma chamber (about 11 m ³ ) and a plurality of electrodes (electrode density about 3.5 electrodes / m ² tissue ), with the following parameters being set:

Frequency: 13.56 MHz

Duration of treatment: 2 min

Power (plasma source): 9 kW

Pressure: 0.3 mbar (30 Pa)

Process gas: O2 (molecular oxygen)

Inert gas: Ar (argon)

Process gas / inert gas ratio: 20 vol.% Ar / 80 vol.% O2. The tissue thus plasma-treated was designated "G-tO-pbh (Ar / O 2)". 2.2 Plasma treatment with inert gas

Another sample of the fabric provided above (see Example 1) was subjected to just as low-pressure plasma activation as described above under 2.1, but only the inert gas argon, but not the process gas molecular oxygen was used (100 vol .-% argon ).

The tissue so plasma-treated was designated "G-tO-pbh (Ar)".

2.3 Plasma treatment with process gas

Another sample of the tissue provided above (see Example 1) was subjected to just as low-pressure plasma activation as described above under 2.1, but only the process gas molecular oxygen, but not the inert gas argon was used (100 vol .-% O2 ).

The tissue thus plasma-treated was designated by "G-tO-pbh (O 2)." Example 3 Preparation of Hvdrophobierunsmittel

The compositions stated below (see Table 1) of aqueous water repellents (hereinafter abbreviated to "HPM") which can be used in the process according to the invention (step (c)) comprising modified polydimethylsiloxane (hereinafter also referred to as " Abbreviated "PDMS").

As chitosan, a chitosan having a degree of deacetylation of 95% and a molecular weight of 300,000 to 500,000 g / mol (Da) was used in each case. The amino-functionalized (styrene) acrylate copolymer was in each case an emulsifier-containing dispersion (about 35% by weight of active content) of an acrylate-styrene copolymer having 25-45% by weight of amino-functional monomers and a molecular weight of between 50,000 and 500,000 g / mol (Da). Table 1: Compositions of water repellents

as an aqueous microemulsion

Example 4: Wet-chemical treatment of a textile surface

4.1 Wet-chemical treatment of a plasma-treated textile surface (according to the invention)

A plasma-treated fabric "G-to-pbh (Ar / O 2)" prepared as described above (see Example 2.1) was prepared in a manner known per se in a padding machine (also known as "padding machine" or "Padding-Mangle ") was impregnated with the aqueous hydrophobing agent HPM3 (concentration: 300 g / L) prepared as described above (see Example 3), the following parameters being set:

Pressure: 300 kPa (3 bar)

Temperature: 21 ° C Feed rate: 2 m / min

Subsequently, the wet-chemically treated (impregnated) fabric was dried for 2 min at 120 ° C on a tenter.

For fixing, the dried tissue was then treated for a further 1 minute on a spreader frame at 180 ° C.

The hydrophobized fabric which had been plasma-treated in this way corresponded to an article produced according to the invention having a hydrophobicized textile surface and was designated "G-tO-pbh (Ar / O 2) -hydr".

The plasma-treated fabric "G-to-pbh (Ar)" and "G-to-pbh (O 2)" prepared as described above (see Examples 2.2 and 2.3) were impregnated in the same manner as stated hereinbefore , dried and fixed. The water-repellent fabrics treated in this way in accordance with the invention corresponded in each case to articles having a hydrophobicized textile surface and according to the invention were designated "G-to-pbh (Ar) -hydr" or "G-to-pbh (O 2) -hydr". 4.2 Wet-chemical treatment of a non-plasma-treated textile surface (comparison)

A non-plasma-treated fabric "G-to" provided as described above (see Example 1) was impregnated in a padding machine with the hydrophobing agent HPM3 prepared as described above in otherwise identical manner as described in Example 4.1, then likewise dried and fixed.

The non-plasma-treated hydrophobized fabric produced in this way was designated "G-to-hydr" and used as comparison fabric produced according to the invention.

Example 5: Determination of the Contact Angle The contact angle Θ of gas-circulated liquids on a solid surface denotes the angle at the phase boundary of gaseous, liquid and solid phases. The size of the contact angle between liquid and solid depends on the interaction between the substances at the interface. The smaller this interaction, the larger the contact angle becomes. From the determination of the contact angle certain properties of the surface of a solid can be determined, for. B. the surface energy. In the special case of the use of water as liquid, the surface is described as hydrophilic at low contact angles (about 0 °), as hydrophobic at angles of 90 ° and as superhydrophobic at even larger angles. The latter is also called the lotus effect at very high angles (about 160 °) and corresponds to an extremely low wettability. By surface treatment, the contact angle can be changed. The contact angle Θ can be measured with a contact angle goniometer.

The contact angles with glycerin (98%) and with water on the tissues "G-to" or "G-to-pbh (Ar / 02)" provided or prepared as indicated above were determined as specimens (strained tissue), according to the standard DIN 55660-2: 201 1-12 (static method). The contact angle was determined in each case 5 seconds after application of the test liquid to the stretched tissue surface. The results of this experiment with glycerol as the test liquid are given below in Table 2:

Table 2: Contact angle of glycerin on tissue surfaces

From the values given in Table 2 it can be seen that when using glycerol (98%) as the test liquid, the tissue surface G-to-pbh (Ar / 02) has become significantly more wettable by the low-pressure plasma treatment (lower value for the contact angle Θ ) as the non-plasma-treated tissue surface G-to-O used for comparison.

From this result it can be concluded that the low-pressure plasma treatment has led to the textile surface being more wettable, which is advantageous for the subsequent wet-chemical treatment. The effects of low-pressure plasma treatment on textile surfaces (better wettability) can be shown particularly well by the use of glycerol, as test liquid with comparatively high viscosity. Example 6 Determination of the Durability of the Hydrophobing (Spray Test)

The durability of the hydrophobization (moisture repellency) of a textile surface which can be achieved by the process according to the invention was determined and compared with that of a non-inventively produced textile surface.

Example 6a: Durability of the Hydrophobing versus Wash-Dry Cycles For this purpose, G-tO-pbh (Ar / O ₂ ) -hydr, G-tO-pbh (Ar) -hydr and G-to-O- were prepared with the fabrics provided or prepared as indicated above. pbh (0 ₂ ) -hydr (each produced according to the invention) and G-to-hydr (comparison) in each case carried out a spray test with water according to the standard AATCC TM22-2014.

This spray test is used to determine the water-repellent properties of textile surfaces with or without equipment. Here, the tensioned textile surface is wetted under controlled conditions with water, whereby a moisture pattern on the textile surface is formed, the expansion of which depends on the relative water repellency of the considered textile surface. Evaluation of the test result as "moisture rejection level" is made by comparing the resulting moisture pattern with corresponding reference standard patterns on a scale of 0 ("full humidification of the entire upper and lower surfaces") to 100 ("no sticking or moistening, too only the upper surface ").

The results of this experiment are given below in Table 3, once for the corresponding fabrics after their preparation or manufacture (see column A: "Initial", ie without prior washing and drying treatment) and once for the same fabrics, but after every five Washing and drying cycles (see column B: "After 5 W / T cycles"). The washing and drying cycles were carried out in accordance with the standard ISO 6330: 2000 (E) (type A washing machine / front loader, washing program 5A "normal" at 40 ± 3 ° C; standard detergent without phosphates, ballast: 2 kg; drying in tumble dryer) at 65 ° C for 30 min.). Example 6b: Durability of the hydrophobing against abrasion

For this purpose, as described above (see Example 6a), a spray test with water according to the standard AATCC TM22-2014 was carried out on the fabrics G-to-pbh (Ar / O 2) -hydro prepared according to the invention or prepared according to the invention. tO-hydr (comparison), namely after an abrasion test according to the standard ASTM D4966-98 (2004) had been carried out with these two fabrics ("Martindale" abrasion test method; conditions: abrasives: wool; weight of abrasives: 12 kPa Number of abrasion cycles: 2000). The results of this experiment were evaluated as indicated above (see Example 6a) and reported below in Table 3 (see column "C: Moisture Repellency Test (Martindale)").

Table 3: Results of the spray test on textile surfaces

"N.b.": Values not determined

It can be seen from the values given in Table 3 that the plasma-treated hydrophobized (impregnated) textile surface of an article produced by the process according to the invention already after its preparation was more moisture-repellent (ie comparatively more hydrophobic) than those according to the same process, but without previous plasma treatment, only by wet-chemical treatment impregnated textile surface (see column "A").

Furthermore, it can be seen from the values given in Table 3 that the difference in the moisture-repellent properties becomes even greater when the corresponding values are compared after five washing and drying cycles (ie after mechanical, chemical and heat stress) had hardly changed moisture-repellent properties of the textile surface of the article produced by the process according to the invention with hydrophobized textile surface (best result for the article G-tO-pbh (Ar / 0 ₂ ) -hydr; standard reference pattern 90 instead of 100), had the moisture-repellent properties of the textile surface used for comparison (G-to-hydr) significantly deteriorated by the previous stress (see column "B").

It can also be seen from the values given in Table 3 that the plasma-treated, hydrophobicized (impregnated) textile surface of an article (G-to-pbh (Ar / 02) -hydr) produced by the process according to the invention has a better abrasion resistance than that according to the same procedure, but without prior plasma treatment, only by wet-chemical treatment impregnated textile surface (G-to-hydr), (see column "C").

It can be concluded from this result that a (impregnated) textile surface produced by the process according to the invention has better, more durable and more resistant hydrophobic (ie water-repellent or water-repellent) properties than a fabricated (impregnated) fabric according to a known process of the prior art ) textile surface.

Example 7: Determination of the extent of hydrophobing (water column) The degree of water resistance of a hydrophobbed textile surface article produced by the method of the present invention was determined and compared with an article made (impregnated) by a known prior art method ,

For this purpose, G-tO-pbh (Ar / O ₂ ) -hydr, G-tO-pbh (Ar) -hydr and G-to-pbh (0 ₂ ) -hydr (each according to the invention) were prepared with the tissues provided or prepared above ) and G-to-hydr (comparative) a test to determine the resistance against the penetration of water according to the standard ISO 81 1: 1981-10 / DIN EN 2081 1: 1992-08 (water column above the textile surface, ie above / facing the plasma-treated textile surface or above / facing the plasma-treated, hydrophobic surface) carried out ("hydrostatic pressure test").

The water resistance is given by this test as the resistance of each considered textile surface against a water column. The height of the water column in cm, which leads to the permeability of the textile surface to water according to the test conditions of the above-mentioned standard, is given as a measure of the water resistance of the textile surface. The results of this experiment are given below in Table 4, once for the corresponding fabrics after their preparation or manufacture (see column A: "Initial", ie without prior washing and drying treatment) and once for the same fabrics, but after every five Washing and drying cycles (see column B: "After 5 W / T cycles"). The washing and drying cycles were carried out according to the standard ISO 6330: 2000 (E) (washing machine type A / front loader, washing program 5A "normal" at 40 ± 3 ° C; standard detergent without phosphates, ballast 2 kg; Tumble dryer at 65 ° C for 30 min.):

Table 4: Results of the hydrostatic pressure test on textile surfaces

B: water resistance

A: water resistance (Was¬

Tissue (water column) [cm] (after column) [cm] (Initial)

5 W / T cycles)

G-to-hydr (comparison) (25) / 13,25 7

G-to-pbh (Ar / O ₂ ) -hydr (Er

(33) / 38,25 24,5

invention)

G-to-pbh (0 ₂ ) -hydr (inventions

24.5 18

dung)

G-to-pbh (Ar) -hydr (inventions

29.5 13.25

dung) The values in brackets in Table 4 (column A) are to be assigned to a separate measurement series. Likewise, the non-bracketed values in Table 4 (column A) are to be assigned to another separate series of measurements.

It can be seen from the values given in Table 4 that the plasma-treated hydrophobized (impregnated) textile surfaces of articles having a hydrophobicized textile surface produced by the process according to the invention already had a significantly higher water resistance after their preparation (ie comparatively more hydrophobic) than one after the same Process only wet-chemically impregnated textile surface, but without prior plasma treatment. The best result was obtained with the article G-to-pbh (Ar / O ₂ ) -hydr (see column A).

Furthermore, it can be seen from the values given in Table 4 that the difference in water resistance in preferred cases becomes even greater when the corresponding values are compared after five washing and drying cycles (ie after mechanical, chemical and heat stress) Had properties of the water resistance of the textile surface of the process according to the invention (low-pressure plasma treatment with at least one oxygen-containing compound) made relatively less hydrophobized textile surface, the properties of the water resistance of the textile surface used for comparison (G-to-hydr) by the previous stress significantly worsened (see column B). The best value for the remaining water resistance after five washing and drying cycles was obtained for the article G-to-pbh (Ar / 02) -hydr.

Claims

claims:

1. A process for producing a textile article having a hydrophobicized textile surface, comprising the following steps:

(a) making or providing an article having a textile surface,

(b) plasma treating the textile surface produced or provided in step (a) to give a plasma treated textile surface,

(c) wet-chemically treating the plasma-treated textile surface resulting in step (b) or a textile surface produced therefrom in further steps with a hydrophobicizing agent so that a plasma-treated hydrophobized textile surface results.

A method according to any one of the preceding claims, wherein the textile surface of the article produced or provided in step (a) comprises one or more materials selected from the group consisting of

a first material, preferably a natural material, preferably selected from the group consisting of cotton, wool, silk, cellulose and cellulose regenerate and mixtures thereof; particularly preferably selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof;

a second material, preferably a synthetic material, preferably selected from the group consisting of polyesters, polyamides, polyamidoimides, polypropylene, polyacrylonitrile and polyacrylic methacrylate and mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; such as their mixtures.

3. The method of claim 1, wherein the textile surface of the article produced or provided in step (a) comprises one or more materials selected from the group consisting of

a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; such as

- their mixtures; wherein preferably the textile surface comprises one or more materials, at least one of which is selected from the group consisting of

a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof.

A method according to any one of the preceding claims, wherein the textile surface of step (a) manufactured or provided article is selected from the group consisting of woven, knitted, crocheted, braided, stitchbonded, felts, nonwoven fabrics, nonwoven fabrics, textile hoses, ropes, fibers, threads , Yarns, rovings and mixtures thereof; preferably selected from the group consisting of woven, knitted, crocheted, nonwoven fabrics, nonwoven fabrics and mixtures thereof; and or

a woven, knitted, knitted, braided, stitchbonded, felted, nonwoven fabric and / or textile hose, preferably a woven fabric and / or a knitted fabric, particularly preferably a woven fabric, which has a basis weight in the region of 20 g / m ² to 500 g / m ² , preferably in the range of 100 g / m ² to 200 g / m ² , and / or

5. The method according to any one of the preceding claims, preferably according to claim 3, wherein the hydrophobizing agent used in step (c)

is an aqueous hydrophobing agent, which preferably comprises modified polydimethylsiloxane, and / or does not comprise fluorine-containing organic compounds.

6. The method of claim 5, wherein the hydrophobing agent is an aqueous hydrophobing agent comprising - modified polydimethylsiloxane, preferably modified polydimethylsiloxane, wherein one or more methyl groups are replaced by substituents having basic functional groups, alkyl groups and / or polyether groups; as well as additional comprising one or more cationic polymers selected from the group consisting of

Polyester,

polypeptides

polyamides

7. The method of claim 6, wherein

the modified polydimethylsiloxane is a modified polydimethylsiloxane,

wherein one or more methyl groups are each replaced by a substituent with a basic functional group, preferably in each case by an aminoalkyl group or an amido-aminoalkyl group, and which preferably comprises terminal methoxy groups; and or

- wherein the one or more cationic polymers are selected from the group consisting of

Polyacrylates which are functionalized by cationic groups or basic groups, preferably by amino groups, preferably styrene-acrylate copolymers, which are functionalized by basic groups, preferably by amino groups;

Polyurethanes functionalized by cationic groups or basic groups, preferably by amino groups;

Polyesters which are functionalized by cationic groups or basic groups, preferably by amino groups;

Chitosan, preferably with a degree of deacetylation> 75%; wherein preferably at least one of the one or more cationic polymers is selected from the group consisting of

Polyacrylates, preferably styrene-acrylate copolymers, which are functionalized by cationic groups or basic groups, preferably by basic groups, more preferably by amino groups, and

Chitosan, preferably with a degree of deacetylation> 75%.

A method according to any one of the preceding claims, wherein the plasma treatment in step (b)

a low pressure plasma treatment, preferably a low pressure plasma activation, is or

9. The method of claim 8, wherein the low pressure plasma treatment is carried out at a pressure in the range of 1 Pa to 20 kPa, preferably at a pressure in the range of 1 Pa to 0.5 kPa, more preferably at a pressure in the range of 10 Pa to 50 Pa.

10. The method according to any one of claims 8 or 9, wherein the Niederdruckplasmabe- treatment with at least one oxygen-containing compound selected from the group consisting of O, O2, O3, NO, N2O and CO2, is performed, so that preferably oxygen-containing functional groups the textile surface are produced, which are preferably covalently bonded to the textile surface.

1 1. The method of claim 10, wherein the at least one oxygen-containing compound

and / or in admixture with at least one inert gas, preferably selected from the group consisting of He, Ar, Ne and Xe, and / or in a gas mixture which comprises O 2 and at least one inert gas selected from the group consisting of He and Ar, preferably the said gas mixture, which is O 2 and at least one inert gas selected from the group consisting of He and Ar, comprises at least 99% by volume of O 2 and at least one inert gas selected from the group consisting of He and Ar, and more preferably contains at least 99% by volume of O 2 and Ar.

12. The method of claim 1 1, wherein the gas mixture has a content of O2 in the range of 70 vol .-% to 90 vol .-% and a content of inert gas, preferably He and / or Ar, in the range of 10 vol. % to 30% by volume.

13. The method of claim 1, wherein the textile surface of the article produced or provided in step (a) comprises one or more materials selected from the group consisting of

a first material selected from the group consisting of cotton, wool, silk, cellulose and cellulose regenerate, and mixtures thereof; particularly preferably selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof;

a second material selected from the group consisting of polyesters, polyamides, polyamideimides, polypropylene, polyacrylonitrile and polyacrylmethacrylate and mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably the biodegradable synthetic see polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; and - their mixtures; the plasma treatment in step (b)

a low-pressure plasma treatment, preferably a low-pressure plasma activation, wherein the low-pressure plasma treatment is carried out with at least one oxygen-containing compound selected from the group consisting of O, O 2, O 3, NO, N 2 O and CO 2, so that preferably oxygen-containing functional groups on the textile surface, preferably covalently bonded to the textile surface, and the hydrophobizing agent used in step (c) is an aqueous hydrophobing agent comprising modified polydimethylsiloxane, preferably modified polydimethylsiloxane, in which one or more methyl groups are substituted by substituents basic functional groups, alkyl groups and / or polyether groups are replaced; and additionally comprises one or more cationic polymers selected from

Group consisting of

Polyacrylates, preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters and optionally other monomers copolymerizable with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters, preferably styrene; Polyurethanes, preferably polyester-type and / or polycarbonate-type polyurethanes;

Polyester,

Polypeptides, polyamides and

14. The method of claim 1, wherein the textile surface of the article produced or provided in step (a) comprises one or more materials selected from the group consisting of

a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; and - their mixtures; wherein preferably the textile surface comprises one or more materials, at least one of which is selected from the group consisting of a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; the plasma treatment in step (b)

a low-pressure plasma treatment, preferably a low-pressure plasma activation, which is carried out in the presence of a gas mixture comprising O 2 and at least one inert gas selected from the group consisting of He and Ar, preferably wherein said gas mixture is at least 99% by volume at O2 and at least one inert gas selected from the group consisting of He and Ar, and particularly preferably said gas mixture contains at least 99 vol .-% of O2 and Ar, and the hydrophobizing agent used in step (c) is an aqueous hydrophobing agent compound comprising modified polydimethylsiloxane, preferably modified polydimethylsiloxane, wherein one or more methyl groups are replaced by substituents with basic functional groups, alkyl groups and / or polyether groups; and additionally comprises one or more cationic polymers selected from the group consisting of

Polyacrylates, preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters and optionally further, with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic esters co-polymerizable monomers, preferably styrene; Polyurethanes, preferably polyester-type and / or polycarbonate-type polyurethanes;

Polyester,

Polypeptides, polyamides and

Method according to one of claims 8 to 14, wherein in step b)

- The low-pressure plasma is generated at a frequency in the range of 10 MHz to 18 MHz, preferably in the range of 1 1 MHz to 15 MHz; and or

- The low-pressure plasma is generated with electrodes, wherein the electrode density preferably in the range of 1 to 10 electrodes / m ² , more preferably in the range of 2 to 5 electrodes / m ² , most preferably in the range of 2.5 to 4 electrodes / m ² , based on the textile surface produced or provided in step (a); and or - The low-pressure plasma treatment with a plasma generating source at a power in the range of 0.05 kW to 100 kW, preferably in the range of 1 kW to 25 kW, more preferably in the range of 2 kW to 15 kW, most preferably in the range of 5 kW to 10 kW, is performed, and / or

16. A method according to any one of the preceding claims, wherein the wet-chemical treatment in step (c) comprises one or more or all of the following measures:

Impregnating, preferably full bath impregnating, particularly preferably by means of padding, the plasma-treated textile surface resulting in step (b) or a textile surface produced therefrom in further steps,

Drying of absorbed hydrophobizing agent on the textile surface,

Fixing absorbed hydrophobing agent on the textile surface, wherein the wet-chemical treatment preferably comprises a full bath impregnation, particularly preferably by means of padding, in step (b) resulting plasma-treated textile surface or a textile surface produced therefrom in further steps, preferably after drying and / or Fix recorded hydrophobicizing agent on the textile surface takes place.

17. The method according to any one of the preceding claims, wherein the after step (c) resulting plasma-treated hydrophobicized textile surface - is comparatively more hydrophobic than the textile surface

the article manufactured or provided in step (a) and / or

the plasma-treated textile surface resulting in step (b), and / or

the article produced or provided in step (a) after only wet-chemical treatment as in step (c) but without prior plasma treatment in step (b), and / or

- Has a comparatively more durable hydrophobic than the corresponding textile surface of the article produced or provided in step (a) after only wet-chemical treatment as in step (c), but without prior plasma treatment in step (b).

18. A textile article comprising a hydrophobicized textile surface, producible by a method according to one of the preceding claims.

19. Use of a low-pressure plasma process for the preliminary treatment of a textile surface of an article, before the wet-chemical hydrophobing of the textile surface.

Use according to claim 19, wherein the low pressure plasma process is performed with a gas mixture comprising O 2 and at least one inert gas selected from the group consisting of He and Ar and the textile surface comprises one or more materials selected from the group consisting of