EP3697958B1 - Method for producing a textile article with hydrophobised textile surface using plasma treatment and wet chemical processing - Google Patents

Description

• a) Herstellen oder Bereitstellen eines Artikels mit einer textilen Oberfläche,
• (b) Plasmabehandeln der in Schritt (a) hergestellten oder bereitgestellten textilen Oberfläche, so dass eine plasmabehandelte textile Oberfläche resultiert,
• (c) nasschemisches Behandeln der in Schritt (b) resultierenden plasmabehandelten textilen Oberfläche oder einer daraus in weiteren Schritten hergestellten textilen Oberfläche mit einem Hydrophobierungsmittel, so dass eine plasmabehandelte hydrophobierte textile Oberfläche resultiert wobei das Plasmabehandeln in Schritt (b)
  • eine Niederdruckplasmabehandlung ist oder
  • eine Niederdruckplasmabehandlung und zumindest einen weiteren Plasmabehandlungsschritt umfasst, wobei die Niederdruckplasmabehandlung mit mindestens einer sauerstoffhaltigen Verbindung, ausgewählt aus der Gruppe bestehend aus O, O₂, O₃, NO, N₂O und CO₂, durchgeführt wird, wobei die mindestens eine sauerstoffhaltige Verbindung in einem Gasgemisch vorliegt, welches O₂ und mindestens ein Inertgas, ausgewählt aus der Gruppe bestehend aus He und Ar, umfasst, wobei das Gasgemisch einen Anteil an O₂ im Bereich von 70 Vol.-% bis 90 Vol.-% und einen Anteil an Inertgas im Bereich von 10 Vol.-% bis 30 Vol.-% enthält.

The present invention relates to a method for producing a textile article with a hydrophobized textile surface comprising the steps:

• a) Manufacturing or providing an article with a textile surface,
• (b) plasma treatment of the textile surface produced or provided in step (a) so that a plasma-treated textile surface results,
• (c) Wet-chemical treatment of the plasma-treated textile surface resulting in step (b) or a textile surface produced therefrom in further steps with a hydrophobing agent, so that a plasma-treated hydrophobed textile surface results, the plasma treatment in step (b)
  • is a low pressure plasma treatment or
  • comprises a low-pressure plasma treatment and at least one further plasma treatment step, the low-pressure plasma treatment being 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 , the at least one oxygen-containing compound is present in a gas mixture which _{comprises O 2} and at least one inert gas selected from the group consisting of He and Ar, the gas mixture having a proportion of O ₂ in the range from 70% by volume to 90% by volume and a proportion of inert gas in the range from 10% by volume to 30% by volume.

Furthermore, the invention also relates to a textile article which can be produced by the method according to the invention. In addition, the invention also relates to the use of a low-pressure plasma process for the preparatory treatment of a textile surface of an article, prior to the wet-chemical hydrophobing of the textile surface, the low-pressure plasma treatment 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 , is carried out, the at least one oxygen-containing compound being present in a gas mixture which _{comprises O 2} and at least one inert gas selected from the group consisting of He and Ar, the gas mixture having a proportion of O ₂ in the range from 70% by volume to 90% by volume and a proportion of inert gas in the range from 10% by volume to 30% by volume.

Textile articles with a hydrophobic surface, for example a water-repellent or waterproof surface, such as outdoor clothing articles, are currently mainly produced by finishing them with fluorine-containing chemicals. Often perfluorinated or polyfluorinated organic compounds, also known as "fluorocarbons", are used for this purpose. However, since such fluorocarbons are very durable and are in the environment as well as accumulate in the human body - although a risk to the environment and the health of living organisms cannot be ruled out - alternatives are sought in the professional world which have similarly advantageous surface properties but avoid the aforementioned disadvantages. Contributions to this discussion can be found in the publication " Perfluorinated and polyfluorinated chemicals - avoiding pollution - protecting the environment "of the Federal Environment Agency from July 2009 and press release no. 32 of the Federal Environment Agency from October 2016 .

As part of the so-called "Detox Campaign" since 2011, numerous manufacturers and sales companies in Germany have also committed themselves to removing perfluorinated and polyfluorinated chemicals classified as potentially dangerous from their supply chains by 2020.

Already known alternatives for equipping textiles with fluorocarbons include the use of low-fluorinated hydrophobic and oleophobic application agents, fluorine-free hydrophobic application agents, including in particular silicones and conventional as well as modified polyurethanes, or plastic membranes or products based on nanoparticles or nanofibers (ie fibers with at least one dimension on the order of nanometers). The publication " Investigation of alternatives to the fluorocarbon finishing of textiles "by M. Schöttner, master's thesis at the University of Technology and Economics, Berlin 2012 .

Plasma treatment is also known per se for modifying textile surfaces. A plasma is a partially ionized gas, which is often referred to as the "fourth physical state of matter". Phenomena such as lightning or the northern lights ( aurora borealis ) are plasmas that occur in nature. Technically, they can be generated by applying electrical fields. Plasmas are interesting because of their physical and chemical properties. Highly excited particles and radicals are generated in them. These can trigger chemical reactions which are not possible under normal conditions. The temperature of the workpieces to be treated with a plasma can be kept very low.

The document DE 101 11 427 A1 teaches a method and an apparatus for cleaning and treating textiles in low pressure plasma.

The document EP 695 622 A2 describes a method and a device for plasma modification of porous objects, for example textiles.

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

From the document WO 2010/139466 A1 Impregnating agents are known 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 which comprises 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 hydrophobization of textile articles, which enables the production of at least water-repellent, ideally waterproof, textile surfaces that are durable and can help to make their use more durable , at best only slowly degradable in the environment, chemicals such as fluorocarbons or alkylphenol ethoxylates to be reduced or at least largely and ideally completely avoided. There is also a need for a process for the production of textiles suitable for numerous purposes (as well as such textiles themselves) which are at least partially and ideally completely biodegradable or compostable and thereby, for example, meet the criteria for certification according to the “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 method for producing a textile article with a hydrophobized textile surface which enables an effective, long-lasting and robust hydrophobization or impregnation of the textile surface and leads to a permanent and resistant, at least water-repellent, ideally waterproof, textile surface.

The textile articles produced according to the aforementioned method should retain the hydrophobic, in particular water-repellent or waterproof, surface properties, preferably even after demanding use - such as professional or industrial use, for example as work clothing - with increased requirements for abrasion resistance and resilience of the surface finish.

Another specific object of the present invention was to provide an environmentally friendly process which reduces or at least largely and ideally completely avoids the use of long-lasting chemicals such as fluorocarbons or alkylphenol ethoxylates that are at best only slowly degradable in the environment. An important aspect of this specific task was also to use the aforementioned environmentally friendly process to produce textile articles which are at least partially and ideally completely biodegradable (i.e. through biological mechanisms such as the action of microorganisms) and thus at least partially or ideally completely compostable and are accordingly suitable for a biological cycle management.

1. (a) Herstellen oder Bereitstellen eines Artikels mit einer textilen Oberfläche,
2. (b) Plasmabehandeln der in Schritt (a) hergestellten oder bereitgestellten textilen Oberfläche, so dass eine plasmabehandelte textile Oberfläche resultiert,
3. (c) nasschemisches Behandeln der in Schritt (b) resultierenden plasmabehandelten textilen Oberfläche oder einer daraus in weiteren Schritten hergestellten textilen Oberfläche mit einem Hydrophobierungsmittel, so dass eine plasmabehandelte hydrophobierte textile Oberfläche resultiert
   wobei das Plasmabehandeln in Schritt (b)
   • eine Niederdruckplasmabehandlung ist oder
   • eine Niederdruckplasmabehandlung und zumindest einen weiteren Plasmabehandlungsschritt umfasst,

wobei die Niederdruckplasmabehandlung mit mindestens einer sauerstoffhaltigen Verbindung, ausgewählt aus der Gruppe bestehend aus O, O₂, O₃, NO, N₂O und CO₂, durchgeführt wird, wobei die mindestens eine sauerstoffhaltige Verbindung in einem Gasgemisch vorliegt, welches O₂ und mindestens ein Inertgas, ausgewählt aus der Gruppe bestehend aus He und Ar, umfasst, wobei das Gasgemisch einen Anteil an O₂ im Bereich von 70 Vol.-% bis 90 Vol.-% und einen Anteil an Inertgas im Bereich von 10 Vol.-% bis 30 Vol.-% enthält.It has now surprisingly been found that the primary object as well as further objects and / or sub-objects of the present invention are achieved by a method according to the invention for producing a textile article with a hydrophobized textile surface, with the following steps:

1. (a) Manufacturing or providing an article with a textile surface,
2. (b) plasma treatment of the textile surface produced or provided in step (a) so that a plasma-treated textile surface results,
3. (c) Wet-chemical treatment of the plasma-treated textile surface resulting in step (b) or a textile surface produced therefrom in further steps with a hydrophobing agent, so that a plasma-treated hydrophobed textile surface results
   wherein the plasma treatment in step (b)
   • is a low pressure plasma treatment or
   • comprises a low-pressure plasma treatment and at least one further plasma treatment step,

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 , the at least one oxygen-containing compound being present in a gas mixture containing O ₂ and comprises at least one inert gas selected from the group consisting of He and Ar, the gas mixture having a proportion of O ₂ in the range from 70% by volume to 90% by volume and a proportion of inert gas in the range from 10% by volume Contains% to 30% by volume.

With the method according to the invention, textile articles with robust, long-lasting water-repellent or waterproof properties can be produced in an environmentally friendly way, even with reduced use or extensive or complete avoidance of long-life chemicals such as fluorocarbons or alkylphenol ethoxylates, which are at best only slowly degradable in the environment.

Textile articles produced by the method according to the invention are suitable for demanding use such as professional or industrial use with its increased requirements for abrasion resistance and resistance of the surface finish, for example for use as work clothing and / or also for industrial washing processes, since the textile articles are advantageous Maintain properties for a long time even under these demanding operating conditions.

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

A further advantage of the textile articles produced by the method according to the invention is their suitability for refreshing the hydrophobization or impregnation or a post-hydrophobization or post-impregnation, if, for example, after prolonged use of the textile article its water-repellent or waterproof property should decrease: a For this purpose, textile articles produced by the process according to the invention can again be given improved hydrophobic or water-repellent or waterproof properties by renewed wet-chemical treatment according to step (c) described above, for example by washing-in impregnation in the washing machine.

The invention and combinations of preferred parameters, properties and / or components of the present invention which are preferred according to the invention are defined in the appended claims. Preferred aspects of the present invention are also given or defined in the following description and in the examples.

The term plasma treatment is generally understood to mean all plasma processes that can be used for surface treatment, in particular for surface treatment of textile articles, especially plasma cleaning, plasma activation, plasma etching and plasma coating. The plasma treatment can comprise one or more of the above-mentioned plasma processes, which are explained in more detail below.

Plasma cleaning often precedes subsequent further plasma treatment steps and is usually carried out in low-pressure plasma. A universally applicable low-pressure plasma system is therefore often equipped in such a way that the essential cleaning processes, in particular cleaning in oxygen plasma, can be carried out. Such a low-pressure plasma system used for cleaning processes is also referred to as a "plasma cleaner".

Plasma activation (or plasma activation) is mostly used to increase the surface tension of non-polar substrates (i.e. materials or substances that are to be processed by plasma activation). For this purpose, oxygen radicals are usually generated in the oxygen plasma (i.e. using oxygen or compounds that form oxygen in the plasma, mostly gases), which, due to their high reactivity, can form bonds to the surface structures of a substrate, thereby increasing the surface tension and / or the wettability of the substrate surface becomes. No polymerizable monomers are used in plasma activation, since the aim is not to directly coat the substrate surface with polymer films. Plasma activation is usually carried out for shorter periods of time, for example in the range of less than 10 minutes. The quality of a plasma activation can be assessed or checked, for example, by means of known contact angle measurements. In this method, the contact angle of a drop of test liquid to the activated surface is measured. The better the activation, the flatter the drop lies on the surface.

Plasma etching refers to material-removing plasma-assisted etching processes on solids. During 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 especially of the radicals is used. The most important criterion when selecting the etching gas is its ability to form a highly 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, perfluorinated hydrocarbons (perfluorocarbons, PFCs) such as tetrafluoromethane (CF ₄ ), hexafluoroethane (C ₂ F ₆ ), perfluoropropane (C ₃ F ₈ ), perfluorobutadiene (C ₄ F ₆ ), unsaturated PFCs, perfluorinated aromatics and perfluorinated heteroaromatics. Inorganic etching gases are suitable 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 changes in physical or mechanical surface properties (mostly with high energy input) is to be achieved. Mixtures of different caustic gases are also common. Plasma etching is usually carried out for longer periods of time, for example in the range from 15 to 120 minutes.

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

In the method according to the invention, the plasma treatment comprises a low-pressure plasma treatment or a low-pressure plasma treatment and at least one further plasma treatment step, the low-pressure plasma treatment being 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 wherein the at least one oxygen-containing compound is present in a gas mixture which _{comprises O 2} and at least one inert gas selected from the group consisting of He and Ar, the gas mixture having a proportion of O ₂ in the range from 70% by volume to 90% by volume and a proportion of inert gas in the range from 10% by volume to 30% by volume.

• vergleichsweise hydrophober ist als die textile Oberfläche
  • des in Schritt (a) hergestellten oder bereitgestellten Artikels und/oder
  • der in Schritt (b) resultierenden plasmabehandelten (vorzugsweise plasmagereinigten und/oder plasmaaktivierten) textilen Oberfläche,
    und/oder
  • des in Schritt (a) hergestellten oder bereitgestellten Artikels nach nur nasschemischem Behandeln wie in Schritt (c), jedoch ohne vorheriges Plasmabehandeln in Schritt (b),
    und/oder
• vergleichsweise dauerhafter hydrophobiert ist als die entsprechende textile Oberfläche des in Schritt (a) hergestellten oder bereitgestellten Artikels nach nur nasschemischem Behandeln wie in Schritt (c), jedoch ohne vorheriges Plasmabehandeln in Schritt (b).
  "Vergleichsweise hydrophober" bedeutet dabei vorzugsweise, dass die nach Schritt (c) resultierende plasmabehandelte hydrophobierte textile Oberfläche einen höheren Wert (in cm) für die gemäß der Norm ISO 811-1981 / DIN EN 20811:1992-08 (Wassersäule oberhalb der textilen Oberfläche, d.h. oberhalb / zugewandt der plasmabehandelten textilen Oberfläche bzw. oberhalb / zugewandt der plasmabehandelten, hydrophobierten Oberfläche) gemessene Wassersäule aufweist, als die entsprechende textile Oberfläche
• des bzw. eines in Schritt (a) hergestellten oder bereitgestellten Artikels, welche keine entsprechende Behandlung gemäß den Schritten (b) und (c) erfahren hat
  und/oder
• des bzw. eines in Schritt (b) hergestellten Artikels, welche keine entsprechende Behandlung gemäß dem Schritt (c) erfahren hat
  und/oder
• des bzw. eines in Schritt (a) hergestellten oder bereitgestellten Artikels nach nur nasschemischem Behandeln wie in Schritt (c), jedoch ohne vorheriges Plasmabehandeln in Schritt (b).

A method according to the invention is preferred, wherein the plasma-treated hydrophobized textile surface resulting from step (c)

• is comparatively more hydrophobic than the textile surface
  • of the article produced 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
  • 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),
    and or
• is comparatively more permanently 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 more hydrophobic” here preferably means that the plasma-treated hydrophobized textile surface resulting from step (c) has a higher value (in cm) for the water column above the textile surface in accordance with the ISO 811-1981 / DIN EN 20811: 1992-08 standard , ie above / facing the plasma-treated textile surface or above / facing the plasma-treated, hydrophobized surface) has measured water column than the corresponding textile surface
• of the article produced or provided in step (a) which has not undergone a corresponding treatment according to steps (b) and (c)
  and or
• of the article produced in step (b) which has not undergone a corresponding treatment in accordance with step (c)
  and or
• of the or an article produced or provided in step (a) after only wet chemical treatment as in step (c), but without prior plasma treatment in step (b).

The textile surface of an article produced or provided in step (a) can - in particular for the purpose of a comparison with a method according to the invention and the textile surfaces resulting from a method according to the invention - be treated directly, i.e. without prior plasma treatment, wet-chemically. If the wet chemical treatment of an article produced or provided in step (a) for the purposes of comparison is carried out in the same way as in step (c) according to the invention, a textile surface is obtained which can be evaluated in direct comparison with regard to its hydrophobicity. A corresponding comparative study is given below in Example 6 (cf. Table 3, values "A: moisture repellency initial").

"Comparatively more permanently hydrophobized" preferably means that the plasma-treated hydrophobized textile surface resulting from step (c) has a higher value determined according to the spray test of the AATCC TM22-2014 standard (in standard values according to the standard specification) 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). Particularly preferably, "comparatively more permanently hydrophobicized" means that the plasma-treated hydrophobicized textile surface resulting from step (c) also after five washing and drying cycles (preferably carried out in accordance with ISO 6330: 2000 (E), conditions: washing machine type A / front loader; Wash program 5A "Normal" at 40 ± 3 ° C; tumble-dry) has a higher value than the one treated for comparison purposes under the same conditions (ie also present after five washing and drying cycles), determined in accordance with the AATCC TM22-2014 standard ) 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).

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

• ein oder mehrere Materialien umfasst, welche ausgewählt sind aus der Gruppe bestehend aus
  • einem ersten Material (hier und im Folgenden gemeint im Sinne einer "ersten Materialgruppe"), vorzugsweise einem natürlichen Material, vorzugsweise ausgewählt aus der Gruppe bestehend aus Baumwolle, Wolle, Seide, Cellulose und Cellulose-Regenerat sowie deren Mischungen; besonders bevorzugt ausgewählt aus der Gruppe bestehend aus Cellulose und Cellulose-Regenerat sowie deren Mischungen;
  • einem zweiten Material (hier und im Folgenden gemeint im Sinne einer "zweiten Materialgruppe"), vorzugsweise einem synthetischen Material, vorzugsweise ausgewählt aus der Gruppe bestehend aus Polyestern, Polyamiden, Polyamidimiden, Polypropylen, Polyacrylnitril und Polyacrylmethacrylat sowie deren Mischungen; besonders bevorzugt ausgewählt aus der Gruppe der synthetischen Polymere, vorzugsweise der biologisch abbaubaren synthetischen Polymere, bestehend aus substituierten Polyestern, unsubstituierten Polyestern, substituierten Polyamiden und unsubstituierten Polyamiden sowie deren Mischungen;
    sowie
  • deren Mischungen (hinsichtlich der Zahl der Bestandteile und ihrer Anteile beliebige Mischungen eines oder mehrerer erster, vorzugsweise natürlicher, Materialien und/oder eines oder mehrerer zweiter, vorzugsweise synthetischer, Materialien)
  und/oder
• ausgewählt ist aus der Gruppe bestehend aus Geweben, Gewirken, Gestricken, Geflechten, Nähgewirken, Filzen, Textilverbundstoffen, Faservliesen, textilen Schläuchen, Seilen, Fasern, Fäden, Garnen, Vorgarnen und deren Mischungen; vorzugsweise ausgewählt ist aus der Gruppe bestehend aus Geweben, Gewirken, Gestricken, Textilverbundstoffen, Faservliesen und deren Mischungen.

Also preferred is a method according to the invention or a preferred method according to the invention 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 (meant here and below 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 regenerated cellulose and mixtures thereof; particularly preferably selected from the group consisting of cellulose and regenerated cellulose and mixtures thereof;
  • a second material (meant here and in the following in the sense of a “second group of materials”), preferably a synthetic material, preferably selected from the group consisting of polyesters, polyamides, polyamide-imides, polypropylene, polyacrylonitrile and polyacryl 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 (with regard to the number of components and their proportions, any 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 fabrics, knitted fabrics, knitted fabrics, braids, stitchbonded fabrics, felts, textile composites, nonwovens, textile tubes, ropes, fibers, threads, yarns, roving yarns and mixtures thereof; is preferably selected from the group consisting of woven fabrics, knitted fabrics, knitted fabrics, textile composites, nonwovens and mixtures thereof.

The one or more materials comprised by the textile surface of the article produced or provided in step (a) of the method according to the invention can be used individually or in combination. For this purpose, one or more materials from a first material (ie selected from the material group of a first material or a first material group as defined above) can be used or one or more materials 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 selected from a second material (ie from the material group of a second material or a second material group as defined above). Combinations of preferred materials (thus) in turn result in preferred materials or material combinations.

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 polyacryl methacrylate and their Mixtures; 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 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 group of materials) consisting of polyesters, polyamides, polyamide-imides, Polypropylene, polyacrylonitrile and polyacryl 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. In this preferred variant of the method according to the invention, the textile surface of the article produced or provided in step (a) does not comprise a first material (preferably natural material), ie no material that is preferably selected from the group (preferably a first material group) consisting of cotton, Wool, silk, cellulose and regenerated cellulose 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 (and therefore biological degradable) material, preferably selected from the group (preferably a first group of materials) consisting of cotton, wool, silk, cellulose and regenerated cellulose; and at least one second material (as defined above), preferably a synthetic material, which is selected from the group (preferably a second group of materials) 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 textile articles produced by the process according to the invention are advantageously at least partially and - depending on the other components of the textile article such as the water repellent - ideally completely biodegradable (ie through biological mechanisms such as the action of microorganisms) and thus at least partially and ideally completely compostable and therefore suitable for biological recycling. This variant of the method according to the invention is therefore preferred.

"Biodegradable" means in the context of the present invention that a textile article, a material, or a substance with this property is compostable and preferably within a period in the range from 12 to 36 months, particularly preferably in the range from 18 to 30 months, and preferably at a temperature in the range from 40 ° C. to 80 ° C., particularly preferably in the range from 50 ° C. to 75 ° C., at least predominantly (ie> 90% by weight, preferably> 95% by weight, of the starting material are biodegraded under the conditions specified here) and ideally practically completely biodegraded (ie by biological mechanisms such as the action of microorganisms).

If the textile surface of the article produced or provided in step (a) comprises one or more materials selected from the group consisting of at least one first material (as defined above), preferably a natural (and therefore biodegradable) material from the group (preferably a first group of materials) consisting of cellulose and regenerated cellulose; and at least one second material (as defined above), preferably a synthetic material selected from the group (preferably a second group of materials) of synthetic polymers, preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides , as well as mixtures of the aforementioned materials, the products produced by the process according to the invention are not only advantageously at least partially and ideally practically completely biodegradable and thus at least partially and ideally completely compostable, but they are also suitable for particularly high requirements their mechanical resilience and the longevity or durability of the to correspond to hydrophobic or water-repellent or waterproof properties. This variant of the method according to the invention is therefore particularly preferred.

• einem ersten Material ausgewählt aus der Gruppe (vorzugsweise einer ersten Materialgruppe) bestehend aus Cellulose und Cellulose-Regenerat sowie deren Mischungen;
• einem zweiten Material ausgewählt aus der Gruppe (vorzugsweise einer zweiten Materialgruppe) bestehend aus substituierten Polyestern, unsubstituierten Polyestern, substituierten Polyamiden und unsubstituierten Polyamiden sowie deren Mischungen;
  wobei vorzugsweise das zweite Material ausgewählt ist aus der Gruppe (vorzugsweise einer zweiten Materialgruppe) der Copolyester, welche als Monomere Terephthalsäure und ein oder mehrere Alkandiole (vorzugsweise ausgewählt aus der Gruppe bestehend aus Ethandiol, 1,3-Propandiol und 1,4-Butandiol, besonders bevorzugt Ethandiol) umfassen
  und welche vorzugsweise mindestens ein weiteres Monomer umfassen;
  sowie
• deren Mischungen;
  wobei vorzugsweise die textile Oberfläche ein oder mehrere Materialien umfasst, wovon mindestens eines ausgewählt ist aus der Gruppe bestehend aus
  • einem zweiten Material ausgewählt aus der Gruppe bestehend aus substituierten Polyestern, unsubstituierten Polyestern, substituierten Polyamiden und unsubstituierten Polyamiden sowie deren Mischungen;
  wobei vorzugsweise das zweite Material ausgewählt ist aus der Gruppe der Copolyester, welche als Monomere Terephthalsäure und ein oder mehrere Alkandiole (vorzugsweise ausgewählt aus der Gruppe bestehend aus Ethandiol, 1,3-Propandiol und 1,4-Butandiol, besonders bevorzugt Ethandiol) umfassen
  und welche vorzugsweise mindestens ein weiteres Monomer umfassen, welches von den vorstehend genannten Monomeren (Terephthalsäure bzw. ein oder mehrere Alkandiole) verschieden ist;

In Schritt (a) des erfindungsgemäßen Verfahrens als erstes, vorzugsweise natürliches, Material einzusetzende Cellulose wird vorzugsweise gewonnen aus dem Holz von Bäumen und/oder aus Pflanzenfasern, vorzugsweise aus Hanf, Flachs, Bambus, Banane und/oder Ramie.Accordingly, a preferred method according to the invention or a method according to the invention described above or below is preferred, the textile surface of the article produced or provided in step (a) comprising 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 regenerated cellulose and mixtures thereof;
• a second material selected from the group (preferably a second group of materials) consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof;
  wherein the second material is preferably selected from the group (preferably a second group of materials) of the copolyester, 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 preferably ethanediol)
  and which preferably comprise at least one further monomer;
  such as
• their mixtures;
  wherein the textile surface preferably 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 comprise terephthalic acid and one or more alkanediols as monomers (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 which is different from the aforementioned monomers (terephthalic acid or one or more alkanediols);

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

In the context of the present invention, the term "regenerated cellulose" preferably includes regenerated fibers. Regenerated fibers are fibers that are produced from naturally occurring, renewable raw materials using chemical processes. These are mainly cellulose derivatives made from wood.

Cellulose (pulp) or regenerated cellulose which can be used in step (a) of the process according to the invention preferably comprise, within the scope of the present invention, the materials (or the fibers from the materials) viscose, modal, lyocell and cupro, particularly preferably lyocell.

Viscose fibers are chemical fibers (regenerated fibers) that are industrially produced using the viscose process, a widely known wet spinning process. The starting raw material of the viscose process is cellulose, mainly in the form of wood, from which the high-purity cellulose is extracted using various processes.

Modal fibers, like viscose fibers, also consist of 100 percent cellulose, but, unlike other regenerated fibers, are mainly made from beech wood. The starting material is beech wood that has been debarked and then chopped into pieces for separation from the lignin. By modifying the manufacturing process, you can achieve at Modal fibers have higher fiber strength and improved fiber properties than other cellulose fibers. In addition, the modal fiber has a higher moisture absorption and dries quickly.

Lyocell is an industrially produced regenerated cellulose fiber, which is known per se and consists of cellulose and which is produced by the direct solvent process known per se. It is used in particular for the production of textiles and nonwovens. Lyocell fibers have high dry and wet strength, are soft and absorb moisture very well. Textiles made from it usually have a smooth and cool handle with a flowing drape, have a low tendency to crease and can be washed and dry-cleaned.

Cupro, also known as copper silk or copper fiber, is a textile fiber made from regenerated cellulose. The properties of cupro are comparable to viscose. Cupro fibers are mainly processed into textile lining materials because they are breathable, hygroscopic and do not become statically charged. In addition, the fabrics have a silky soft feel and are smooth and shiny. Cupro can be washed and ironed, but it is not iron-free. Cupro is usually produced using the copper oxide-ammonia process (Cuoxam process).

Second, preferably synthetic, material which can be used in step (a) of the method according to the invention also comprises elastomers, preferably biodegradable elastomers.

Particularly preferred synthetic polymers to be used as the second material in step (a) of the process according to the invention, preferably biodegradable synthetic polymers, comprise 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, the second, preferably synthetic, material to be used in step (a) comprises terephthalic acid and one or more alkanediols (preferably an alkanediol, ie an alkanediol of one type) selected from the group consisting of ethanediol as monomers , 1,3-propanediol and 1,4-butanediol (preferably ethanediol), and preferably comprise at least one further monomer. Examples of particularly according to the invention 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).

Preferred polyamides which can be used in step (a) of the process according to the invention are or include polyamide-imides and aramids (the latter are also referred to as "aromatic polyamides"), preferably according to the definition of the US Federal Trade Commission, according to which aramids are polyamides with aromatic groups in of the main chain 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 known polyamide 6. An example of a biodegradable polyamide particularly preferred 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, threads, fibers or yarns made from one or more of the materials specified above can be used individually or in combination. For example, threads made of at least one synthetic material and / or threads made of at least one natural material can be spun individually or together to form yarns, or such different threads can be processed individually or together to form a fleece, fabric or fabric, for example joined, woven or knitted , become.

In step (a) of the method according to the invention, textile articles produced or provided are preferably used, the textile surface of which is selected from the group consisting of woven and knitted fabrics. The plasma treatment of woven and knitted fabrics in step (b) of the method according to the invention can be carried out particularly efficiently and effectively. Textile fabrics or knitted fabrics produced by the method according to the invention can be further processed directly into ready-made textile articles, for example into textile articles for daily use, such as outdoor clothing.

The aforementioned materials (for example cellulose or regenerated cellulose and / or one or more synthetic polymers as defined above) and the aforementioned types of textile surfaces (for example woven or knitted fabrics) can preferably be combined and such combinations, in particular combinations of preferred Materials with preferred types of textile surfaces result in preferred variants of the method according to the invention.

• ein Flächengewicht im Bereich von 20 g/m² bis 500 g/m², vorzugsweise im Bereich von 100 g/m² bis 200 g/m², aufweist
  und/oder
• eine Fadendichte im Bereich von 80 bis 120 Kettfäden/cm und 40 bis 80 Schussfäden/cm aufweist.

Also preferred is a method according to the invention or a method according to the invention described above or below as preferred, wherein the textile surface of the article produced or provided in step (a) is a woven fabric, knitted fabric, braid, stitched fabric, felt, nonwoven fabric and / or a textile tube , preferably a fabric and / or a knitted fabric, particularly preferably a fabric, which or which

• has a weight per unit area in the range from 20 g / m ² to 500 g / m ² , preferably in the range from 100 g / m ² to 200 g / m ²
  and or
• has a thread density in the range from 80 to 120 warp threads / cm and 40 to 80 weft threads / cm.

It has been shown in our own tests that these aforementioned preferred textile surfaces, in particular woven and / or knitted fabrics, are particularly well suited for plasma treatment in step (b) of the method according to the invention and thus particularly good plasma activation and particularly good subsequent hydrophobization enable textile surface.

• ein wässriges Hydrophobierungsmittel ist, das vorzugsweise modifiziertes Polydimethylsiloxan umfasst,
  und/oder
• keine fluorhaltigen organischen Verbindungen umfasst.

Preference is also given to a method according to the invention or a method according to the invention described above or below as preferred, wherein the hydrophobizing agent used in step (c)

• is an aqueous waterproofing agent, which preferably comprises modified polydimethylsiloxane,
  and or
• does not include any fluorine-containing organic compounds.

An aqueous waterproofing agent allows the process to be carried out as an aqueous process (i.e. carried out at least in the presence of water), ideally without the presence of organic solvents. In this way, few or no organic solvents get into the environment without the need for complex filtering or retention measures or there are few organic or no organic solvent residues that could affect the environment or would have to be disposed of in a costly manner. Polydimethylsiloxanes are known to be at most slightly toxic and at least largely chemically inert, so that when they are used in the method according to the invention, health damage to living organisms can be at least largely and ideally completely excluded.

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

• modifiziertes Polydimethylsiloxan, vorzugsweise modifiziertes Polydimethylsiloxan, worin eine oder mehrere Methylgruppen durch Substituenten mit basischen funktionellen Gruppen, Alkylgruppen und/oder Polyethergruppen ersetzt sind, umfasst;
  sowie zusätzlich
• ein oder mehrere kationische Polymere umfasst, welche ausgewählt sind aus der Gruppe bestehend aus
  • Polyacrylate, vorzugsweise ausgewählt aus der Gruppe bestehend aus Homopolymeren und Copolymeren von Acrylsäure, Acrylsäureestern, Methacrylsäure, Methacrylsäureestern und gegebenenfalls weiteren, mit Acrylsäure, Acrylsäureestern, Methacrylsäure und/oder Methacrylsäureestern co-polymerisierbaren Monomeren, vorzugsweise Styrol;
  • Polyurethane, vorzugsweise Polyurethane vom Polyester-Typ und/oder vom Polycarbonat-Typ, welche vorzugsweise durch Polykondensation von Dialkoholen oder Polyalkoholen mit Diisocyanaten und/oder Polyisocyanaten gebildet werden;
  • Polyester, welche vorzugsweise durch Polykondensation von Dialkoholen oder Polyalkoholen mit Dicarbonsäuren und/oder Polycarbonsäuren gebildet werden;
  • Polypeptide, welche vorzugsweise durch Polykondensation von Aminosäuren gebildet werden,
  • Polyamide, welche vorzugsweise durch Polykondensation von Aminosäuren gebildet werden,
  • vorzugsweise synthetische Biopolymere, vorzugsweise Polypeptide oder Polyamide, welche jeweils vorzugsweise durch Polykondensation von Aminosäuren gebildet werden;
    und
  • Polysaccharide, vorzugsweise ausgewählt aus der Gruppe bestehend aus Chitin und Chitosan (zu Modifizierungen und dergleichen siehe unten),
  umfasst.

In the method according to the invention or in a method according to the invention described above or below as preferred, the water repellent is preferably an aqueous water repellent which

• modified polydimethylsiloxane, preferably modified polydimethylsiloxane, in which one or more methyl groups are replaced by substituents with basic functional groups, alkyl groups and / or polyether groups;
  as well as 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 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, each of which is 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),
  includes.

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, can optionally contain further monomer units which can be copolymerized with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters contain. “Optionally” in this context means that the homopolymers and copolymers are formed from monomers of acrylic acid, acrylic acid esters, methacrylic acid and methacrylic acid esters, whereby (depending on the requirements of the individual case) further monomers co-polymerizable with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters are integrated or not integrated.

The modified polydimethylsiloxane is preferably used in the aqueous waterproofing agent in step (c) of the process according to the invention in a weight ratio in the range from 1:20 to 20: 1, preferably in the range from 1:10 to 10: 1, particularly preferably in the range from 7: 1 to 1: 7, used in relation to the one or more cationic polymers.

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% % By weight and particularly preferably in the range from 0.3% by weight to 10% by weight, based on the total weight of the aqueous waterproofing 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% by weight and particularly preferably in the range from 0.15% by weight to 5% by weight, based on the total weight of the aqueous waterproofing agent.

The modified polydimethylsiloxane which can be used in step (c) of the method according to the invention preferably comprises one or more polydimethylsiloxanes which are selected from the group consisting of aminoalkyl-polydimethylsiloxane, amidoaminoalkyl-polydimethylsiloxane, alkyl-aminoalkyl-polydimethylsiloxane, alkyl-amidoaminoalkyl-polydimethylsiloxane, alkyl-amidoaminoalkylsiloxanydimethylsiloxanydimethylsiloxanydimethylsiloxanydimethylsiloxanydimethylsiloxanydimethylsiloxanydimethylsiloxanydimethylsiloxane and alkyl polyoxyalkylene polydimethylsiloxane. Examples of such modified polydimethylsiloxanes, which are also preferably used in step (c) of the process according to the invention, are in particular in the document WO 2010/139466 disclosed.

The aforementioned modified polydimethylsiloxanes can be used individually or in combination with one another.

The cationic polymers that can be used in step (c) of the process according to the invention are preferably homopolymers or copolymers which, as constituents of the side chains of the corresponding monomers, comprise uncharged basic groups, preferably primary, secondary or tertiary amino groups, which contain cationic groups ^{by taking up H + ions} can form. Examples of such cationic polymers which are preferably used in step (c) of the process according to the invention are in particular in the document WO 2010/139466 disclosed.

The aforementioned cationic polymers can be used individually or in combination with one another.

In the context of the present invention, the term "polysaccharide" includes modified and unmodified polysaccharides, preferably modified chitin and modified and unmodified chitosan, with differences in the molar masses, in terms of degrees of deacetylation and in terms of polysaccharide derivatives suitable according to the invention, such as preferably chitosan derivatives. Chitosan derivatives to be preferably used in the method according to the invention include chitosan succinate (N-succinyl-chitosan), chitosan propionate (N-propionyl-chitosan) and chitosan adipate (N-adipyl-chitosan).

Cationic polymers to be used with preference in the above-mentioned process according to the invention are the biopolymers chitin and / or chitosan and their derivatives, preferably chitosan and its derivatives. If there are more deacetylated than acetylated 2-amino-2-deoxy-ß-D-glucopyranose units in the overall biopolymer molecule (> 50% deacetylated units), this is indicated in the present text, in accordance with the usual understanding in the specialist field, called chitosan. If there are more acetylated than deacetylated 2-amino-2-deoxy-ß-D-glucopyranose units in the overall biopolymer molecule (<50% deacetylated units), this is indicated in the present text, in accordance with the usual understanding in the specialist field, called chitin. The degree of the resulting deacetylation in the chitin or chitosan can 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 deacetylation, chitosan is a polycation with a high charge density in acidic solution.

For use in step (c) of the process according to the invention, a chitosan with a degree of deacetylation of> 75% is preferred, particularly preferably with a degree of deacetylation of> 85% and very particularly preferably with 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 a range from 10,000 Daltons to 5,000,000 Daltons, particularly preferably in a range from 100,000 Daltons to 2,000,000 Daltons and very particularly preferably in a range from 150,000 Daltons up to 1,000,000 daltons. Examples of chitosan types which can be used or preferably used in step (c) of the method according to the invention are in particular in the document WO 2010/139466 disclosed.

• das modifizierte Polydimethylsiloxan ein modifiziertes Polydimethylsiloxan ist,
  • worin eine oder mehrere Methylgruppen jeweils durch einen Substituenten mit basischer funktioneller Gruppe, vorzugsweise jeweils durch eine Aminoalkylgruppe oder eine Amido-Aminoalkylgruppe, ersetzt sind,
    und welches vorzugsweise terminale Methoxygruppen umfasst;
  und/oder (vorzugsweise "und")
• wobei die ein oder mehreren kationischen Polymere ausgewählt sind aus der Gruppe bestehend aus
  • Polyacrylate, welche durch kationische Gruppen oder basische Gruppen, vorzugsweise durch Aminogruppen, funktionalisiert sind, wobei die Funktionalisierung vorzugsweise durch entsprechend substituierte bzw. funktionalisierte (Meth)acrylsäureester bewirkt wird;
    vorzugsweise Styrol-Acrylat-Copolymere, welche durch basische Gruppen, vorzugsweise durch Aminogruppen, funktionalisiert sind;
  • Polyurethane, welche durch kationische Gruppen oder basische Gruppen, vorzugsweise durch Aminogruppen, funktionalisiert sind;
  • Polyester, welche durch kationische Gruppen oder basische Gruppen, vorzugsweise durch Aminogruppen, funktionalisiert sind;
  • Polypeptide umfassend eine oder mehrere basische Aminosäuren, vorzugsweise ausgewählt aus der Gruppe bestehend aus Lysin, Arginin, Histidin, Citrullin und Ornithin,
    und
  • Chitosan, vorzugsweise mit einem Deacetylierungsgrad > 75 %;
    wobei vorzugsweise mindestens eines der ein oder mehreren kationischen Polymere ausgewählt ist aus der Gruppe bestehend aus
  • Polyacrylate, vorzugsweise Styrol-Acrylat-Copolymere, welche durch kationische Gruppen oder basische Gruppen, vorzugsweise durch basische Gruppen, besonders bevorzugt durch Aminogruppen, funktionalisiert sind,
    und
  • Chitosan, vorzugsweise mit einem Deacetylierungsgrad > 75 %.

Accordingly, an inventive method or a preferred inventive method described above or below is also preferred, 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 each 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, the functionalization preferably being 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 which are 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, particularly 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 be specified in more detail in individual cases) is also referred to as “functionalization”. Correspondingly, in the present text the terms “substituted” and “functionalized” (where appropriate, each designated in more detail in each individual case) are used synonymously.

In the context of the present invention, the terms "polyamides" and "polypeptides" (i.e. a natural or synthetic polymer linked by peptide bonds between amino acids) are used synonymously and are used differently depending on the objective context. The term “polypeptide” is usually used in connection with corresponding natural polymers.

Examples of aqueous, fluorine-free water repellants which are preferably used in step (c) of the process according to the invention are in particular in the document WO 2010/139466 disclosed.

• eine Niederdruckplasmabehandlung, vorzugsweise eine Niederdruckplasma-Aktivierung, ode umfasst
• eine Niederdruckplasmabehandlung, vorzugsweise eine Niederdruckplasma-Aktivierung, und zumindest einen weiteren Plasmabehandlungsschritt.

In the method according to the invention, the plasma treatment in step (b)

• a low-pressure plasma treatment, preferably a low-pressure plasma activation, or comprises
• 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 that is considerably lower than the pressure of the earth's atmosphere. Due to the large (mean) free path 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 cover the entire volume of a plasma chamber.

In the preferred variant of the method according to the invention specified above, the at least one further plasma treatment step preferably comprises plasma cleaning, particularly preferably plasma cleaning, of the textile surface produced or provided in step (a) before plasma activation of said textile surface is carried out. The plasma cleaning is thus followed by the low-pressure plasma treatment, preferably the low-pressure plasma activation.

A method according to the invention or a method according to the invention described above or below as preferred is 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 range of 1 Pa (0.01 mbar) to 0.5 kPa (5 mbar), particularly preferably at a pressure in the range from 10 Pa to 50 Pa (0.1 mbar to 0.5 mbar).

It has been found in our own tests that in the pressure ranges specified above as preferred or particularly preferred, a good or even the best success is achieved with regard to the penetration of the textile surface by means of the low-pressure plasma treatment, which is decisive for the long-term stability of the treatment is, and on the other hand the process speed, which is important for the economic implementation of the process. A higher gas pressure usually leads to faster plasma activation, but its long-term stability is limited. The use of a lower gas pressure (for example <10 Pa), on the other hand, generally leads to an advantageous penetration of the textile surface by means of the low-pressure plasma treatment, but requires longer treatment times. In the worst case, too high a gas pressure can even lead to a significant decrease in the success of the treatment (reduction in the wettability of the treated tissue).

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

Preference is given to a method according to the invention or a method according to the invention described above or below as preferred, the low-pressure plasma treatment (step (b)) being 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 process, in particular a low-pressure plasma process or low-pressure plasma activation process in the specified temperature range and under the conditions or preferred conditions specified above and below, one usually speaks of a "low temperature plasma process" ("LTP") . If step (b) of the process according to the invention is carried out at temperatures below the specified temperature range or preferred temperature range, undesired side reactions, for example, can increasingly occur. If step (b) of the process according to the invention is carried out at temperatures above the specified temperature range or preferred temperature range, the rate of deposition of constituents of the gas or gas mixture forming the plasma can be undesirably reduced, which can impair the desired effect of the plasma treatment.

The low-pressure plasma treatment, preferably the low-pressure plasma activation, in step (b) of the method according to the invention is carried out in the presence of a reactive gas and an inert gas.

The reactive gas used is one or more oxygen-containing compounds which release or make available molecular oxygen at least as an intermediate (e.g. precursors or "precursors" of oxygen) at least under the conditions of low-pressure plasma activation.

It is therefore a method according to the invention in which 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 (preferably - OH, -CO, -CHO or -COOH) are generated on the textile surface, which are preferably covalently bound to the textile surface.

The detection of the generation of such oxygen-containing functional groups on the or the detection of their covalent bond to the textile surface can be carried out 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).

• in einem Gemisch, vorzugsweise einem Gasgemisch, vorliegt, welches O₂ und mindestens ein Inertgas, ausgewählt aus der Gruppe bestehend aus He und Ar, umfasst wobei das Gasgemisch einen Anteil an O₂ im Bereich von 70 Vol.-% bis 90 Vol.-% und einen Anteil an Inertgas im Bereich von 10 Vol.-% bis 30 Vol.-% enthält. wobei vorzugsweise das Gemisch (vorzugsweise das besagte Gasgemisch, welches O₂ und mindestens ein Inertgas, ausgewählt aus der Gruppe bestehend aus He und Ar, umfasst) mindestens 99 Vol.-% an O₂ und mindestens einem Inertgas, ausgewählt aus der Gruppe bestehend aus He und Ar, enthält
  und besonders bevorzugt mindestens 99 Vol.-% an O₂ und Ar enthält.

It is accordingly a method according to the invention, wherein the at least one oxygen-containing compound

• 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, the gas mixture having a proportion of O ₂ in the range from 70% by volume to 90% by volume. % and a proportion of inert gas in the range from 10% by volume to 30% by volume. wherein preferably the mixture (preferably said gas mixture which O ₂ and at least one inert gas selected from the group consisting of He and Ar comprises) at least 99 vol .-% of O ₂ and at least one inert gas selected from the group consisting of He and Ar, contains
  and particularly preferably contains at least 99% by volume of O ₂ and Ar.

The low-pressure plasma treatment, preferably the low-pressure plasma activation, is preferably carried out in step (b) of the method according to the invention with a gas or gas mixture which (before the transition to the plasma state) does not contain more than 1% by volume besides the oxygen-containing gas (s) , comprises gaseous components. By keeping the proportion of further constituents as low as this, in particular undesirable side reactions caused by further constituents of the gas mixture which would otherwise be present can largely be avoided or even prevented.

The method according to the invention contains the aforementioned mixture, preferably said gas mixture, which _{comprises O 2} and at least one inert gas selected from the group consisting of He and Ar (before the transition to the plasma state) a proportion of O ₂ in the range of 70 vol. -% to 90% by volume and a proportion of inert gas, preferably He and / or Ar, in the range of 10% by volume to 30% by volume. In our own tests, it was found that a gas mixture of this preferred composition gives very good or even the best results with regard to the preparatory plasma activation of a textile surface according to the method according to the invention, so that very good or even the best results with regard to the moisture-repellent properties of the according to the invention Plasma-treated hydrophobized textile surface produced by the method and the durability of these moisture-repellent properties result (see, for example, the results of Example 6, Table 3 or Example 7, Table 4 below).

• einem ersten Material, vorzugsweise einem natürlichen Material, ausgewählt aus der Gruppe bestehend aus Baumwolle, Wolle, Seide, Cellulose und Cellulose-Regenerat sowie deren Mischungen; besonders bevorzugt ausgewählt aus der Gruppe bestehend aus Cellulose und Cellulose-Regenerat sowie deren Mischungen;
• einem zweiten Material, vorzugsweise einem synthetischen Material, ausgewählt aus der Gruppe bestehend aus Polyestern, Polyamiden, Polyamidimiden, Polypropylen, Polyacrylnitril und Polyacrylmethacrylat sowie deren Mischungen; besonders bevorzugt ausgewählt aus der Gruppe der synthetischen Polymere, vorzugsweise der biologisch abbaubaren synthetischen Polymere, bestehend aus substituierten Polyestern, unsubstituierten Polyestern, substituierten Polyamiden und unsubstituierten Polyamiden sowie deren Mischungen;
  sowie
• deren Mischungen;
  wobei vorzugsweise die textile Oberfläche ein oder mehrere Materialien umfasst, wovon mindestens eines ausgewählt ist aus der Gruppe bestehend aus
  • einem zweiten Material vorzugsweise einem synthetischen Material, vorzugsweise ausgewählt aus der Gruppe bestehend aus Polyestern, Polyamiden, Polyamidimiden, Polypropylen, Polyacrylnitril und Polyacrylmethacrylat sowie deren Mischungen; besonders bevorzugt ausgewählt aus der Gruppe der synthetischen Polymere, vorzugsweise der biologisch abbaubaren synthetischen Polymere, bestehend aus substituierten Polyestern, unsubstituierten Polyestern, substituierten Polyamiden und unsubstituierten Polyamiden sowie deren Mischungen;
  das Plasmabehandeln in Schritt (b)
• eine Niederdruckplasmabehandlung, vorzugsweise eine Niederdruckplasma-Aktivierung, ist, wobei die Niederdruckplasmabehandlung mit mindestens einer sauerstoffhaltigen Verbindung, ausgewählt aus der Gruppe bestehend aus O, O₂, O₃, NO, N₂O und CO₂, durchgeführt wird, wobei die mindestens eine sauerstoffhaltige Verbindung in einem Gasgemisch vorliegt, welches O₂ und mindestens ein Inertgas, ausgewählt aus der Gruppe bestehend aus He und Ar, umfasst, wobei das Gasgemisch einen Anteil an O₂ im Bereich von 70 Vol.-% bis 90 Vol.-% und einen Anteil an Inertgas im Bereich von 10 Vol.-% bis 30 Vol.-% enthält, Z so dass vorzugsweise sauerstoffhaltige funktionelle Gruppen auf der textilen Oberfläche erzeugt werden, die vorzugsweise kovalent an die textile Oberfläche gebunden sind,
  und
  das in Schritt (c) eingesetzte Hydrophobierungsmittel ein wässriges Hydrophobierungsmittel ist, das
  • modifiziertes Polydimethylsiloxan umfasst, vorzugsweise modifiziertes Polydimethylsiloxan, worin eine oder mehrere Methylgruppen durch Substituenten mit basischen funktionellen Gruppen, Alkylgruppen und/oder Polyethergruppen ersetzt sind;
  • sowie zusätzlich
  • ein oder mehrere kationische Polymere umfasst, welche ausgewählt sind aus der Gruppe bestehend aus
    • Polyacrylate, vorzugsweise ausgewählt aus der Gruppe bestehend aus Homopolymeren und Copolymeren von Acrylsäure, Acrylsäureestern, Methacrylsäure, Methacrylsäureestern und gegebenenfalls weiteren, mit Acrylsäure, Acrylsäureestern, Methacrylsäure und/oder Methacrylsäureestern co-polymerisierbaren Monomeren, vorzugsweise Styrol;
    • Polyurethane, vorzugsweise Polyurethane vom Polyester-Typ und/oder vom Polycarbonat-Typ;
    • Polyester,
    • Polypeptide,
    • Polyamide
      und
    • Polysaccharide, vorzugsweise ausgewählt aus der Gruppe bestehend aus Chitin und Chitosan.

Also preferred is a method according to the invention or a method according to the invention described above or below as preferred,
in which
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, preferably a natural material, selected from the group consisting of cotton, wool, silk, cellulose and regenerated cellulose and mixtures thereof; particularly preferably selected from the group consisting of cellulose and regenerated cellulose and mixtures thereof;
• a second material, preferably a synthetic material selected from the group consisting of polyesters, polyamides, polyamide-imides, polypropylene, polyacrylonitrile and polyacryl 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;
  wherein the textile surface preferably 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 polyacryl 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;
  the plasma treatment in step (b)
• a low-pressure plasma treatment, preferably a low-pressure plasma activation, is 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 , wherein the at least one oxygen-containing compound is present in a gas mixture which _{comprises O 2} and at least one inert gas selected from the group consisting of He and Ar, the gas mixture having a proportion of O ₂ in the range from 70% by volume to 90% by volume and contains a proportion of inert gas in the range from 10% by volume to 30% by volume, Z so that preferably oxygen-containing functional groups are generated on the textile surface, which are preferably covalently bonded to the textile surface,
  and
  the water repellent used in step (c) is an aqueous water repellent which
  • comprises 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;
  • as well as 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 which can be copolymerized 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;
    • Polyester,
    • Polypeptides,
    • Polyamides
      and
    • Polysaccharides, preferably selected from the group consisting of chitin and chitosan.

• einem ersten Material ausgewählt aus der Gruppe bestehend aus Cellulose und Cellulose-Regenerat sowie deren Mischungen;
• einem zweiten Material ausgewählt aus der Gruppe bestehend aus substituierten Polyestern, unsubstituierten Polyestern, substituierten Polyamiden und unsubstituierten Polyamiden sowie deren Mischungen;
  wobei vorzugsweise das zweite Material ausgewählt ist aus der Gruppe der Copolyester, welche als Monomere Terephthalsäure und ein oder mehrere Alkandiole (vorzugsweise ausgewählt aus der Gruppe bestehend aus Ethandiol, 1,3-Propandiol und 1,4-Butandiol, besonders bevorzugt Ethandiol) umfassen
  und welche vorzugsweise mindestens ein weiteres Monomer umfassen, welches von den vorstehend genannten Monomeren (Terephthalsäure bzw. ein oder mehrere Alkandiole) verschieden ist;
  sowie
• deren Mischungen;
  wobei vorzugsweise die textile Oberfläche ein oder mehrere Materialien umfasst, wovon mindestens eines ausgewählt ist aus der Gruppe bestehend aus
  • einem zweiten Material ausgewählt aus der Gruppe bestehend aus substituierten Polyestern, unsubstituierten Polyestern, substituierten Polyamiden und unsubstituierten Polyamiden sowie deren Mischungen;
    wobei vorzugsweise das zweite Material ausgewählt ist aus der Gruppe der Copolyester, welche als Monomere Terephthalsäure und ein oder mehrere Alkandiole (vorzugsweise ausgewählt aus der Gruppe bestehend aus Ethandiol, 1,3-Propandiol und 1,4-Butandiol, besonders bevorzugt Ethandiol) umfassen
    und welche vorzugsweise mindestens ein weiteres Monomer umfassen, welches von den vorstehend genannten Monomeren (Terephthalsäure bzw. ein oder mehrere Alkandiole) verschieden ist;
  das Plasmabehandeln in Schritt (b)
• eine Niederdruckplasmabehandlung, vorzugsweise eine Niederdruckplasma-Aktivierung, ist, welche in Anwesenheit eines Gasgemisches durchgeführt wird, welches O₂ und mindestens ein Inertgas, ausgewählt aus der Gruppe bestehend aus He und Ar, umfasst wobei die mindestens eine sauerstoffhaltige Verbindung in einem Gasgemisch vorliegt, welches O₂ und mindestens ein Inertgas, ausgewählt aus der Gruppe bestehend aus He und Ar, umfasst, wobei das Gasgemisch einen Anteil an O₂ im Bereich von 70 Vol.-% bis 90 Vol.-% und einen Anteil an Inertgas im Bereich von 10 Vol.-% bis 30 Vol.-% enthält, wobei vorzugsweise das besagte Gasgemisch mindestens 99 Vol.-% an O₂ und mindestens einem Inertgas, ausgewählt aus der Gruppe bestehend aus He und Ar, enthält
  und wobei besonders bevorzugt das besagte Gasgemisch mindestens 99 Vol.-% an O₂ und Ar enthält,

und
das in Schritt (c) eingesetzte Hydrophobierungsmittel ein wässriges Hydrophobierungsmittel ist, das

• modifiziertes Polydimethylsiloxan umfasst, vorzugsweise modifiziertes Polydimethylsiloxan, worin eine oder mehrere Methylgruppen durch Substituenten mit basischen funktionellen Gruppen, Alkylgruppen und/oder Polyethergruppen ersetzt sind;
• sowie zusätzlich
• ein oder mehrere kationische Polymere umfasst, welche ausgewählt sind aus der Gruppe bestehend aus
  • Polyacrylate, vorzugsweise ausgewählt aus der Gruppe bestehend aus Homopolymeren und Copolymeren von Acrylsäure, Acrylsäureestern, Methacrylsäure, Methacrylsäureestern und gegebenenfalls weiteren, mit Acrylsäure, Acrylsäureestern, Methacrylsäure und/oder Methacrylsäureestern co-polymerisierbaren Monomeren, vorzugsweise Styrol;
  • Polyurethane, vorzugsweise Polyurethane vom Polyester-Typ und/oder vom Polycarbonat-Typ;
  • Polyester,
  • Polypeptide,
  • Polyamide
    und
  • Polysaccharide, vorzugsweise ausgewählt aus der Gruppe bestehend aus Chitin und Chitosan.

Particularly preferred is a method according to the invention or a method according to the invention described above or below as preferred,
in which
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 regenerated cellulose 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 the second material is preferably selected from the group of copolyesters, which comprise terephthalic acid and one or more alkanediols as monomers (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 which is different from the aforementioned monomers (terephthalic acid or one or more alkanediols);
  such as
• their mixtures;
  wherein the textile surface preferably 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 comprise terephthalic acid and one or more alkanediols as monomers (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 which is different from the aforementioned 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 which _{comprises O 2} and at least one inert gas selected from the group consisting of He and Ar, the at least one oxygen-containing compound being present in a gas mixture which O ₂ and at least one inert gas selected from the group consisting of He and Ar, the gas mixture having a proportion of O ₂ in the range from 70% by volume to 90% by volume and a proportion of inert gas in the range of 10 Contains% by volume to 30% by volume, said gas mixture preferably containing at least 99% by volume of O ₂ and at least one inert gas selected from the group consisting of He and Ar
  and wherein said gas mixture particularly preferably contains at least 99% by volume of O ₂ and Ar,

and
the water repellent used in step (c) is an aqueous water repellent which

• comprises 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;
• as well as 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 which can be copolymerized 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;
  • Polyester,
  • Polypeptides,
  • Polyamides
    and
  • Polysaccharides, preferably selected from the group consisting of chitin and chitosan.

• die Niederdruckplasmabehandlung für eine Dauer im Bereich von 10 sec bis 10 min, vorzugsweise im Bereich von 30 sec bis 5 min, besonders bevorzugt im Bereich von 1 min bis 3 min, durchgeführt wird;
  und/oder
• das Niederdruckplasma bei einer Frequenz im Bereich von 10 MHz bis 18 MHz, vorzugsweise im Bereich von 11 MHz bis 15 MHz, erzeugt wird,
  und/oder
• das Niederdruckplasma mit Elektroden erzeugt wird, wobei die Elektrodendichte vorzugsweise im Bereich von 1 bis 10 Elektroden/m², besonders bevorzugt im Bereich von 2 bis 5 Elektroden/m², ganz besonders bevorzugt im Bereich von 2,5 bis 4 Elektroden/m², bezogen auf die in Schritt (a) hergestellte oder bereitgestellte textile Oberfläche, liegt;
  und/oder
• die Niederdruckplasmabehandlung mit einer Plasmaerzeugungsquelle bei einer Leistung im Bereich von 0,05 kW bis 100 kW, vorzugsweise im Bereich von 1 kW bis 25 kW, besonders bevorzugt im Bereich von 2 kW bis 15 kW, ganz besonders bevorzugt im Bereich von 5 kW bis 10 kW durchgeführt wird,
  und/oder
• die Niederdruckplasmabehandlung in einer Plasmabehandlungskammer bei einer Leistung im Bereich von 0,25 kW/m³ bis 2,0 kW/m³, vorzugsweise im Bereich von 0,5 kW/m³ bis 1,5 kW/m³, durchgeführt wird.

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

• the low-pressure plasma treatment is carried out for a duration in the range from 10 sec to 10 min, preferably in the range from 30 sec to 5 min, particularly preferably in the range from 1 min to 3 min;
  and or
• the low-pressure plasma is generated at a frequency in the range from 10 MHz to 18 MHz, preferably in the range from 11 MHz to 15 MHz,
  and or
• the low-pressure plasma is generated with electrodes, the electrode density preferably in the range from 1 to 10 electrodes / m ² , particularly preferably in the range from 2 to 5 electrodes / m ² , very particularly preferably in the range from 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 generation source at an output in the range from 0.05 kW to 100 kW, preferably in the range from 1 kW to 25 kW, particularly preferably in the range from 2 kW to 15 kW, very particularly preferably in the range from 5 kW to 10 kW is carried out,
  and or
• the low-pressure plasma treatment is carried out in a plasma treatment chamber at an output in the range from 0.25 kW / m ³ to 2.0 kW / m ³ , preferably in the range from 0.5 kW / m ³ to 1.5 kW / m ³ .

The parameters of the low-pressure plasma treatment in step (b) of the method according to the invention specified above as preferred or particularly preferred can preferably be combined and, in combination, result in particularly preferred method 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 from 1 Pa (0.01 mbar) to 0.5 kPa (5 mbar) and for a duration is carried out in the range of 30 seconds to 5 minutes. In addition, variants of the method 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 from 10 Pa to 50 Pa (0.1 mbar to 0.5 mbar) and for a duration is carried out in the range of 1 minute to 3 minutes.

As already stated above, under these preferred conditions of pressure and duration ranges, the best effect or the best compromise of the method according to the invention with regard to penetration of the textile surface by means of the low-pressure plasma treatment, longevity of the activation achieved and subsequent hydrophobization of the textile surface as well as economical implementation of the method given.

If the low-pressure plasma is generated with electrodes in step (b) of the method according to the invention, the electrode density preferably being in the above range, a particularly effective and uniform (homogeneous) activation and subsequent hydrophobization 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 with an output in the above-mentioned range or with a plasma generation source with an output in the above-mentioned range, particularly good results are achieved with regard to the activation of the textile surface or the subsequent Hydrophobization and its longevity achieved.

It has been shown that particularly good or even the best results with regard to the preparatory plasma activation of a textile surface using the method according to the invention and thus also very good or even the best results with regard to the moisture-repellent properties of the plasma-treated hydrophobized textile surface and the durability of the moisture-repellent properties result when the method according to the invention (in step (b)) is carried out as a low-pressure plasma treatment with a plasma generation source at an output in the range specified above or in the preferred range specified above. For example, if the power of the plasma generation source is lower than the values given above, there may be insufficient plasma activation of the textile surface, which ultimately also leads to unsatisfactory moisture-repellent properties of the treated textile surface and / or unsatisfactory durability of these moisture-repellent properties. On the other hand, if the power of the plasma generation source is higher than the values given above, the textile surface used may even be damaged.

• Imprägnieren, vorzugsweise Vollbadimprägnieren, besonders bevorzugt mittels Foulardieren, der in Schritt (b) resultierenden plasmabehandelten textilen Oberfläche oder einer daraus in weiteren Schritten hergestellten textilen Oberfläche,
• Trocknen aufgenommenen Hydrophobierungsmittels auf der textilen Oberfläche,
• Fixieren aufgenommenen Hydrophobierungsmittels auf der textilen Oberfläche,

wobei das nasschemische Behandeln vorzugsweise eine Vollbadimprägnierung, besonders bevorzugt eine Vollbadimprägnierung mittels Foulardieren, der in Schritt (b) resultierenden plasmabehandelten textilen Oberfläche oder einer daraus in weiteren Schritten hergestellten textilen Oberfläche umfasst,
wobei bevorzugt danach das Trocknen und/oder Fixieren aufgenommenen Hydrophobierungsmittels auf der textilen Oberfläche erfolgt.A method according to the invention or a method according to the invention described above or below as preferred is preferred, the wet-chemical treatment in step (c) comprising one or more or all of the following measures:

• Impregnation, preferably full bath impregnation, particularly preferably by means of padding, of the plasma-treated textile surface resulting in step (b) or a textile surface produced therefrom in further steps,
• Drying absorbed water repellant on the textile surface,
• Fixing absorbed water repellant on the textile surface,

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

In the context of the present invention, the impregnation in the course of the aforementioned wet chemical treatment in step (c) of the method according to the invention can be carried out using any method suitable for this purpose, for example by spraying, dipping, pressure impregnation, patting ("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.

According to the invention, the impregnation is preferably carried out by full bath impregnation, particularly preferably by means of padding, preferably if the wet chemical treatment is an aqueous wet chemical treatment. In this way, the plasma-treated hydrophobized textile surface obtained in step (c) of the method according to the invention is most effectively brought into contact with the hydrophobing agent and a particularly completely and permanently hydrophobized textile surface results.

• ein wässriges nasschemisches Behandeln (wie vorstehend erklärt) ist, welches ein Imprägnieren (wie vorstehend erklärt), vorzugsweise Vollbadimprägnieren, besonders bevorzugt mittels Foulardieren umfasst, der in Schritt (b) resultierenden plasmabehandelten textilen Oberfläche oder einer daraus in weiteren Schritten hergestellten textilen Oberfläche, mit einem wässrigen Hydrophobierungsmittel, das modifiziertes Polydimethylsiloxan umfasst, wobei das modifizierte Polydimethylsiloxan in einer Konzentration im Bereich von 200 g/L bis 400 g/L, vorzugsweise im Bereich von 250 g/L bis 350 g/L, bezogen auf die beim nasschemischen Behandeln in Schritt (c) eingesetzte Gesamtmenge an wässriger Flüssigkeit, eingesetzt wird.

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

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

If the above-defined wet chemical treatment with a modified polydimethylsiloxane (as described above, or with such a modified polydimethylsiloxane described as preferred) in a concentration in the range from 200 g / L to 400 g / L, preferably in the range from 250 g / L up 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 as described above of an article produced or provided in step (a) which contains one or more materials comprises, which are selected from the group consisting of a first material selected from the group consisting of cellulose and regenerated cellulose and mixtures thereof), the best results are achieved according to the method according to the invention in terms of moisture-repellent properties of the resulting impregnated fabric and durability of the impregnation. For example, concentrations of modified polydimethylsiloxane lower than those indicated above can result in unsatisfactory moisture-repellent properties of the treated textile surface. In contrast, higher than the above-specified concentrations of modified polydimethylsiloxane can even lead to a reduced durability of the moisture-repellent properties of the treated textile surface.

• bei einem Druck im Bereich von 100 kPa bis 500 kPa, vorzugsweise im Bereich von 200 kPa bis 400 kPa durchgeführt wird
  und/oder
• bei einer Durchlauf-Geschwindigkeit der textilen Oberfläche (Längenmaß der textilen Oberfläche) durch das der Imprägnierung dienende Vollbad im Bereich von 0,5 m/min bis 5 m/min, vorzugsweise im Bereich von 1 m/min bis 3 m/min, durchgeführt wird,
  und/oder (vorzugsweise "und")
• bei einer Temperatur im Bereich von 15 °C bis 35 °C, vorzugsweise im Bereich von 18 °C bis 25 °C, durchgeführt wird.

Particularly preferred is a method according to the invention or a method according to the invention described above or below as preferred, the wet-chemical treatment in step (c) being 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 a textile surface produced therefrom in further steps, wherein the full bath impregnation, preferably 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 of the textile surface) through the full bath used for impregnation in the range from 0.5 m / min to 5 m / min, preferably in the range from 1 m / min to 3 m / min becomes,
  and / or (preferably "and")
• at a temperature in the range from 15 ° C to 35 ° C, preferably in the range from 18 ° C to 25 ° C.

• bei einer Temperatur im Bereich von 100 °C bis 140 °C, vorzugsweise im Bereich von 110 °C bis 130 °C,
  und/oder (vorzugsweise "und")
• für eine Dauer im Bereich von 30 sec bis 5 min, vorzugsweise im Bereich von 1 min bis 4 min,
  und/oder (vorzugsweise "und")
• in einem Spannrahmen.

Also preferred is a method according to the invention or a method according to the invention described above or below as preferred, wherein the wet chemical treatment in step (c) is an aqueous wet chemical treatment and comprises drying of absorbed hydrophobing agent on the textile surface, the drying being carried out

• at a temperature in the range from 100 ° C to 140 ° C, preferably in the range from 110 ° C to 130 ° C,
  and / or (preferably "and")
• for a duration in the range from 30 sec to 5 min, preferably in the range from 1 min to 4 min,
  and / or (preferably "and")
• in a tenter frame.

• bei einer Temperatur im Bereich von 120 °C bis 190 °C, vorzugsweise im Bereich von 140 °C bis 180 °C, besonders bevorzugt im Bereich von 150 °C bis 170 °C,
  und/oder (vorzugsweise "und")
• für eine Dauer im Bereich von 20 sec bis 4 min, vorzugsweise im Bereich von 30 sec bis 3 min, besonders bevorzugt im Bereich von 1 min bis 3 min,
  und/oder (vorzugsweise "und")
• in einem Spannrahmen.

Preference is given to a method according to the invention or a method according to the invention described above or below as preferred, the wet-chemical treatment in step (c) being an aqueous wet-chemical treatment and fixing of absorbed hydrophobizing agent on the textile surface, the fixing being carried out

• at a temperature in the range from 120 ° C to 190 ° C, preferably in the range from 140 ° C to 180 ° C, particularly preferably in the range from 150 ° C to 170 ° C,
  and / or (preferably "and")
• for a duration in the range from 20 sec to 4 min, preferably in the range from 30 sec to 3 min, particularly preferably in the range from 1 min to 3 min,
  and / or (preferably "and")
• in a tenter frame.

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

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

The textile article according to the invention is preferably selected from the group consisting of weather protection clothing; Outdoor clothing, functional clothing; Work clothes, preferably for outdoor use; Rain cloaks; Ponchos; Tarpaulins for motor vehicles or construction; Awnings; Sunroofs; Umbrellas; Parasols; Tent sheets; Tents and transport containers, preferably suitcases, carrier bags, sports bags, rucksacks and panniers.

With regard to preferred configurations of a textile article according to the invention, the explanations given above for the method according to the invention apply accordingly, and vice versa.

The present invention also relates to the use of a low-pressure plasma process for the preparatory treatment of a textile surface of an article, prior to the wet-chemical hydrophobing of the textile surface, the low-pressure plasma treatment 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 , the at least one oxygen-containing compound being present in a gas mixture which _{comprises O 2} and at least one inert gas selected from the group consisting of He and Ar, the gas mixture having a proportion of O ₂ in the range from 70% by volume to 90% by volume and a proportion of inert gas in the range from 10% by volume to 30% by volume.

With regard to preferred embodiments of the use according to the invention, the explanations given above for the method according to the invention and / or for the textile article according to the invention apply accordingly, and vice versa.

• einem ersten Material ausgewählt aus der Gruppe bestehend aus Cellulose und Cellulose-Regenerat sowie deren Mischungen;
• einem zweiten Material ausgewählt aus der Gruppe bestehend aus substituierten Polyestern, unsubstituierten Polyestern, substituierten Polyamiden und unsubstituierten Polyamiden sowie deren Mischungen;
  wobei vorzugsweise das zweite Material ausgewählt ist aus der Gruppe der Copolyester, welche als Monomere Terephthalsäure und ein oder mehrere Alkandiole (vorzugsweise ausgewählt aus der Gruppe bestehend aus Ethandiol, 1,3-Propandiol und 1,4-Butandiol, besonders bevorzugt Ethandiol) umfassen
  und welche vorzugsweise mindestens ein weiteres Monomer umfassen, welches von den vorstehend genannten Monomeren (Terephthalsäure bzw. ein oder mehrere Alkandiole) verschieden ist;
  sowie
• deren Mischungen;
  wobei vorzugsweise die textile Oberfläche ein oder mehrere Materialien umfasst, wovon mindestens eines ausgewählt ist aus der Gruppe bestehend aus
  • einem zweiten Material ausgewählt aus der Gruppe bestehend aus substituierten Polyestern, unsubstituierten Polyestern, substituierten Polyamiden und unsubstituierten Polyamiden sowie deren Mischungen;
    wobei vorzugsweise das zweite Material ausgewählt ist aus der Gruppe der Copolyester, welche als Monomere Terephthalsäure und ein oder mehrere Alkandiole (vorzugsweise ausgewählt aus der Gruppe bestehend aus Ethandiol, 1,3-Propandiol und 1,4-Butandiol, besonders bevorzugt Ethandiol) umfassen
    und welche vorzugsweise mindestens ein weiteres Monomer umfassen, welches von den vorstehend genannten Monomeren (Terephthalsäure bzw. ein oder mehrere Alkandiole) verschieden ist;
  vor dem nasschemischen Hydrophobieren der textilen Oberfläche.

Preferred is a use according to the invention or a use according to the invention of a low-pressure plasma process described above or below as preferred for the preparatory treatment of a textile surface of an article,
wherein the textile surface comprises one or more materials which are selected from the group consisting of

• a first material selected from the group consisting of cellulose and regenerated cellulose 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 the second material is preferably selected from the group of copolyesters, which comprise terephthalic acid and one or more alkanediols as monomers (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 which is different from the aforementioned monomers (terephthalic acid or one or more alkanediols);
  such as
• their mixtures;
  wherein the textile surface preferably 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 comprise terephthalic acid and one or more alkanediols as monomers (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 which is different from the aforementioned monomers (terephthalic acid or one or more alkanediols);
  before the wet chemical hydrophobization of the textile surface.

Examples:

The following examples are intended to describe and explain the invention in more detail without restricting its scope of protection.

Example 1: Providing an article with a textile surface

As an article with a textile surface, a fabric was used (provided) in each of the examples given below, which is made from 100% individual threads of a biodegradable synthetic polymer (a copolyester comprising as Monomers terephthalic acid and ethanediol and at least one other monomer) existed. The weight per unit area of the fabric was approx. 150 g / m ² and the thread density was approx. 100 warp threads / cm and approx. 50 weft threads / cm.

The tissue provided in this way was designated "G-tO".

Similar convincing results as set out below, in particular with regard to the improvement in the water-repellent properties that can be achieved by the process according to the invention, are also obtained when using other textile surfaces, for example when using one of the textile surfaces which can be used according to the invention or which can preferably be used, for example. Examples include a lyocell (cellulose) -based fabric (such as 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 a plasma chamber (approx. 11 m ³ ) and a plurality of electrodes (electrode ^{density approx. 3.5 electrodes / m 2 of} tissue) subject, whereby the following parameters were set: Frequency: 13.56 MHz Duration of treatment: 2 min Power (plasma source): 9 kW Print: 0.3 mbar (30 Pa) Process gas: O ₂ (molecular oxygen) Inert gas: Ar (argon) Process gas / inert gas ratio: 20 vol% Ar / 80 vol% O ₂

The tissue treated with plasma in this way was designated “G-tO-pbh (Ar / O ₂ )”.

2.2 Plasma treatment with inert gas (not according to the invention)

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

The tissue treated with plasma in this way was designated "G-tO-pbh (Ar)".

2.3 Plasma treatment with process gas (not according to the invention)

Another sample of the fabric provided above (see Example 1) was subjected to the same low-pressure plasma activation as described above under 2.1, but only the process gas molecular oxygen, but not the inert gas argon (100% by volume O ₂ ) was used. .

The tissue treated with plasma in this way was designated "G-tO-pbh (O ₂ )".

Example 3: Production of water repellants

In a manner known per se, the compositions indicated below (cf. Table 1) of aqueous hydrophobizing agents (hereinafter also abbreviated as "HPM") which can be used in the process according to the invention (step (c)) and containing modified polydimethylsiloxane (hereinafter also abbreviated as "PDMS") were used ) produced.

A chitosan with a degree of deacetylation of 95% and a molecular weight of 300,000 to 500,000 g / mol (Da) was used as the chitosan.

An emulsifier-containing dispersion (approx. 35% by weight active content) of an acrylate-styrene copolymer with 25-45% by weight of amino-functional monomers and a molecular weight between 50,000 and 500,000 g / mol (Da) is used. <u> Table 1 </u>: compositions of water repellants component function HPM 1 HPM 2 HPM 3 Amount [wt .-%] Amount [wt .-%] Amount [wt .-%] Amino-amido-siloxane ¹ Modified PDMS 0.6 0 0 Amino-functionalized polydimethylsiloxane ¹ Modified PDMS 0 1.7 5.1 Amino-functionalized (styrene) acrylate copolymer Cationic polymer 0 0.25 0.74 Chitosan Cationic polymer 0.5 0 0.1 Formic acid acid 0.25 0.06 0.06 water Solvents (including preservatives) ad 100 ad 100 ad 100 ¹ : 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 )” produced as indicated above (cf. Example 2.1) was processed in a manner known per se in a padding machine (also known as a “padding machine” or “padding mangle ") impregnated with the aqueous hydrophobing agent HPM3 (concentration: 300 g / L) prepared as above (cf. Example 3), the following parameters being set: Print: 300 kPa (3 bar) Temperature: 21 ° C Feed rate: 2 m / min

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

For fixation, the dried fabric was then treated on a tenter at 180 ° C. for a further 1 min.

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

The plasma-treated fabrics "G-tO-pbh (Ar)" and "G-tO-pbh (O ₂ )" produced as indicated above (cf. Reference Examples 2.2 and 2.3) were impregnated and dried in the same way as indicated above and fixed. The hydrophobized fabrics plasma-treated in this way corresponded in each case to articles produced according to the invention with a hydrophobized textile surface and were correspondingly referred to as “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 indicated above (cf. Example 1) was impregnated in a padding machine with the hydrophobicizing agent HPM3 prepared as indicated above in otherwise the same manner as described in Example 4.1, then likewise dried and fixed.

The non-plasma-treated hydrophobic fabric produced in this way was designated “G-tO-hydr” and used as a comparison fabric not produced according to the invention.

Example 5: Determination of the contact angle

The contact angle 0 of liquids surrounded by gas on a solid surface denotes the angle at the phase boundary between gaseous, liquid and solid phases. The size of the contact angle between liquid and solid depends on the interaction between the fabrics at the contact surface. The smaller this interaction, the larger the contact angle. By determining the contact angle, certain properties of the surface of a solid can be determined, e.g. B. the surface energy. In the special case of using water as a liquid, the surface is called hydrophilic at low contact angles (approx. 0 °), hydrophobic at angles around 90 ° and superhydrophobic at even larger angles. The latter is also known as the lotus effect at very high angles (approx. 160 °) and corresponds to extremely low wettability. The contact angle can be changed by surface treatment. The contact angle 0 can be measured with a contact angle goniometer.

The contact angles with glycerol (98%) and with water on the fabrics "G-tO" or "G-tO-pbh (Ar / O ₂ )" provided or produced as specified above as test bodies (tensioned fabric) were determined, according to the standard DIN 55660-2: 2011-12 (static method). The contact angle was determined 5 seconds after the test liquid had been applied to the tensioned tissue surface. The results of this experiment with glycerine as the test liquid are given in Table 2 below: <u> Table </u> 2: Contact angle of glycerine on tissue surfaces tissue Contact angle θ against glycerine (98%) [°] G-tO 60 G-tO-pbh (Ar / O ₂ ) 25th

The values given in Table 2 show that when glycerine (98%) is used as the test liquid, the G-tO-pbh (Ar / O ₂ ) fabric surface has become significantly better wettable as a result of the low-pressure plasma treatment (lower value for the contact angle θ) as the non-plasma-treated tissue surface G-tO used for comparison.

From this result it can be concluded that the low-pressure plasma treatment of the textile surface has led to its better wettability, which is advantageous for the subsequent wet chemical treatment is. The effects of low-pressure plasma treatment on textile surfaces (better wettability) can be demonstrated particularly well by using glycerine as a test liquid with a comparatively high viscosity.

Example 6: Determination of the durability of the hydrophobization (spray test)

The durability of the hydrophobization (moisture repellency) achievable by the process according to the invention of a textile surface was determined and compared with that of a textile surface not produced according to the invention.

Example 6a: Durability of the water repellency in relation to washing-drying cycles

For this purpose, G-tO-pbh (Ar / O ₂ ) -hydr, (manufactured according to the invention) G-tO-pbh (Ar) -hydr (not according to the invention) and G-tO-pbh ( O ₂ ) -hydr (not according to the invention) and G-tO-hydr (comparison) each carried out a spray test with water according to the AATCC TM22-2014 standard.

This spray test is used to determine the water-repellent properties of textile surfaces with or without finishing. Here, the stretched textile surface is wetted with water under controlled conditions, creating a moisture pattern on the textile surface, the extent of which depends on the relative water repellency of the textile surface under consideration. The evaluation of the test result as the degree of "moisture repellency" is carried out by comparing the resulting moisture pattern with corresponding reference standard samples on a scale from 0 ("complete moistening of the entire upper and lower surfaces") to 100 ("no sticking or no moistening either." only the upper surface ").

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

Example 6b: Durability of the hydrophobization against abrasion

For this purpose, as stated above (see Example 6a), a spray test with water according to the AATCC TM22-2014 standard was carried out on the fabrics G-tO-pbh (Ar / O ₂ ) -hydr (produced according to the invention) and G -tO-hydr (comparison) after an abrasion test in accordance with the ASTM D4966-98 (2004) standard had been carried out with these two fabrics ("Martindale" abrasion test method; conditions: abrasive: wool; applied weight of the abrasive: 12 kPa; number of abrasion cycles: 2000). The results of this test were evaluated as stated above (see Example 6a) and stated below in Table 3 (see column “C: Moisture repellency after abrasion test (Martindale)”). <u> Table 3 </u>: Results of the spray test on textile surfaces tissue A: moisture repellency (initial) B: moisture repellency (after 5 W / T cycles) C: moisture repellency according to abrasion test (Martindale) G-tO-hydr (comparison) 90 60 70 G-tO-pbh (Ar / O ₂ ) -hydr (invention) 100 90 90 G-tO-pbh (O ₂ ) -hydr (not according to the invention) 100 80 nb G-tO-pbh (Ar) -hydr (not according to the invention) 100 70-80 nb "nb": values not determined

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

It can also be seen from the values given in Table 3 that the difference in the moisture-repellent properties becomes even greater if the corresponding values are compared after five washing and drying cycles (i.e. after mechanical, chemical and heat exposure): While the moisture-repellent properties the textile surface of the article with a hydrophobized textile surface produced by the method according to the invention had hardly changed (best result for the article G-tO-pbh (Ar / O ₂ ) -hydr; reference standard sample 90 instead of 100), the moisture-repellent properties had improved the textile surface used for comparison (G-tO-hydr) significantly deteriorated due to the previous exposure (see column "B").

It can also be seen from the values given in Table 3 that the plasma-treated hydrophobized (impregnated) textile surface of an article (G-tO-pbh (Ar / O ₂ ) -hydr) produced by the method according to the invention has better abrasion resistance than that according to same process, but without prior plasma treatment, only by wet chemical treatment impregnated textile surface (G-tO-hydr), (see column "C").

From this result it can be concluded that an (impregnated) textile surface produced according to the method according to the invention has better, more permanent and more resistant hydrophobic (ie here: water-repellent or waterproof) properties than one produced (impregnated) according to a known method of the prior art ) textile surface.

Example 7: Determination of the degree of hydrophobization (water column)

The degree of water resistance of an article with a hydrophobized textile surface produced according to the method according to the invention was determined and compared with an article which had been produced (impregnated) according to a known method of the prior art.

For this purpose, G-tO-pbh (Ar / O ₂ ) -hydr, (manufactured according to the invention) G-tO-pbh (Ar) -hydr (not according to the invention) and G-tO-pbh (O ₂ ) -hydr (not according to the invention) and G-tO-hydr (comparison) a test for determining the resistance against the penetration of water according to the standard ISO 811: 1981-10 / DIN EN 20811: 1992-08 (water column above the textile surface, i.e. above / facing the plasma-treated textile surface or above / facing the plasma-treated, hydrophobized surface) ( "hydrostatic pressure test").

According to this test, the water resistance is given as the resistance of the textile surface under consideration to a water column. The height of that water column in cm which, according to the test conditions of the above-mentioned standard, leads to the permeability of the textile surface to water 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 provision or production (see column A: "Initial", ie without prior washing and drying treatment) and once for the same fabrics, but after every five Wash and dry cycles (see column B: "After 5 W / T cycles"). The washing and drying cycles were carried out in accordance with the ISO 6330: 2000 (E) standard (washing machine type A / front loader; washing program 5A "Normal" at 40 ± 3 ° C; standard detergent without phosphates, ballast 2 kg; drying in a tumble dryer at 65 ° C for 30 min.): <u> Table 4 </u>: Results of the hydrostatic pressure test on textile surfaces tissue A: Water resistance (water column) [cm] (initial) B: Water resistance (water column) [cm] (after 5 W / T cycles) G-tO-hydr (comparison) (25) / 13.25 7th G-tO-pbh (Ar / O ₂ ) -hydr (invention) (33) / 38.25 24.5 G-tO-pbh (O ₂ ) -hydr (not according to the invention) 24.5 18th G-tO-pbh (Ar) -hydr (not according to the invention) 29.5 13.25

The values in brackets in Table 4 (column A) are to be assigned to a separate series of measurements. The values not in brackets in Table 4 (column A) are also to be assigned to a further separate measurement series.

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

It can also be seen from the values given in Table 4 that the difference in water resistance is even greater in preferred cases when the corresponding values are compared after five washing and drying cycles (ie after mechanical, chemical and heat exposure): While the Properties of the water resistance of the textile surface of the article with a hydrophobized textile surface produced by the method according to the invention (low-pressure plasma treatment with at least one oxygen-containing compound) had changed relatively less, the properties of the water resistance of the textile surface used for comparison (G-tO-hydr) had changed 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 / O ₂ ) -hydr.

Claims (15)

1. Method for producing a textile article having a hydrophobized textile surface, comprising the following steps:

   (a) producing 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 hydrophobizing agent, to give a plasma-treated hydrophobized textile surface,
   wherein the plasma treating in step (b)

   - is a low-pressure plasma treatment
   or

   - comprises a low-pressure plasma treatment and at least one further plasma treatment step,

   wherein the low-pressure plasma treatment, in both cases, is carried out with at least one oxygen-containing compound selected from the group consisting of O, O₂, O₃, NO, N₂O and CO₂,
   wherein the at least one oxygen-containing compound is present in a gas mixture which comprises O₂ and at least one inert gas selected from the group consisting of He and Ar,
   wherein the gas mixture contains a fraction of O₂ in the range from 70 vol% to 90 vol% and a fraction of inert gas in the range from 10 vol% to 30 vol%.
2. Method according to any preceding claim, 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 regenerated cellulose and also mixtures thereof, more preferably selected from the group consisting of cellulose and regenerated cellulose and also mixtures thereof;

   - a second material, preferably a synthetic material, preferably selected from the group consisting of polyesters, polyamides, polyamideimides, polypropylene, polyacrylonitrile and polyacryl methyacrylate and also mixtures thereof, more preferably selected from the group of the synthetic polymers, preferably the biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and also mixtures thereof;
   and also

   - mixtures thereof.
3. Method according to either of the preceding claims, preferably according to Claim 2, 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 cellulose and regenerated cellulose and also mixtures thereof;

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

   - mixtures thereof;
   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 also mixtures thereof.
4. Method according to any of the preceding claims, wherein the textile surface of the article produced or provided in step (a)

   - is selected from the group consisting of wovens, formed-loop knits, drawn-loop knits, braids, stitchbondeds, felts, textile composites, fibre webs, textile hoses, ropes, fibres, threads, yarns, rovings and mixtures thereof, preferably selected from the group consisting of wovens, formed-loop knits, drawn-loop knits, textile composites, fibre webs and mixtures thereof;
   and/or

   - comprises a woven, formed-loop knit, drawn-loop knit, braid, stitch-bonded, felt, fibre web and/or a textile hose, preferably a woven and/or a drawn-loop knit, more preferably a woven, which

   - has a basis weight in the range from 20 g/m² to 500 g/m², preferably in the range from 100 g/m² to 200 g/m²,
   and/or

   - has a thread density in the range from 80 to 120 warp threads/cm and 40 to 80 weft threads/cm.
5. Method according to any of the preceding claims, preferably according to Claim 3, wherein the hydrophobizing agent used in step (c)

   - is an aqueous hydrophobizing agent which comprises preferably modified
   polydimethylsiloxane, and/or

   - comprises no fluorine-containing organic compounds
   and/or
   wherein the hydrophobizing agent is an aqueous hydrophobizing agent which

   - comprises modified polydimethylsiloxane, preferably modified polydimethylsiloxane in which one or more methyl groups have been replaced by substituents having basic functional groups, alkyl groups and/or polyether groups;
   and also 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 esters, methacrylic acid, methacrylic esters and optionally further monomers copolymerizable with acrylic acid, acrylic esters, methacrylic acid and/or methacrylic esters, preferably styrene;

   - polyurethanes, preferably polyurethanes of the polyester type and/or of the polycarbonate type;

   - polyesters,

   - polypeptides,

   - polyamides
   and

   - polysaccharides, preferably selected from the group consisting of chitin and chitosan,

   and/or
   wherein the hydrophobizing agent is an aqueous hydrophobizing agent which comprises a modified polydimethylsiloxane, wherein

   - the modified polydimethylsiloxane is a modified polydimethylsiloxane

   - in which one or more methyl groups have been replaced in each case by a substituent having a basic functional group, preferably in each case by an aminoalkyl group or an amido-aminoalkyl group,

   and which comprises preferably terminal methoxy groups;
   and/or

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

   - polyacrylates functionalized by cationic groups or basic groups, preferably by amino groups, preferably styrene-acrylate copolymers functionalized by basic groups, preferably by amino groups;

   - polyurethanes functionalized by cationic groups or basic groups, preferably by amino groups;

   - polyesters 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 omithine,
   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, functionalized by cationic groups or basic groups, preferably by basic groups, more preferably by amino groups,
   and

   - chitosan, preferably having a degree of deacetylation > 75%.
6. Method according to any of the preceding claims, wherein the plasma treating in step (b)

   - is a low-pressure plasma activation
   or

   - comprises a low-pressure plasma activation and at least one further plasma treatment step

   and/or
   wherein the low-pressure plasma treatment takes place at a pressure in the range from 1 Pa to 20 kPa, preferably at a pressure in the range from 1 Pa to 0.5 kPa, more preferably at a pressure in the range from 10 Pa to 50 Pa.
7. Method according to Claim 6, wherein the low-pressure plasma treatment is carried out with at least one oxygen-containing compound selected from the group consisting of O, O₂, O₃, NO, N₂O and CO₂, to produce oxygen-containing functional groups on the textile surface which are bonded preferably covalently to the textile surface.
8. Method according to Claim 7, wherein the at least one oxygen-containing compound

   - is present in a gas mixture which comprises O₂ and at least one inert gas selected from the group consisting of He and Ar,

   wherein said gas mixture which comprises O₂ and at least one inert gas selected from a group consisting of He and Ar comprises at least 99 vol% of O₂ and at least one inert gas selected from the group consisting of He and Ar,
   and more preferably comprises at least 99 vol% of O₂ and Ar, where preferably the gas mixture comprises a fraction of O₂ in the range from 70 vol% to 90 vol% and a fraction of He and/or Ar in the range from 10 vol% to 30 vol%.
9. Method according to any 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 selected from the group consisting of cotton, wool, silk, cellulose and regenerated cellulose and also mixtures thereof, more preferably selected from the group consisting of cellulose and regenerated cellulose and also mixtures thereof;

   - a second material selected from the group consisting of polyesters, polyamides, polyamideimides, polypropylene, polyacrylonitrile and polyacryl methacrylate and also mixtures thereof, more preferably selected from the group of the synthetic polymers, preferably of the biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and also mixtures thereof;
   and also

   - mixtures thereof;
   the plasma treating in step (b)

   - is 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, O₂, O₃, NO, N₂O and CO₂, to produce preferably oxygen-containing functional groups on the textile surface which are bonded preferably covalently to the textile surface,
   and
   the hydrophobizing agent used in step (c) is an aqueous-hydrophobizing agent which
   comprises modified polydimethylsiloxane, preferably modified polydimethylsiloxane in which one or more methyl groups have been replaced by substituents having basic functional groups, alkyl groups and/or polyether groups;
   and also 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 esters, methacrylic acid, methacrylic esters and optionally further monomers copolymerizable with acrylic acid, acrylic esters, methacrylic acid and/or methacrylic esters, preferably styrene;

   - polyurethanes, preferably polyurethanes of the polyester type and/or of the polycarbonate type;

   - polyesters,

   - polypeptides,

   - polyamides,
   and

   - polysaccharides, preferably selected from the group consisting of chitin and chitosan.
10. Method according to any of the preceding claims, preferably according to Claim 9,
    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 cellulose and regenerated cellulose and also mixtures thereof;

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

    - mixtures thereof;
    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 also mixtures thereof;
    the plasma treating in step (b)

    - is a low-pressure plasma treatment, preferably a low-pressure plasma activation, which is carried out in the presence of a gas mixture which comprises O₂ and at least one inert gas selected from the group consisting of He and Ar, wherein preferably said gas mixture comprises at least 99 vol% of O₂ and at least one inert gas selected from the group consisting of He and Ar,
    and wherein more preferably said gas mixture comprises at least 99 vol% of O₂ and Ar,
    and
    the hydrophobizing agent used in step (c) is an aqueous hydrophobizing agent which
    comprises modified polydimethylsiloxane, preferably modified polydimethylsiloxane in which one or more methyl groups have been replaced by substituents having basic functional groups, alkyl groups and/or polyether groups;
    and also 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 esters, methacrylic acid, methacrylic esters and optionally further monomers copolymerizable with acrylic acid, acrylic esters, methacrylic acid and/or methacrylic esters, preferably styrene;

    - polyurethanes, preferably polyurethanes of the polyester type and/or of a polycarbonate type;

    - polyesters,

    - polypeptides,

    - polyamides
    and

    - polysaccharides, preferably selected from the group consisting of chitin and chitosan.
11. Method according to any of Claims 6 to 10, wherein in step b)

    - the low-pressure plasma treatment is carried out for a duration in the range from 10 sec to 10 min, preferably in the range from 30 sec to 5 min, more preferably in the range from 1 min to 3 min;
    and/or

    - the low-pressure plasma is generated at a frequency in the range from 10 MHz to 18 MHz, preferably in the range from 11 MHz to 15 MHz;
    and/or

    - the low-pressure plasma is generated with electrodes, wherein the electrode density is preferably in the range from 1 to 10 electrodes/m², more preferably in the range from 2 to 5 electrodes/m², very preferably in the range from 2.5 to 4 electrodes/m², based on the textile surface produced or provided in step (a);
    and/or

    - the low-pressure plasma treatment is carried out with a plasma generation source at a power in the range from 0.05 kW to 100 kW, preferably in the range from 1 kW to 25 kW, more preferably in the range from 2 kW to 15 kW, very preferably in the range from 5 kW to 10 kW,
    and/or

    - the low-pressure plasma treatment is carried out in a plasma treatment chamber at a power in the range from 0.25 kW/m³ to 2.0 kW/m³, preferably in the range from 0.5 kW/m³ to 1.5 kW/m³.
12. Method according to any of the preceding claims, wherein the wet-chemical treating in step (c) comprises one or more or all of the following measures:

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

    - drying of hydrophobizing agent taken up on the textile surface,

    - fixing of hydrophobizing agent taken up on the textile surface,

    wherein the wet-chemical treating
    preferably comprises a full bath impregnation, more preferably by padding, of the plasma-treated textile surface resulting in step (b) or a textile surface produced therefrom in further steps,
    where preferably thereafter the hydrophobizing agent taken up is dried and/or fixed on the textile surface.
13. Method according to any of the preceding claims, wherein the plasma-treated hydrophobized textile surface resulting after step (c)

    - is comparatively more hydrophobic than the textile surface

    - of the article produced or provided in step (a)
    and/or

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

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

    and/or

    - is comparatively hydrophobized more durably than the corresponding textile surface of the article produced or provided in step (a) after only wet-chemical treating as in step (c), but without prior plasma treating in step (b).
14. Textile article comprising a hydrophobized textile surface producible by a method according to any of the preceding claims.
15. Use of a low-pressure plasma method for preparatory treatment of a textile surface of an article, before the wet-chemical hydrophobizing of the textile surface, wherein the low-pressure plasma treatment is carried out with at least one oxygen-containing compound selected from the group consisting of O, O₂, O₃, NO, N₂O and CO₂,
    wherein the at least one oxygen-containing compound is present in a gas mixture which comprises O₂ and at least one inert gas selected from the group consisting of He and Ar,
    wherein the gas mixture comprises a fraction of O₂ in the range from 70 vol% to 90 vol% and a fraction of inert gas in the range from 10 vol% to 30 vol%.