RS61750B1 - Method for producing a textile article with hydrophobised textile surface using plasma treatment and wet chemical processing - Google Patents

Description

DESCRIPTION OF THE INVENTION

The proposed invention relates to a process for the production of textile articles with hydrophobic textile surfaces, which includes the following production steps:

(a) Production of an object that has a textile surface or an object on which a textile surface is placed,

(b) Processing the plasma produced or placed textile surface produced in step (a) so as to obtain a plasma treated textile surface,

(c) Wet chemical treatment with an agent for hydrophobization of the textile surface that has already been treated with plasma in step (b), or of the textile surface that has been produced from it in further steps, so that as a result of the process a hydrophobic surface of the textile treated with plasma is obtained, whereby the plasma treatment from step (b) implies

- processing with low-temperature plasma or

- low-temperature plasma treatment and at least one further step of plasma treatment, whereby the low-pressure plasma treatment is carried out using at least one compound containing oxygen, selected from the group consisting of O, O2, O3, NO, N2O and CO2, whereby at least one compound containing O2 and at least one inert gas selected from the group consisting of He and Ar are present in the gas mixture, with the proportion of O2 in the gas mixture ranging from 70% volume up to 90% by volume, while the share of inert is in the range from 10% by volume to 30% by volume.

Furthermore, the invention also relates to a textile product that can be produced by a process according to the invention. In addition, the invention also relates to the use of a low-pressure plasma treatment process for the preparatory treatment of the textile surface of the object, prior to wet chemical hydrophobization of the textile surface, wherein at least one oxygen-containing compound selected from the group consisting of O, O2, O3, NO, N2O and CO2 is used for the low-pressure plasma treatment, wherein at least one oxygen-containing compound is present in the gas mixture containing O2 and at least one inert gas selected from the group consisting of He and Ar, where in the mixture of gases O2 has a volume share ranging from 70% volume to 90% volume, while the share of inert is in the range from 10% volume to 30% volume.

Textile products with a hydrophobic surface, for example a water-repellent or water-resistant surface, such as garments intended for outdoor wear, are currently generally produced by finishing them with fluorine-containing chemicals. Perfluorinated or polyfluorinated organic compounds, also known as "fluorocarbons", are often used for this purpose. However, considering that such fluorocarbons are very long-lived and can be deposited in the environment - whereby the risk to the environment and the health of all living organisms cannot be ruled out - the industry is looking for alternatives that would have similar advantages when it comes to the properties of the obtained surfaces, but which would avoid the disadvantages mentioned in the previous part of the text. Contributions to this discussion can be found in the publication "Perfluorinated and polyfluorinated chemicals - Avoidance of intake - Environmental protection" published by the German Federal Environment Agency in July 2009 and from press release no. 32 German Federal Environment Agency from October 2016.

Also, as part of the so-called "Detox campaign", a large number of manufacturers and distribution companies in Germany committed in 2011 to remove perfluorinated and polyfluorinated chemicals classified as potentially dangerous from their supply chains by 2020.

Known alternative solutions for the enrichment of textiles with fluorocarbons include the use and application of low-fluorinated hydrophobic and oleophobic agents, fluorine-free hydrophobizing agents, which in particular include silicones, conventional polyurethanes as well as modified polyurethanes, plastic membranes or products based on nanoparticles or nano fibers (i.e. fibers with at least one dimension of the order of nanometers). The 2012 publication "Investigation of Alternatives for Fluorocarbon Textile Finishing" by M. Schottner, a master's thesis at the University of Applied Sciences Berlin, from 2012, provides an overview of such known alternatives.

As a solution for modifying textile surfaces, plasma treatment is also known by itself. Plasma is a partially ionized gas, and is often called the "fourth physical state of matter." Phenomena such as lightning or aurora borealis are forms of plasma that occur in nature. Technically speaking, plasma can be created by applying electric fields. Plasma is also interesting because of its physical and chemical properties. In it, particles and free radicals are created in a highly excited state. They can initiate chemical reactions that are not possible under normal conditions. In this sense, the temperature of the workpiece processed by plasma can be very low.

Patent document DE 101 11 427 A1 describes a procedure and device for cleaning and treating textiles with low-temperature plasma.

Patent document EP 695 622 A2 describes a method and device for modifying porous objects, for example textiles, using plasma.

Patent document WO 2016/193486 A1 describes a process for applying a halogen-free water-repellent nano-layer to textiles using a low-pressure plasma polymerization process.

Active impregnation ingredients containing non-fluorinated silicones and at least one cationic polymer are known from the patent document WO 2010/139466 A1.

Patent document JP S62104975 A describes a process for the production of a water-repellent fabric which includes applying to the fabric a liquid containing organopolysiloxanes and/or fluorine compounds, treating it with a low-pressure plasma and, after that, re-applying said liquid. Patent document JP S60194183 A describes a permanently coated synthetic or natural fabric consisting of a silicone rubber film placed over a base fabric.

However, considering the state of the art, there is still a need for a simple, efficient and environmentally friendly process of hydrophobization of textile products, which would enable the production of water-repellent, or at best perfectly water-resistant, durable textile surfaces, which could contribute to reducing as much as possible, or at best completely avoiding, the use of more durable chemicals such as fluorocarbons or alkylphenol ethoxylates, which at best degrade slowly in the environment. Also needed is a process for the production of multipurpose textiles (as well as the textiles themselves) that are at least partially, or at best, fully biodegradable or compostable (degradable in air), and at the same time meet the criteria for certification according to the standards for "cradle-to-cradle" products (a concept based on zero-waste production systems that do not harm the environment) established by the "Cradle-to-Cradle Product Innovation Institute", from Auckland, in USA, ("Cradle-to-Cradle Certified ™").

Therefore, the primary goal of this invention was to provide a process for the production of textile items with a hydrophobized textile surface that would enable efficient, long-lasting and robust hydrophobization or impregnation of the textile surface, and which would result in a durable and resistant textile surface that would be at least water-repellent, and in the best case, perfectly waterproof.

Textile products produced according to the above procedure must retain hydrophobic properties, especially water-repellent or water-resistant surface properties, preferably even after very demanding use - such as, for example, professional or industrial use, say for work clothes - with increased requirements in terms of wear resistance and elasticity of the surface finish.

Another special goal of this invention was to provide an environmentally acceptable process that could contribute to reducing as much as possible, or in the best case completely avoiding, the use of more durable or hard-to-degrade chemicals such as fluorocarbon or alkylphenol ethoxylates, which at best degrade slowly in the environment. An important aspect of this special task was the use of the above-mentioned environmentally friendly process for the production of textile items that are at least partially, and in the best case completely, biodegradable (i.e. degradable by means of biological mechanisms such as the action of microorganisms), and based on this property, they should be at least partially, and in the best case completely, compostable, and based on that, in the biological sense, they would also be suitable for recycling.

It can be stated that the primary objective and additional objectives and/or sub-objectives of this invention are achieved by the process carried out in accordance with this invention for the production of textile articles with a hydrophobized textile surface, which contains the following working steps:

(a) Production of an object that has a textile surface or an object on which a textile surface is placed,

(b) Treatment of the plasma-produced or placed textile surface referred to in step (a) so as to obtain a plasma-treated textile surface,

(c) Wet chemical treatment with an agent for hydrophobization of the textile surface that has already been treated with plasma in step (b), or of the textile surface that has been produced from it in further steps, so that as a result of the process a hydrophobic surface of the textile treated with plasma is obtained, whereby the plasma treatment from step (b) implies

- processing using low-pressure plasma or

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

wherein the low-pressure plasma treatment is performed using at least one oxygen-containing compound selected from the group consisting of O, O2, O3, NO, N2O and CO2, wherein at least one oxygen-containing compound is present in the gas mixture A containing O2 and at least one inert gas selected from the group consisting of He and Ar, wherein the proportion of O2 in the gas mixture ranges from 70% by volume to 90% by volume, while the proportion of inert in the range of 10% by volume to 30% by volume.

With the process carried out in accordance with the invention, textile products with robust, long-lasting water-repellent or water-resistant properties can be produced, and in an environmentally friendly way that implies reduced use, i.e. greatly reduced use, or complete avoidance of the use of long-lasting chemicals such as fluorocarbons or alkylphenol ethoxylates, which at best degrade slowly in the environment.

The textile products produced by the process according to the invention are suitable for very demanding use such as professional or industrial use which entails increased demands in terms of wear resistance and surface treatment resistance, for example for use in the form of work clothes and/or for industrial washing processes, since such textile items maintain their properties for a long time, even under such demanding conditions of use.

In many cases, the surfaces of textile products produced by the process in accordance with the present invention also have additional beneficial properties, for example, they can be additionally dirt-repellent, weather-resistant, easy to clean, and/or have little or no adhesion ("lotus effect").

A further advantage of the textile products produced by the process according to the present invention is that they are suitable for refreshing the hydrophobization or impregnation, or for post-hydrophobization or post-impregnation, when, for example after prolonged use, the water-repellent or water-resistant properties of the textile products are reduced: for this purpose, the textile products produced by the process according to the present invention can be improved again by means of repeated wet chemical treatment according to by step (c) described above, for example by impregnation in a washing machine, so that after it they regain their hydrophobic or water-repellent or water-resistant properties.

The invention and combinations of parameters, properties and/or components of this invention that are desirable in accordance with this invention are defined in the appended patent claims. Preferred aspects of the present invention are also set forth or defined in the descriptions of the invention below, as well as in the derived examples thereof.

The term plasma treatment generally refers to all processes during which plasma can be used for surface treatment, especially for surface treatment of textile objects, in particular for plasma cleaning, plasma functionalization, plasma etching and plasma coating. Plasma processing may include one or more of the aforementioned plasma-based processes, which are explained in more detail below.

Plasma cleaning often precedes further plasma processing steps and is usually performed with a low-pressure plasma. A universally applicable low-pressure plasma treatment system is therefore often equipped in such a way that basic cleaning processes can be performed with it, especially oxygen plasma cleaning. Such a low-pressure plasma system used for cleaning processes is also called a "plasma cleaner".

Plasma functionalization (or "plasma activation") is mainly used to increase the surface tension of non-polar substrates (ie materials or substances to be processed by plasma activation). For this purpose, oxygen free radicals are usually created in the oxygen plasma (i.e. by using oxygen or compounds that generate oxygen in the plasma, mainly gases), which, due to their high reactivity, can create bonds with the surface structures of the substrate, thereby increasing the surface tension and/or humidity of the surface of the substrate. During plasma activation, monomers that can polymerize are not used, because the goal is not to directly coat the surface of the substrate with a polymer layer. Activation - plasma functionalization is usually performed over a shorter period of time, for example in the range of less than 10 minutes. The quality of the plasma activation can be evaluated or verified, for example, by means of known contact angle measurements. This method is applied by measuring the contact angle of a drop of the test liquid with the treated surface. The better the plasma activation is performed, the more flattened the droplet will be while lying on the surface of the workpiece.

Plasma etching refers to processes of etching solid workpieces with the help of plasma. During plasma etching, parts of the substrate surface are removed by a chemical reaction with the process gas. During that process, the high reactivity of excited atoms and molecules, especially free radicals, is used. The most important criterion in selecting an etching gas is its ability to form a highly volatile reaction product in reaction with the solid being etched. Etch rates vary greatly (are selective) depending on different substrates. Suitable organic etching gases are, for example, perfluorinated hydrocarbons (perfluorocarbons, fluorocarbons) such as tetrafluoromethane (CF4), hexafluoroethane (C2F6), perfluoropropane (C3F8), perfluorobutadiene (C4F6), unsaturated fluorocarbons, perfluorinated aromatic compounds (aromatics) and perfluorinated heteroaromatics. Suitable inorganic etching gases are, 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 it is desired to achieve the removal of a large amount of material with significant changes in the physical or mechanical properties of the surface (mainly with a high energy input). Mixtures of different caustic gases are also often used. Plasma etching is typically performed over a longer period of time, for example, in the range of 15 to 120 minutes.

During the plasma coating process (deposition of thin layers), polymerizable monomers are introduced into the plasma treatment chamber, usually in a low-pressure plasma, which are then polymerized by the action of the plasma. The thicknesses of the layers obtained by this plasma polymerization are usually in the order of micrometers. The process technology used in the plasma coating process is much more complex than, for example, the technology used for plasma activation.

In the process carried out in accordance with the invention, the plasma treatment includes low-pressure plasma treatment or low-pressure plasma treatment and at least one further step of plasma treatment, wherein the low-pressure plasma treatment is performed using at least one oxygen-containing compound selected from the group consisting of O, O2, O3, NO, N2O and CO2, wherein at least one oxygen-containing compound is present in the gas mixture containing O2 and at least one inert gas selected from the group consisting of consists of He and Ar, while in the mixture of gases O2 has a share ranging from 70% of volume to 90% of volume, while the share of inert gas is in the range of 10% of volume to 30% of volume.

In accordance with the invention, a favorable performance of the procedure implies that the hydrophobized textile surface is treated with plasma in accordance with step (c)

- it is relatively more hydrophobic compared to a textile surface

- items produced or equipped with textiles described in step (a) and/or

- plasma treated textile surfaces described in step (b) (primarily plasma cleaned and/or plasma activated)

and/or

- a product produced or equipped with the textile described in step (a) after only the wet chemical treatment described in step (c), but without the prior plasma treatment described in step (b),

and/or

- it is relatively more permanently hydrophobic compared to the corresponding textile surfaces of the object produced or equipped with the textile described in step (a) after only the wet chemical treatment carried out in accordance with the description from step (c), but without the previous plasma treatment described in step (b).

The term "relatively hydrophobic" here primarily means that the resulting plasma-treated hydrophobized textile surface resulting from step (c) has a higher value (in centimeters) of the water column than the corresponding comparative textile surface, in accordance with ISO 81-1981 / DIN EN 20811: 1992-08 (the standard relating to the height of the water column above the textile surface, i.e. the column above/facing the textile surface being treated by plasma, i.e. which is above/facing the surface of the textile that has been treated with plasma or is above/facing the surface treated with plasma that has been hydrophobized).

- or a product that has been produced or equipped with textiles in accordance with the description from step (a), and which has not undergone the appropriate processing described in steps (b) and (c)

and/or

- of the product produced in accordance with step (b) which has not been subjected to the appropriate treatment described in step (c)

and/or

- a product manufactured or equipped with textiles in accordance with the description from step (a), which has undergone only the wet chemical treatment described in step (c), but without the previous plasma treatment described in step (b).

The textile surface of the product that is produced or equipped with textiles in accordance with the description from step (a) can - especially for the purpose of comparing the procedure performed in accordance with the invention and the textile surfaces obtained by performing the procedure in accordance with the invention - be processed directly by wet chemical treatment, i.e. without prior plasma treatment. If the wet chemical treatment of the article produced or equipped with textiles in accordance with the description from step (a) for the purpose of comparison is carried out in exactly the same way as in accordance with the invention and carried out in step (c), a textile surface is obtained that can be evaluated by direct comparison of its hydrophobic properties. A corresponding comparative study is given below in Example 6 (compare the values of "A: initial moisture rejection" from Table 3).

The term "relatively more permanently hydrophobic" here primarily means that the plasma-treated hydrophobized textile surface resulting from step (c) has a higher value obtained in the spray test according to the AATCC TM22-2014 standard (in standard values according to the specification of the standard) compared to the corresponding textile surface of a product manufactured or equipped with a textile according to the description of step (a) which has been treated under the same conditions only by wet chemical treatment according to the description of step (c), but without the previous plasma treatment described in step (b). It is particularly preferred that the term "relatively more permanently hydrophobic" means that the plasma-treated hydrophobized surface of the textile obtained in step (c) and after five washing and drying cycles (preferably carried out in accordance with ISO 6330: 2000 (E), conditions: washing machine type A/with front loading of laundry; Washing program 5A "Normal" at 40 ± 3 °C; clothes dryer) has a higher value in accordance with the said standard AATCC TM22-2014 than that of the corresponding textile surface of a product manufactured or equipped with textiles in accordance with the description of step (a) which, for the purpose of comparison, under the same conditions (i.e. also after five washing and drying cycles) has been treated only with the wet chemical treatment described in step (c), but without the prior plasma treatment described in step (b).

It is preferable that the wet chemical treatment described in step (c) of the procedure carried out in accordance with the invention is an aqueous wet chemical treatment, i.e. wet chemical processing, during which the surface of the textile is treated with plasma in contact with both a hydrophobizing agent and water, preferably at the same time.

In accordance with the invention, it is desirable to perform a procedure that is carried out in the manner described in the previous part of the text, or in the part of the text that follows, whereby the specified textile surface of the product that is manufactured or equipped with textiles in accordance with the description from step (a)

- contains one or more materials selected from the group they comprise

- the first material (here and in the rest of the description the term is used in the sense of "the first group of materials"), primarily a natural material, primarily selected from the group consisting of cotton, wool, silk, cellulose and regenerated cellulose, as well as mixtures of these materials; wherein it is particularly advantageous to be selected from the group consisting of cellulose, regenerated cellulose and their mixtures;

- other material (here and in the rest of the description, the term is used in the sense of "another group of materials"), primarily a synthetic material, primarily selected from the group consisting of polyester, polyamide, polyamide-imide, polypropylene, polyacrylonitrile and polyacrylic methacrylate, as well as mixtures of these materials; wherein it is particularly advantageous to be selected from the group consisting of synthetic polymers, particularly advantageous to be biodegradable synthetic polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and their mixtures;

as well as

- their mixtures (in terms of the number of components and their proportions, any mixture of one or more first, primarily natural materials and/or one or more other, primarily synthetic materials)

and or

- is selected from the group consisting of woven, knitted, knitted, braided, stitched, felted or textile composite materials, non-woven textiles, textile hoses, ropes, fibers, threads, yarns, trenches and mixtures thereof; preferably, it is selected from the group consisting of woven, knitted, knitted materials, textile composite materials, non-woven textile materials, as well as mixtures of these materials.

Articles with a textile surface that are produced or equipped with textiles as described in step (a) of the method of execution according to the invention contain one or more materials that can be used individually or in combination. For this purpose, one or more first materials can be used (i.e. materials selected from the group of first materials or the first group of materials, as defined in the previous section of the text) or one or more other materials (i.e. materials selected from the group of other materials or the second group of materials, as defined in the previous section of the text) or a mixture or combination of one or more first materials (i.e. materials selected from the group of first materials or the first group of materials, as defined in the previous section of the text) with one or more other materials (i.e. materials selected from the group of other materials or another group of materials, as defined in the previous part of the text). Combinations of favorable materials (therefore) result in favorable-preferred materials or combinations of materials.

In an advantageous variant of carrying out the procedure according to the invention, the textile surface of the product produced or equipped with textiles as described in step (a) contains at least one other material selected from the group (preferably another group of materials) consisting of polyester, polyamide, polyamide-imide, polypropylene, polyacrylonitrile and polyacrylmethacrylate, as well as their mixtures; it is particularly advantageous for the material to be selected from the group of synthetic polymers, primarily biodegradable synthetic polymers, which consists of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures.

In the next advantageous variant of carrying out the procedure according to the invention, the textile surface of the product that is manufactured or equipped with textiles as described in step (a) contains only another material selected from the group (ie one or more materials that are selected from another group of materials) consisting of polyester, polyamide, polyamide-imide, polypropylene, polyacrylonitrile and polyacryl-methacrylate, as well as their mixtures; it is particularly preferable that the material is selected from the group of synthetic polymers, primarily biodegradable synthetic polymers, which consists of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures. In this advantageous variant of carrying out the procedure according to the invention, the textile surface of the product which is manufactured or equipped with textiles as described in step (a) does not contain the first material (primarily natural material), that is, it is advantageous that no material is selected from the group (primarily the first group of materials) consisting of cotton, wool, silk, cellulose and regenerated cellulose, as well as their mixtures.

If the textile surface of the product that is manufactured or equipped with textiles as described in step (a) consists of one or more materials which - as stated in the previous part of the text - are selected from the group consisting of at least one first material (as defined in the previous part of the text), primarily a natural (and therefore biodegradable) material, which is preferably selected from the group (primarily the first group of materials) consisting of cotton, wool, silk, cellulose and regenerated cellulose; and from at least one other material (as defined in the previous part of the text), primarily a synthetic material, which is selected from the group (primarily another group of materials) of synthetic polymers, primarily biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as mixtures of these materials, textile articles produced by the process performed in accordance with the invention are in a favorable case at least partially a - in depending on the other ingredients of textile products, such as a hydrophobization agent - ideally completely biodegradable (ie degradable by biological mechanisms, such as the action of microorganisms), and thus they are, at least partially, and ideally completely compostable, and accordingly suitable for recycling. Therefore, this variant of carrying out the procedure according to the invention is very desirable. The term "biodegradable" in the context of the present invention means that a textile product, material or substance with that property can be composted and is preferably within a period of 12 to 36 months, and particularly preferably within a period of 18 to 30 months, and preferably at a temperature in the range of 40 °C to 80 °C, and particularly preferably in the range of 50 °C to 75 °C, at least predominantly (i.e., more than 90 percent by mass, and preferably more than 95 percent of the mass of the starting material is biologically degradable under the specified conditions), and in the ideal case it is practically completely biodegradable (ie degradable by biological mechanisms such as the action of microorganisms).

If the textile surface of the product that is manufactured or equipped with textiles as described in step (a) contains one or more materials selected from the group consisting of at least one first material (as defined in the previous part of the text), primarily natural (and therefore biodegradable) material from the group (primarily the first group of materials) consisting of cellulose and regenerated cellulose; and at least one other material (as defined in the previous part of the text), primarily a synthetic material selected from the group (primarily another group of materials) of synthetic polymers, preferably biodegradable synthetic polymers, which consists of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as a mixture of these materials, the products produced by the process carried out in accordance with the invention are not only in a favorable performance, at least partially, and in the perfect case, practically completely biodegradable and thus at least partially, and in the perfect case, completely compostable, they are also suitable for meeting particularly high requirements regarding their mechanical strength and durability or durability of hydrophobic or water-repellent or water-resistant properties. This is why this variant of carrying out the procedure according to the invention is particularly advantageous.

Accordingly, it is advantageous that the method carried out in accordance with the invention or the advantageous method described in the previous or subsequent part of the text, has a textile surface of the product that is produced or equipped with textiles as described in step (a) that contains one or more materials selected from the group consisting of

- the first material selected from the group (primarily from the first group of materials) consisting of cellulose and regenerated cellulose and their mixtures;

- another material selected from the group (primarily from the second group of materials) consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures;

wherein it is preferable that the second material is selected from the group (primarily from the second group of materials) of copolyester consisting of monomers of terephthalic acid and one or more alkanediols (primarily selected from the group consisting of ethylene glycol (ethanediol), 1,3-propanediol and 1,4-butanediol, and it is especially preferable that it be ethanediol)

wherein it is primarily advantageous for them to contain at least one additional monomer; as well as

- mixtures thereof;

whereby it is primarily preferable that the textile surface contains one or more materials, at least one of which is selected from the group they comprise

- another material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures;

wherein it is primarily preferable that the second material be prohibited from the group of copolyesters consisting of monomers of terephthalic acid and one or more alkanediols (primarily selected from the group consisting of ethylene glycol (ethanediol), 1,3-propanediol and 1,4-butanediol, and it is particularly advantageous for it to be ethanediol), wherein it is preferable that they contain at least one additional monomer that differs from the above-mentioned monomers (terephthalic acid or one or more alkanediols);

It is preferable that the cellulose used as the first, primarily natural material, in step (a) of the process performed according to the invention, is obtained from wood-based raw materials and/or from plant fibers, primarily from hemp, flax, bamboo, banana and/or ramie.

In the context of the present invention, the preferred term "regenerated cellulose" includes regenerated fibers. Regenerated fibers are fibers that are produced from renewable raw materials of natural origin using chemical processes. These are mainly cellulose derivatives obtained from wood-based raw materials.

It is advantageous that within the scope of this invention the cellulose (pulp) or regenerated cellulose that can be used in step (a) of the procedure carried out in accordance with the invention, contains materials (or fibers made of these materials) viscose, modal (rayon fabric from beech fibers), lyocell (material from the wood pulp of the eucalyptus plant) and cupro (a type of viscose), and it is especially desirable that it contains lyocell.

Viscose fibers are chemical fibers (chemically regenerated fibers) that are industrially produced by the well-known technological process of wet spinning. Starting raw material

1

process for obtaining viscose is cellulose, mainly in the form of wood-based raw material, from which high purity cellulose is extracted using various processes.

Modal fibers also consist of 100 percent cellulose, like viscose fibers, but unlike other recycled fibers, they are mostly made from beech wood. The starting raw material for their production is beech wood that has been peeled and then chopped into pieces for separation from lignin. Modal fibers can be modified to improve their strength and other properties compared to other cellulosic fibers. In addition, modal fibers have a higher ability to absorb moisture and dry faster.

Lyocell is an industrially produced regenerated cellulosic fiber, well known in the prior art, consisting of cellulose and produced by a direct solvent process, which is also well known in its own right. It is especially used for the production of textiles and non-woven textiles. Lyocell fibers have high strength both when dry and when wet, are soft and absorb moisture very well. Textiles made from this material are usually smooth and soft to the touch, have a gentle and regular fall and 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 that is also made from regenerated cellulose. The properties of this material can be compared to those of viscose. Cupro fibers are mainly processed into textile coverings because they are breathable, hygroscopic and resistant to static electricity. In addition, the fabrics feel silky soft to the touch, smooth and shiny. Cupro can be washed and ironed, and cannot be considered a wrinkle-resistant material. Cupro is usually produced by the copper-oxide-ammonia treatment process (the so-called "Cuoxam" process).

It is primarily preferred that the second synthetic material that can be used in step (a) of the process performed in accordance with the invention also contains elastomers, preferably biodegradable elastomers.

It is particularly advantageous that the synthetic polymers used as the second material in step (a) of the procedure performed according to the invention, primarily biodegradable synthetic polymers, contain substituted and/or unsubstituted polyesters, and it is particularly desirable that they contain copolyesters of aromatic and aliphatic monomers. It is also advantageous that those particularly desirable copolyesters of aromatic and aliphatic monomers, as monomers, contain terephthalic acid and one or more alkanediols, primarily selected from the group consisting of ethylene glycol (ethanediol), 1,3-propanediol and 1,4-butanediol. In a particularly advantageous variant of carrying out the process according to the invention, the second, primarily synthetic material used in step (a) as monomers contains terephthalic acid and one or more alkanediols (primarily one alkanediol, i.e. one type of alkanediol) selected from the group consisting of glycol (ethanediol), 1,3-propanediol and 1,4-butanediol (preferably ethanediol), and it is advantageous that they also contain at least one more additional monomer. Examples of biodegradable substituted or unsubstituted polyesters or fibers of such biodegradable substituted or unsubstituted polyesters that are particularly used in accordance with the invention are polybutylene adipate terephthalate ("PBAT"), Ecoflex® (by BASF) and infinito® (by Lauffenmühle GmbH & Co. KG).

Preferably, the polyamides that can be used in step (a) of the process according to the invention are, or include, polyamidimides and aramids (also called "aromatic polyamides"), primarily according to the definition of the US Federal Trade Commission according to which aramids are polyamides with aromatic groups in the main chain in which at least 85% of the amide groups are directly attached to two aromatic rings.

It is particularly advantageous for the biodegradable polyamide used in step (a) of the process according to the invention to be the known polyamide 6. An example of a biodegradable polyamide which is particularly preferred according to the invention is Amni Soul Eco® (Rhodia/Solvay).

Variants of the textile surface of a product manufactured or equipped with textiles as described in step (a) listed in the previous section of the text can be used individually or in combination (together). For example, threads, fibers or yarns made from one or more of the listed materials can be used separately or in combination with each other. For example, yarns made of at least one synthetic material and/or yarns of at least one natural material can be twisted individually or together with other fibers to create a yarn, or such different yarns can be individually or together processed by joining, weaving or twisting to create a yarn, woven material or fabric.

Primarily, in step (a) of the procedure carried out in accordance with the invention, textile products are used which are produced or equipped with textiles whose textile surface is selected from the group consisting of woven and knitted materials. The plasma treatment of woven and knitted fabrics in step (b) of the procedure carried out in accordance with the invention can be carried out particularly rationally and efficiently. Textile fabrics or knitted fabrics produced by the process according to the invention can be further directly processed into finished textile products, for example into textile products for everyday use, such as clothing intended for outdoor wear.

The materials mentioned in the previous part of the text (for example, cellulose or regenerated cellulose and/or one or more synthetic polymers that are defined in the previous part of the text) and the types of textile surfaces mentioned in the previous part of the text (for example, woven or knitted materials) can be advantageously combined, and such combinations, especially combinations of favorable materials with desirable types of textile surfaces, result in equally favorable variants of carrying out the procedure according to the invention.

It is also desirable to carry out the procedure performed in accordance with the invention or procedures performed in accordance with the invention, which are characterized as favorable in the previous and subsequent parts of the text, in which the textile surface of the products that are produced or equipped with textiles in accordance with the description of step (a), is a fabric obtained by weaving, knitting, knitting, braiding, quilting, felting, or non-woven textile fabric and/or textile tube, preferably fabric and/or knitted fabric, and a fabric/fabrics which are particularly advantageous

- has a weight per unit area in the range of 20 g/m<2> to 500 g/m<2>, primarily in the range of 100 g/m<2> to 200 g/m<2>

and/or

- has a thread density in the range of 80 to 120 threads/cm warp, and 40 to 80 threads/cm weft.

During our own tests, it turned out that the favorable textile surfaces mentioned in the previous part of the text, especially woven and/or knitted fabrics, are particularly suitable for plasma treatment in step (b) of performing the procedure according to the invention, which enables particularly successful execution of plasma activation and particularly good subsequent hydrophobization of the textile surface.

It is also desirable to carry out a procedure performed in accordance with the invention or procedures performed in accordance with the invention, which are characterized as favorable in the previous and subsequent parts of the text, in which the hydrophobization agent is the sparing agent used in step (c)

- a water-based hydrophobization agent that primarily contains modified polydimethylsiloxane

and/or

- a hydrophobization agent that does not contain organic compounds containing fluorine.

A water-based hydrophobizing agent allows the entire procedure to be performed on a water basis (ie, to be performed at least in the presence of water), and ideally without the presence of organic solvents. In this way, very few organic solvents will penetrate into the environment, or they will not penetrate at all, without the need to implement complex filtering or retention measures, that is, in this way, only little or no residues of organic solvents are deposited that could affect the environment or would have to be eliminated, which is carried out in a very complex way. Polydimethylsiloxanes are known to be at worst very slightly toxic and to a great extent chemically inert, so that when used in the process carried out in accordance with the invention, the danger to living organisms can be excluded to the greatest extent, or ideally completely excluded.

Since organic compounds containing fluorine, such as perfluorinated or polyfluorinated organic compounds (fluorocarbons), are eliminated from the process carried out in accordance with the invention at least extensively, and in the ideal case completely, the typical disadvantages of those types of substances in terms of their effect on the environment are avoided, which gives an additional contribution to the high degree of ecological sustainability of the process carried out in accordance with the invention.

In the process carried out in accordance with the invention or the process described in the previous or subsequent part of the text as desirable, it is advantageous for the water-repellent ingredient to be a water-based hydrophobizing agent containing

- modified polydimethylsiloxane, primarily modified polydimethylsiloxane in which one or more methyl groups are replaced by substituents with basic functional groups, alkyl groups and/or polyether groups;

and additionally

- contains one or more cationic polymers selected from the group they comprise

- polyacrylates, preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, esters of acrylic acid, methacrylic acid, methacrylic acid esters and optionally other monomers that copolymerize with acrylic acid, acrylic acid esters, methacrylic acid and/or methacrylic acid esters, primarily styrene;

- polyurethanes, primarily polyester-type and/or polycarbonate-type polyurethanes, which are preferably formed by polycondensation of dihydric alcohols or polyhydric alcohols with diisocyanates and/or polyisocyanates;

- polyesters, which are primarily formed by polycondensation of dihydric alcohols or polyhydric alcohols with dicarboxylic acids and/or polycarboxylic acids;

- polypeptides, which are primarily formed by polycondensation of amino acids,

- polyamides, which are primarily formed by polycondensation of amino acids,

- primarily synthetic biopolymers, primarily polypeptides or polyamides, which are conveniently formed by polycondensation of amino acids;

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- polysaccharides, which are primarily selected from the group consisting of chitin and chitosan (for modifications and the like, see the following description)

Polyacrylates that can be used in step (c) of the procedure carried out in accordance with the invention, and for which it is suitable to be selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, methacrylic acid esters and methacrylic acid, can optionally contain monomer units that can be copolymerized with acrylic acid, acrylic acid esters, methacrylic acid esters and/or methacrylic acid. "Optional" in this context means that the homopolymers and copolymers are formed from acrylic acid monomers, acrylic acid esters, methacrylic acid and methacrylic acid esters, wherein (depending on the requirements of the particular individual case) additional monomers that can be copolymerized with acrylic acid, acrylic acid esters, methacrylic acid esters and/or methacrylic acid are integrated or not integrated.

It is preferable that in the water-based hydrophobization agent described in step (c) of the procedure, which is carried out in accordance with the invention, modified polydimethylsiloxane is used in a weight ratio ranging from 1:20 to 20:1, preferably in the range from 1:10 to 10:1, and particularly preferably in the range from 7:1 to 1:7, in relation to the weight proportion of one or more cationic polymers.

It is primarily preferred that the water-based hydrophobizing agent described in step (c) of the process carried out in accordance with the invention contains modified polydimethylsiloxane in a total amount ranging 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, relative to the total weight of the water-based hydrophobizing agent water.

It is primarily preferred that the water-based hydrophobizing agent described in step (c) of the process carried out in accordance with the invention contains one or more cationic polymers whose total amount is in the range of 0.05 mass percent to 15 mass percent, particularly preferably in the range of 0.1 mass percent to 10 mass percent, and preferably in the range of 0.15 mass percent to 5 mass percent, relative to the total weight of the water-based hydrophobizing agent water.

Primarily modified polydimethylsiloxane, which can be used in step (c) of the process carried out in accordance with the invention, should contain one or more polydimethylsiloxane selected from the group consisting of polydimethylsiloxane with aminoalkyl groups, polydimethylsiloxane with amidoalkyl and aminoalkyl groups, polydimethylsiloxane with alkyln and aminoalkyln groups, polydimethylsiloxane with polyoxyalkylene groups and polydimethylsiloxane with alkyl and polyoxyalkylene groups. Examples of such modified polydimethylsiloxanes, which are also advantageously used in step (c) of the process carried out according to the invention, are specifically mentioned in patent document WO 2010/139466.

The modified polydimethylsiloxanes mentioned in the previous part of the text can be used individually or in combination with each other.

Cationic polymers that can be used in step (c) of the procedure carried out in accordance with the invention are primarily homopolymers or copolymers, which as components of the side chains of the corresponding monomers contain basic functional groups that are not charged, primarily primary, secondary or tertiary amino groups, which can form cationic groups by taking H+ ions. Examples of such cationic polymers which are preferably used in step (c) of the process carried out in accordance with the invention are specifically listed in patent document WO 2010/139466.

The cationic polymers mentioned in the previous part of the text can be used individually or in combination with each other.

In the context of this invention, the term "polysaccharide" includes modified and unmodified polysaccharides, primarily modified chitin and modified and unmodified chitosan, whereby there may be differences in molar masses, in terms of the degree of deacetylation and in terms of polysaccharide derivatives suitable for use in accordance with the invention, such as in a favorable embodiment chitosan derivatives. Chitosan derivatives that are used in the convenient method of carrying out the procedure according to the invention include chitosan succinate (N-succinylchitosan), chitosan propionate (N-propionyl-chitosan) and chitosan adipate (N-adipyl-chitosan).

Cationic polymers which are advantageously used in the process performed in accordance with the invention are biopolymers chitin and/or chitosan, as well as their derivatives, primarily chitosan and its derivatives. If in the biopolymer molecule there are more 2-amino-2-deoxy-ß-D-glucopyranose units obtained by deacetylation than by the acetylation process (> 50% of deacetylated units), it will, as indicated in this description, be called chitosan in accordance with the usual practices in this special technological field. If there are more acetylated than deacetylated 2-amino-2-deoxy-ß-D-glucopyranose units (<50% deacetylated units), that chemical compound will be referred to as chitin in this specification in accordance with common practice in this specialized art. The degree of resulting deacetylation to chitin or chitosan can be variable. In order to improve the solubility in aqueous solutions and/or reduce the viscosity, the chain length and/or degree of deacetylation of the polysaccharide (chitin or chitosan) can be changed. Due to the free amino groups created by deacetylation, chitosan is a polycation with a high charge density in acidic solution.

Primarily, in step (c) of the procedure performed according to the invention, chitosan with a degree of deacetylation >75% is used, it is particularly advantageous for the degree of deacetylation to be >85%, and in the ideal case it is particularly advantageous for the degree of deacetylation to be >90%. It is preferable that the molecular weight of the chitosan used in step (c) of the procedure carried out in accordance with the invention is in the range of 10,000 Daltons to 5,000,000 Daltons, particularly preferably in the range of 100,000 Daltons to 2,000,000 Daltons and preferably in the range of 150,000 Daltons to 1,000,000 Daltons. Examples of chitosan species that can be used or are primarily used in step (c) of the process, which is carried out in accordance with the invention, are specifically listed in the document WO 2010/139466.

Based on this, it is advantageous to carry out the procedure in accordance with the invention or procedures that are described in accordance with the invention in the previous and in the following part of the description, whereby

- modified polydimethylsiloxane represents modified polydimethylsiloxane

- in which one or each of several methyl groups is replaced by a substituent containing a basic functional group, each of which is preferably replaced by an aminoalkyl group or an amido-aminoalkyl group, and which preferably contains terminally placed methoxy groups;

and/or (primarily "and")

- whereby one or more cationic polymers are selected from the group they comprise

- polyacrylates that are functionalized with cationic groups or basic groups, primarily amino groups, whereby it is preferable that the functionalization is performed with appropriately substituted or functionalized esters of acrylic or methacrylic acid;

primarily styrene acrylate copolymers functionalized with basic groups, preferably amino groups;

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- polyurethanes functionalized with cationic groups or basic groups, primarily amino groups;

- polyesters that are functionalized by means of cationic groups or basic groups, primarily with amino groups;

- polypeptides containing one or more essential amino acids, primarily selected from the group consisting of lysine, arginine, histidine, citrulline and ornithine,

and

- chitosan, primarily with a degree of deacetylation that is greater than 75%;

whereby it is preferable that at least one of the cationic polymers, of which there may be more, is selected from the group they comprise

- polyacrylates, preferably styrene acrylate copolymers, which are functionalized by means of cationic groups or basic groups, primarily with basic groups, especially preferably with amino groups, and

- chitosan, primarily with a degree of deacetylation that is greater than 75%.

Within the description of this procedure, the substitution of, for example, a side chain of a molecule, with a functional group (which can be specified exactly in individual cases) is also called "functionalization". Accordingly, in this text the terms "substituted" and "functionalized" (where necessary, each of them is explained in more detail on a case-by-case basis) are used synonymously.

In the context of this invention, the terms "polyamides" and "polypeptides" (ie, a natural or synthetic polymer in which amino acids are joined by peptide bonds) are used synonymously, but may also be used in different meanings, depending on the objective context. The term "polypeptide" is usually used in connection with the corresponding natural polymers.

Examples of water-based, fluorine-free hydrophobizing agents that are preferably used in step (c) of the process according to the invention are specifically set forth in WO 2010/139466.

In the process carried out in accordance with the invention, the plasma treatment described in step (b) is

- low-pressure plasma treatment, preferably low-pressure plasma activation, or includes

- low-pressure plasma treatment, preferably low-pressure plasma activation, and at least one additional plasma treatment step.

As a rule, low-pressure plasma is created in high-frequency electromagnetic fields between two or more electrodes, under a pressure that is significantly lower than atmospheric pressure. Due to the large (mean) free path traversed by the excited particles created in this way, the plasma expansion can exceed the effective range of the high-frequency field and cover the entire volume of the plasma treatment chamber.

In an advantageous variant of carrying out the procedure in accordance with the invention mentioned in the previous part of the description, said at least one additional step of plasma processing primarily includes plasma cleaning, where it is particularly desirable that this plasma cleaning be

1

plasma cleaning of a textile surface produced or placed in accordance with the description of step (a) carried out prior to plasma activation of said textile surface. After plasma cleaning, low-pressure plasma treatment follows, preferably low-pressure plasma activation.

It is preferable that with regard to the procedure carried out in accordance with the invention or the procedures carried out in accordance with the invention described in the preceding or in the following part of the description, the low-pressure plasma treatment is carried out under a pressure ranging from 1 Pa (0.01 mbar) to 20 kPa (200 mbar), more preferably under a pressure in the range from 1 Pa (0.01 mbar) to 0.5 kPa (5 mbar), and in particular advantageously under pressure in the range of 10 Pa to 50 Pa (0.1 mbar to 0.5 mbar).

The tests that we carried out ourselves as part of the investigation of the invention found that during processing with low-pressure plasma in the favorable or especially favorable pressure ranges mentioned above, good or even perfect success is achieved in terms of the depth of penetration through the surface of the textile, where the depth of penetration is decisive for the long-term stability of the processing, and on the other hand, for a higher speed of the processing process, which is important for the economic application of the process. Higher gas pressure usually leads to faster plasma activation, but its long-term stability is limited. On the other hand, the use of a lower gas pressure (eg <10 Pa) usually results in a favorable penetration depth through the textile surface during low-pressure plasma treatment, but requires a longer treatment time. In the worst case, too high gas pressure can even lead to a significant reduction in the effectiveness of the treatment (reduction of the hydrophobic properties of the treated textile).

Therefore, it is advantageous to combine the pressure ranges listed in step (b) as favorable or particularly favorable for low-pressure plasma processing during the performance of the procedure in accordance with the invention, i.e. to primarily activate the low-pressure plasma with the pressure ranges listed below as favorable or particularly favorable ranges for performing the low-pressure plasma processing described in step (b).

It is primarily preferred that the low-pressure plasma treatment from (step (b)) of the method performed in accordance with the invention or the procedures performed in accordance with the invention described as favorable in the previous or in the following part of the text, is performed at a temperature ranging from 10 °C to 50 °C, preferably at a temperature from 15 °C to 40 °C. When a plasma treatment process, especially a low-pressure plasma treatment process or a low-pressure plasma activation process, is performed in a certain temperature range and under favorable conditions or particularly desirable conditions that are specified in the previous or in the following part of the description, it is usually referred to as a "low-pressure plasma treatment process". If step (b) of the process according to the invention, for example, is carried out at temperatures below the stated temperature range or favorable temperature range, for example, unwanted side reactions may occur more often. If step (b) of the process according to the invention is carried out at temperatures above the specified temperature range or favorable temperature range, it can be reduced as an undesirable side effect, for example, the rate of deposition of the constituents of the gas or mixture of gases from which the plasma is formed, which can significantly reduce the desired effect of the plasma treatment.

The low-pressure plasma treatment, which is preferably the low-pressure plasma activation, described in step (b) of the process according to the invention, is performed 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 in the form of intermediate reaction products (eg in the form of "precursors" of oxygen in the preliminary phase), and at least in the conditions in which activation is carried out with low-pressure plasma.

1

Therefore, the method according to the invention in which the low-pressure plasma treatment is performed using at least one compound containing oxygen, which is selected from the group consisting of O, O2, O3, NO, N2O and CO2, so that functional groups containing oxygen (preferably -OH, -CO, -CHO or -COOH) are preferably created on the surface of the textile, which are preferably bound to the surface of the textile by covalent bonds.

Determining whether such oxygen-containing functional groups have formed on the surface of the textile, or whether they have been covalently bonded to the surface of the textile, can be done using appropriate physical or physicochemical methods, for example Fourier Transform Infrared Spectroscopy (FTIR Spectroscopy) or X-ray Photoelectron Spectroscopy (XPS) for Electron Spectroscopic Chemical Analysis (ESCA).

Therefore, the process carried out in accordance with the invention is such that at least one compound contains oxygen

- present in the mixture, primarily in the mixture of gases, which contains O2 and at least one more inert gas that is selected from the group consisting of He and Ar, whereby in the mixture of gases O2 has a volume fraction that ranges from 70% by volume to 90% by volume, while the fraction of inert is in the range from 10% by volume to 30% by volume, whereby it is preferable that the mixture (primarily the aforementioned mixture of gases consisting of O2 and at least one inert gas selected from the group consisting of He and Ar) contains at least 99% by volume of O2 and at least one other inert gas selected from the group consisting of He and Ar,

and it is particularly desirable that it contains at least 99% by volume of O2 and Ar.

Low-pressure plasma treatment, primarily low-pressure plasma activation, which is primarily performed in step (b) of the process according to the invention using a gas or a mixture of gases which (before transition to the plasma state) does not contain more than 1% by volume of gaseous components, except the gas or gases containing oxygen. If the proportion of other ingredients in the mixture is kept at such a low level, it is particularly advantageous that unwanted reactions caused by other ingredients that would otherwise be present in the gas mixture can be largely avoided, or even completely prevented.

The method performed in accordance with the invention contains the above-mentioned mixture, primarily the specified mixture of gas or gases, which contains O2 and at least one inert gas selected from the group consisting of He and Ar (before transitioning to the plasma state), whereby the volume fraction of O2 is in the range of 70% volume to 90% volume, and the fraction of inert gas, primarily He and/or Ar, is in the range of 10% volume to 30% volume. During the tests we carried out ourselves as part of the invention test, it was determined that the mixture of gases of this advantageous composition gives very good, or even the best results, in terms of the preliminary plasma activation of the textile surface from the process performed in accordance with the invention, so that very good, or even the best results, are achieved in terms of the water-repellent properties of the hydrophobized textile surface treated with plasma in accordance with the process according to the invention, as well as the durability of those water-repellent properties that result in moisture repellence (see, for example, the results of Example 6, Table 3 or Example 7, Table 4, below).

Also advantageous is the procedure carried out in accordance with the invention or the procedures carried out in accordance with the invention described as advantageous in the previous or subsequent part of the text,

whereby

the textile surface of the product which is produced or placed in accordance with the description of step (a) contains one or more materials which are selected from the group consisting of

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- the first material, primarily a natural material, selected from the group consisting of cotton, wool, silk, cellulose and regenerated cellulose, as well as their mixtures; particularly advantageously selected from the group consisting of cellulose and regenerated cellulose, as well as their mixtures;

- another material, primarily a synthetic material, selected from the group consisting of polyester, polyamide, polyamide-imide, polypropylene, polyacrylonitrile and polyacrylic methacrylate, as well as mixtures of these materials; wherein it is particularly desirable to be selected from the group consisting of synthetic polymers, primarily biodegradable synthetic polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and their mixtures;

as well as

- mixtures thereof;

wherein it is preferable that the surface of the textile contains one or more materials, at least one of which is selected from the group they comprise

- another material, primarily a synthetic material, for which it is preferable to be selected from the group consisting of polyester, polyamide, polyamide-imide, polypropylene, polyacrylonitrile and polyacryl-methacrylate, as well as mixtures of these materials; it is particularly preferable that it is primarily selected from the group consisting of synthetic polymers, primarily biodegradable synthetic polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and their mixtures;

where the plasma treatment is described in step (b)

- low-pressure plasma treatment, which is primarily carried out through low-pressure plasma activation, whereby the low-pressure plasma treatment is performed using at least one compound containing oxygen, which is selected from the group consisting of O, O2, O3, NO, N2O and CO2, whereby at least one compound containing oxygen is present in the gas mixture, that is, it contains O2 and at least one inert gas selected from the group consisting of He and Ar, while the gas mixture O2 has a volume share that ranges from 70% volume to 90% volume, while the share of inert gas is in the range from 10% volume to 30% volume, so that functional groups that contain oxygen are primarily created on the surface of the textile, which are favorably bound to the surface of the textile by covalent bonds,

and

the hydrophobizing agent used in step (c) is a water-based hydrophobizing agent which

contains a modified polydimethylsiloxane, preferably a 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 containing additional and

one or more cationic polymers selected from the group consisting of

1

- polyacrylates, primarily selected from the group consisting of homopolymers and copolymers of acrylic acid, esters of acrylic acid, methacrylic acid, esters of methacrylic acid and optionally other monomers that copolymerize with acrylic acid, esters of acrylic acid, methacrylic acid and/or esters of methacrylic acid, primarily styrene;

- polyurethanes, primarily polyester-type and/or polycarbonate-type polyurethanes;

- polyester,

- polypeptides,

- polyamides

and

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

Particularly preferred is the process according to the invention or the process according to the invention which is described as desirable in the preceding or part of the text that follows,

whereby

textile surface of a product manufactured or equipped with a textile in accordance with the description in step (a) containing one or more materials selected from the group consisting of

- the first material selected from the group consisting of cellulose and regenerated cellulose and their mixtures;

- another material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures; wherein it is preferable that the second material is selected from the group of copolyesters, which consists of monomers of terephthalic acid and one or more alkanediols (primarily selected from the group consisting of ethylene glycol (ethanediol), 1,3-propanediol and 1,4-butanediol, and it is especially preferable that it be ethanediol)

and it also advantageously contains at least one additional monomer, different from the above-mentioned monomers (terephthalic acid or one or more alkanediols);

as well as

- mixtures thereof;

wherein the textile surface primarily contains one or more materials, at least one of which is selected from the group they comprise

- another material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and their mixtures; whereby it is primarily preferable that the second material be selected from the group of copolyesters, which consists of monomers of terephthalic acid and one or more alkanediols (primarily selected from the group consisting of ethylene glycol (ethanediol), 1,3-propanediol and 1,4-butanediol, and it is particularly advantageous for it to be ethanediol),

and it is also primarily preferred that it contains at least one additional monomer, different from the above-mentioned monomers (terephthalic acid or one or more alkanediols);

2

wherein the plasma treatment in step (b)

low-pressure plasma treatment, primarily low-pressure plasma activation, which is carried out in the presence of a gas mixture containing O2 and at least one other inert gas selected from the group consisting of He and Ar, whereby at least one compound containing oxygen is present in the gas mixture, represented by O2 and at least one other inert gas selected from the group consisting of He and Ar, with the volume fraction of O2 in the gas mixture ranging from 70% by volume to 90% by volume, while the proportion of inert is in the range from 10% by volume to 30% by volume, wherein it is preferable that the mixture contains at least 99% by volume of O2 and at least one inert gas that is selected from the group consisting of He and Ar, and it is particularly desirable that said mixture contains at least 99% by volume of O2 and Ar,

and

that the hydrophobizing agent used in step (c) is a water-based hydrophobizing agent which

contains modified polydimethylsiloxane, whereby it is primarily modified polydimethylsiloxane, in which one or more methyl groups are replaced by substituents with basic functional groups, alkyl groups and/or polyether groups;

and additionally contains

one or more cationic polymers selected from the group consisting of

- polyacrylates, primarily selected from the group consisting of homopolymers and copolymers of acrylic acid, esters of acrylic acid, methacrylic acid, esters of methacrylic acid and optionally other monomers that can be copolymerized with acrylic acid, esters of acrylic acid, methacrylic acid and/or esters of methacrylic acid, primarily styrene;

- polyurethanes, primarily polyester-type and/or polycarbonate-type polyurethanes; - polyester,

- polypeptides,

- polyamides

and

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

Also preferred is the process carried out in accordance with the invention or the process in accordance with the invention described as advantageous in the preceding or part of the text that follows, wherein in step (b)

- treatment with low-pressure plasma is performed for a duration of 10 seconds to 10 minutes, primarily for a duration of 30 seconds to 5 minutes, and particularly advantageous for a duration of 1 minute to 3 minutes;

and/or

- low-pressure plasma is created at a frequency ranging from 10 MHz to 18 MHz, primarily in the range from 11 MHz to 15 MHz,

and/or

- low-pressure plasma is created using electrodes, where it is desirable that the density of electrodes be in the range of 1 to 10 electrodes/m<2>, particularly advantageously in the range of 2 to 5 electrodes/m<2>, and in the ideal case it is particularly favorable that this density be in the range of 2.5 to 4 electrodes/m<2>, in relation to the surface of the textile that was produced or placed in step (a);

and/or

- that the low-pressure plasma treatment is performed using a plasma production system operating at a power in the range from 0.05 kW to 100 kW, primarily in the range from 1 kW to 25 kW, particularly preferably in the range from 2 kW to 15 kW, and in the perfect case particularly advantageously in the range from 5 kW to 10 kW,

and/or

- that low-pressure plasma processing is performed in a plasma processing chamber at a power ranging from 0.25 kW/m<3> to 2.0 kW/m<3>, primarily in the range from 0.5 kW/m<3> to 1.5 kW/m<3>.

The low-pressure plasma treatment parameters from step (b) of the procedures performed in accordance with the invention, which are indicated in the previous part of the text as favorable or particularly favorable, can be combined in a favorable performance of the procedure, and by combining them, particularly favorable conditions for the performance of step (b) can be obtained.

Variants of the procedure performed in accordance with the invention are particularly favorable, in which in step (b) low-pressure plasma treatment is performed, primarily low-pressure plasma activation, at a pressure ranging from 1 Pa (0.01 mbar) to 0.5 kPa (5 mbar), with the duration of the treatment being in the range from 30 seconds to 5 minutes. In addition, variants of the procedure carried out in accordance with the invention are particularly favorable, in which in step (b) processing with low-pressure plasma is carried out, primarily activation with low-pressure plasma, at a pressure ranging from 10 Pa to 50 Pa (0.1 mbar to 0.5 mbar), where the duration of the treatment is in the range of 1 minute to 3 minutes.

As already stated in the previous part of the description, under these favorable conditions of the pressure range and duration of processing, the best effect of the procedure performed in accordance with the invention is achieved, as well as the best compromise regarding the penetration of low-pressure plasma through the surface of the textile, the longevity of the achieved activation and the subsequent hydrophobic properties of the textile surface, as well as the economy of the application of the procedure.

If in step (b) of the procedure performed in accordance with the invention, the low-pressure plasma is created using electrodes, it is preferable that the density of these electrodes be within the range specified in the previous part of the text, in order to achieve a particularly efficient and uniform (homogeneous) activation and subsequent hydrophobization of the textile surface.

If, in step (b) of the procedure performed according to the invention, the low-pressure plasma treatment is performed in a plasma treatment chamber with an output power that is in the range specified in the previous part of the text or with a plasma generating device whose output power is in the range specified in the previous part of the text, particularly good results are achieved in terms of the activation of the textile surface or its subsequent hydrophobization, as well as in terms of the achieved longevity of these treatments.

It has been shown that the results regarding the preliminary plasma activation of the textile surface performed by the method according to the invention, and therefore the results regarding the water-repellent properties of the plasma-treated textile surfaces, as well as the durability of those water-repellent properties, are particularly good, or even the best, when the method according to the invention (in step (b)) is performed as a low-pressure plasma treatment with a plasma generating device operating at a power ranging from the range specified in the previous part of the text, or in the favorable range specified in the previous part of the text. For example, if the power of the source of plasma generation is lower than the values mentioned in the previous part of the text, perhaps the degree of activation of the textile surface by plasma will not be sufficient, which will eventually lead to an unsatisfactory degree of hydrophobic properties of the treated textile surface and/or an unsatisfactory degree of durability of those hydrophobic properties. On the other hand, if the power of the plasma generating device is higher than the values mentioned in the previous part of the text, the treated textile surface may even be damaged.

Also advantageous is the process carried out in accordance with the invention or the process in accordance with the invention described as advantageous in the previous or part of the text that follows, where the wet chemical treatment described in step (c) includes one, or more processes, or all of the following processing processes:

- impregnation of the textile surface resulting from the plasma treatment from step (b) or the textile surface produced from it in further steps, primarily impregnation by complete immersion in a bath, especially advantageously using coatings,

- drying of the absorbed agent for hydrophobization on the textile surface,

- fixing the absorbed hydrophobizing agent on the surface of the textile,

wherein it is preferable that the wet chemical treatment includes impregnation by complete immersion in a bath, whereby it is particularly advantageous that the impregnation of the surface of the textile resulting from the plasma treatment from step (b) or the textile surface produced from it in further steps is carried out by complete immersion in the bath using a coating,

wherein it is advantageous that the drying and/or solidification of the absorbed hydrophobization agent takes place on the surface of the textile.

In the context of the present invention, the impregnation during the wet chemical treatment described in the work step (c) of the process carried out in accordance with the invention, mentioned in the previous part of the text, can be carried out by any process suitable for that purpose, for example by spraying, dipping, impregnation under pressure, tapping (the so-called "kiss-and-roll" impregnation), impregnation by washing with an impregnating detergent, for example, in a washing machine, impregnation by complete immersion in bath (preferably) or a combination of several methods mentioned above.

In accordance with the invention, it is advantageous that the impregnation is carried out by complete immersion in a bath, and particularly advantageously by means of coatings, and it is advantageous that the wet chemical treatment is a water-based wet chemical treatment. In this way, the plasma-treated and hydrophobized surface of the textile obtained in step (c) of the procedure carried out in accordance with the invention is most effectively brought into contact with the hydrophobization agent and a particularly completely and permanently hydrophobized surface of the textile is obtained.

Also favorable is the procedure performed in accordance with the invention, or the procedure described as favorable in the previous or subsequent part of the text, in which the wet chemical treatment from step (c)

2

- water-based wet chemical treatment (as explained in the previous part of the text), which includes impregnation (as explained in the previous part of the text), primarily impregnation by complete immersion in a bath, particularly advantageously by means of coatings, the textile surface pre-treated with plasma obtained as a result of the treatment from step (b) or the textile surface produced from it in further steps, wherein the water-based hydrophobizing agent contains modified polydimethylsiloxane, wherein the modified polydimethylsiloxane present in a concentration of 200 g/L to 400 g/L, preferably in a concentration of 250 g/L to 350 g/L, reduced to the total amounts of liquid used during the wet chemical processing described in step (c).

If the wet chemical treatment described above is with a modified polydimethylsiloxane (as described in the preceding part of the description, or with such a modified polydimethylsiloxane described as advantageous) at a concentration of 200 g/L to 400 g/L, preferably at a concentration of 250 g/L to 350 g/L, based on the total amount of liquid used during the wet chemical treatment described in step (c) (especially at the textile surface described in the previous part of the text, located on the product described in step (a) which is produced or equipped with that textile surface, wherein it contains one or more materials, which are selected from the group consisting of the first material selected from the group consisting of cellulose and regenerated cellulose and their mixtures), the best results are obtained in terms of the water-repellent properties achieved by the impregnation of the fabric, as well as in terms of the durability of that impregnation, this being achieved by carrying out the process in according to the invention in such a way as it is described in the procedure. For example, concentrations of modified polydimethylsiloxane, which are lower than those mentioned in the previous part of the text, can result in unsatisfactory hydrophobic properties of the treated textile surface. Conversely, concentrations of modified polydimethylsiloxane, which are higher than those mentioned in the previous part of the text, can even lead to reduced durability of the hydrophobic properties of the treated textile surface.

Particularly preferred is a procedure performed in accordance with the invention or a procedure performed in accordance with the invention that is described as favorable in the previous or in the following part of the text, during which the wet chemical treatment from step (c) is a water-based wet chemical treatment of the plasma-treated textile surface resulting from the treatment in step (b) or the textile surface produced from it in further steps, impregnation by complete immersion in a bath, preferably by means of coatings, wherein the impregnation by complete immersion in the bath, primarily carried out with the help of poultices,

- under pressure in the range of 100 kPa to 500 kPa, primarily in the range of 200 kPa to 400 kPa

and/or

- at the speed of passage of the textile surface (along the lengthwise measure of the textile surface) through the bath used for impregnation, whereby the speed is in the range of 0.5 m/min to 5 m/min, and primarily the speed is in the range of 1 m/min to 3 m/min,

and/or (primarily "and")

- at a temperature that is in the range of 15 °C to 35 °C, and primarily the temperature is in the range of 18 °C to 25 °C.

Also advantageous is the procedure carried out in accordance with the invention or the procedure carried out in accordance with the invention which is described as advantageous in the previous or in the following part of the text, during which the wet chemical treatment from step (c) includes the wet chemical treatment of the textile surface on a water basis, as well as the drying of the absorbed agent for hydrophobization on the surface of the textile, whereby the drying is carried out

- at a temperature ranging from 100 °C to 140 °C, primarily at a temperature ranging from 110 °C to 130 °C,

and/or (preferably "and")

- for a duration of 30 seconds to 5 minutes, primarily for a duration of 1 minute to 4 minutes, and/or (primarily "and")

- in the tension frame of the tenter dryer.

Also preferred is a procedure performed in accordance with the invention or a procedure performed in accordance with the invention that is described as advantageous in the previous or subsequent part of the text, during which the wet chemical treatment from step (c) includes the wet chemical treatment of the surface of the textile on a water basis, as well as the fixing of the absorbed agent for hydrophobization on the surface of the textile, whereby the fixing is carried out

- at a temperature in the range from 120 °C to 190 °C, primarily at a temperature in the range from 140 °C to 180 °C, and especially preferably in the range from 150 °C to 170 °C,

and/or (primarily "and")

- lasting in the interval from 20 seconds to 4 minutes, preferably in the interval from 30 seconds to 3 minutes, and especially preferably in the interval from 1 minute to 3 minutes, and/or (primarily "and")

- in the tension frame of the tenter dryer.

It is desirable that parts of the procedure within the wet chemical treatment from step (c) of the procedure performed in accordance with the invention, which are listed in the previous part of the text, or parts of the procedure indicated as (especially) favorable, including drying and hardening, are combined with each other, which results in particularly desirable variants of the procedure according to the invention that are particularly effective and/or make textile surfaces permanently hydrophobic. Such, especially permanently hydrophobized textile surfaces retain their useful, especially water-repellent or water-resistant properties, for a very long time and are particularly resistant to mechanical stresses, for example due to abrasion or washing or drying processes.

This proposed invention also relates to a textile product containing a hydrophobized textile surface, which can be produced by carrying out the process according to the invention, and which is primarily produced by the process according to the invention, which is described in the previous part of the text as favorable.

Primarily, the textile product according to the invention is selected from the group consisting of clothing for protection against external weather conditions; clothing intended for outdoor wear, functional clothing; work clothes which, if possible, are intended for outdoor wear; raincoats; poncho robes; tarpaulins for motor vehicles or metal structures; awnings; canopy; umbrella; parasol; materials for making tents; textile articles for carrying tents and transport, preferably suitcases, carrier bags, sports bags, backpacks and packing baskets.

2

As regards the design of the textile articles which are desirable according to the invention, the previously given explanations regarding the process carried out in accordance with the invention apply also with respect to the textile articles, and vice versa.

This proposed invention also relates to the use of a low-pressure plasma treatment procedure for the purpose of preliminary treatment of the textile surface of the object, before its wet chemical hydrophobization, wherein the low-pressure plasma treatment is performed using at least one oxygen-containing compound selected from the group consisting of O, O2, O3, NO, N2O and CO2, wherein at least one oxygen-containing compound is present in the gas mixture containing O2 and at least one inert gas selected from the group consisting of He and Ar. where in the mixture of gases O2 has a share ranging from 70% volume to 90% volume, while the share of inert is in the range from 10% volume to 30% volume.

With regard to advantageous examples of the design of the product performed in accordance with the invention, the previously given explanations regarding the process performed according to the invention and/or the explanations regarding the textile products according to the invention also apply with respect to the design, and vice versa.

Preference is given to performing the procedure in accordance with the invention of processing with low-pressure plasma or performing procedures in accordance with the invention that are described in the previous or subsequent part of the text as favorable for the preparatory treatment of the textile surface of the object,

wherein said textile surface contains one or more materials selected from the group they comprise

- the first material selected from the group consisting of cellulose and regenerated cellulose, as well as their mixtures;

- another material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures; wherein it is preferable that the second material is selected from the group of copolyesters consisting of terephthalic acid monomers and one or more alkanediols (primarily selected from the group consisting of ethylene glycol (ethanediol), 1,3-propanediol and 1,4-butanediol, and it is particularly advantageous for it to be ethanediol)

and which primarily contain at least one additional monomer different from the aforementioned monomers (terephthalic acid or one or more alkanediols);

as well as

- mixtures thereof;

wherein the textile surface primarily contains one or more materials, at least one of which is selected from the group they comprise

- another material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures; wherein it is advantageous for the second material to be selected from the group of copolyesters consisting of terephthalic acid monomers and one or more alkanediols (primarily selected from the group consisting of ethylene glycol (ethanediol), 1,3-propanediol and 1,4-butanediol, and it is particularly advantageous for it to be ethanediol)

and which primarily contain at least one additional monomer different from the aforementioned monomers (terephthalic acid or one or more alkanediols);

before wet chemical hydrophobization of the textile surface.

Examples:

2

The following examples are intended to describe and explain the invention in more detail, without limiting the scope of its application and the area protected by it.

Example 1: Preparation of objects with a textile surface

In each of the examples given below, a fabric (prepared fabric) was used as a product with a textile surface, consisting of 100% single strands of a biodegradable synthetic polymer (a copolyester containing terephthalic acid and ethylene glycol as monomers, as well as at least one additional monomer). The weight per unit area of the fabric was approximately 150 g/m2 and the weave density was approximately 100 warp threads/cm and approximately 50 weft threads/cm.

In this way, the fabric marked "G-tO" was prepared.

Similar convincing results that are listed below, especially with regard to the improvement of the water-repellent properties that can be achieved by performing the procedure in accordance with the invention, are also achieved when using other textile surfaces, for example when using one of the textile surfaces for which it is stated in the previous part of the text that they can be used in accordance with the invention, or for which it is stated that their use is advantageous. Examples include lyocell (cellulose) based fabric (such as Tencel®) or laminated polyester.

Example 2: Treatment of a textile surface with plasma

2.1 Plasma treatment using a gas mixture

A fabric sample prepared as described in the previous part of the text (see "Example 1") was subjected to low-pressure plasma activation in the plasma processing chamber of the industrial vacuum plasma reactor Nano-plasmacoater BAG (volume approximately 11 m<3>) using a larger number of electrodes (electrode density was about 3.5 electrodes/m<2> fabric), with the following parameters set:

Frequency: 13.56 MHz

Processing time: 2 min.

Power (plasma source): 9 kW

Pressure: 0.3 mbar (30 Pa)

Process gas: O2 (molecular oxygen)

Inert gas: Ar (argon)

Process gas/inert gas ratio: 20% by volume Ar / 80% by volume O2

The cloth treated with plasma in this way was given the designation "G-tO-pbh (Ar/O2)".

2.2 Plasma treatment using an inert gas (not in accordance with the invention)

Another fabric sample prepared according to the description in the previous part of the text (see "Example 1)" was subjected to the same low-pressure plasma activation, in the manner described in the previous part of the text under point 2.1, but only inert gas argon was used for processing, and not the process gas molecular oxygen (100% of the gas volume was argon).

The cloth treated with plasma in this way was given the designation "G-tO-pbh (Ar)".

2.3 Plasma treatment using a process gas (not in accordance with the invention)

2

Another fabric sample described in the previous part of the text (see "Example 1") was subjected to the same low-pressure plasma activation, in the manner described in the previous part of the text under point 2.1, but only with the process gas of molecular oxygen, and not with the inert gas of argon (100% of the gas volume was O2).

The cloth treated with plasma in this way was given the designation "G-tO-pbh (O2)".

Example 3: Production of hydrophobization agents

In a way that is already known in the state of the art, water-based hydrophobization agents were produced whose compositions (see Table 1) are listed in the following part of the text (hereinafter also listed as the abbreviation "HPM"), and which can be used in the process carried out in accordance with the invention (step (c)) and contain modified polydimethylsiloxane (hereinafter also listed as the abbreviation "PDMS").

Chitosan with a degree of deacetylation of 95% and a molar mass of 300,000 to 500,000 g/mol (Da) was used as chitosan.

As an amino-functionalized (styrene)-acrylate copolymer, a dispersion was used that contained an emulsifier (approximately 35% by weight of the active content) of an acrylate-styrene copolymer with a 25-45% share of functional amino group monomers and a molecular weight between 300,000 and 500,000 g/mol (Da).

T l 1 i r z hi r f iz i

Example 4: Wet chemical treatment of textile surface

4.1 Wet chemical treatment of the textile surface treated with plasma (in accordance with the invention)

The fabric "G-tO-pbh (Ar / O2)" which was treated by plasma and produced in the manner indicated in the previous part of the text (see Example 2.1) and which is known per se in the existing state of the art, was impregnated with a hydrophobizing agent HPM3 (in concentration: 300 g/L), prepared in the way indicated in the previous part of the text (see Example 3) in a fuller machine (a machine used for dyeing, impregnation etc. respectively for

2

even application of liquid on wide webs of fabric), while processing was carried out in accordance with the following parameters:

Pressure: 300 kPa (3 bar) Temperature: 21 ° C

Textile processing speed: 2 m/min

The fabric processed by the wet chemical process (impregnated fabric) was then dried for 2 minutes at a temperature of 120 °C in a stenter dryer in a tension frame.

To fix, the dried fabric was then centrifuged at 180 °C for an additional 1 minute.

A fabric thus hydrophobized by plasma treatment corresponds to a product with a hydrophobized textile surface produced in accordance with the invention, and is designated as "G-tO-pbh (Ar/O2)-hydr".

Plasma-treated "G-tO-pbh (Ar)" and "G-tO-pbh (O2)" fabrics produced in the manner indicated in the previous section of the text (see Reference Examples 2.2 and 2.3) were also impregnated, dried and fixed in the same manner as previously indicated. Fabrics thus hydrophobized by plasma treatment corresponded in each case to products with a hydrophobized textile surface produced in accordance with the invention, and received the respective names "G-tO-pbh (Ar)-hydr" and "G-tO-pbh (O2)-hydr".

4.2 Wet chemical treatment of non-plasma treated textile surface (comparison)

The "G-tO" fabric, which was not pre-treated with plasma, as mentioned in the previous part of the text (see Example 1), was impregnated in a fullar machine in the same way as described in Example 4.1, using the hydrophobizing agent HPM3 which was prepared in the way mentioned in the previous part of the text, and then it was dried and fixed in the same way.

The fabric produced in this way and hydrophobized without prior plasma treatment was designated "G-tO-hydr" and was used as a comparative fabric not produced in accordance with the invention.

Example 5: Determination of the contact angle

The contact angle θ of a liquid surrounded by a gas with a solid surface denotes the angle that the imaginary boundary lines of the gas, liquid and solid phases overlap. The size of the contact angle between a liquid and a solid depends on the interaction of the substances on the contact surface. The smaller the interaction, the larger the contact angle. By determining the contact angle, certain properties of the solid surface can be determined, e.g. its surface energy. In the special case of using water as a liquid, the surface will be called hydrophilic if the contact angles are small (approximately 0°), hydrophobic if the contact angles are around 90° and superhydrophobic if the contact angles are even larger. Superhydrophobic surfaces are also known as surfaces that show the "lotus effect", the liquid has very large contact angles with them (approximately 160°), and they absorb water extremely poorly. The contact angle can be changed by surface treatment. The contact angle θ can be measured with a contact angle goniometer.

The contact angles of glycerin (98%) and water with fabrics "G-tO" or "G-tO-pbh (Ar/O2)" which were obtained or produced in accordance with the procedure mentioned in the previous part of the text, and which were used as test samples (tensioned fabrics), were determined in accordance with the standard DIN 55660-2: 2011-12 (static method). The contact angle is determined for 5 seconds

2

after applying the sample liquid to the tensioned surface of the fabric. The results of this experiment with glycerin as the test liquid are listed in the following Table 2:

T l 2 K n k ni li rin by the width of the fabric

From the values given in Table 2, it can be seen that in the case where glycerin (98%) was used as the sample liquid, the surface of the G-tO-pbh (Ar/O2) fabric turned out to be significantly more hydrophilic due to the low-pressure plasma treatment (lower value of the contact angle θ) than the untreated surface of the G-tO fabric used for comparison.

From this result, it can be concluded that the treatment of the textile surface with low-pressure plasma led to a better ability to absorb moisture, which is favorable for the subsequent wet chemical treatment.

The effects of low-pressure plasma treatment on textile surfaces (better ability to absorb moisture) can be particularly well demonstrated using glycerin as a test liquid due to its relatively high viscosity.

Example 6: Determination of hydrophobization durability (splash test)

The durability of the hydrophobization (moisture repellency) achieved by the method according to the invention of the textile surface was determined and compared with the durability of the textile surface not produced according to the invention.

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

In order to test the durability of the hydrophobic properties of the fabric, a water spray test was carried out according to the AATCC TM22-2014 standard on fabrics G-tO-pbh (Ar/O2)-hydr (produced in accordance with the invention), G-tO-pbh (Ar)-hydr (not produced in accordance with the invention), G-tO-pbh (O2)-hydr (not produced in accordance with the invention) and G-tO-hydr (for comparison).

This spray test is used to determine the water repellency of textile surfaces with or without a finish. During the test, the stretched textile surface is moistened with water under controlled conditions, which creates a wet pattern on the textile surface, the spread of which depends on the relative water repellency of the textile surface being tested. The evaluation of the test results given in terms of the degree of "moisture rejection" is done by comparing the resulting moisture sample with the corresponding reference standard samples on a scale from 0 ("complete wetting of all upper and lower surfaces") to 100 ("no sticking or any wetting except that on the upper surface").

The results of this experiment are listed below, in Table 3, first for the respective fabrics after their acquisition or manufacture (see column A: "Initial", i.e. without pretreatment by washing and drying) and secondly for the same fabrics, but after five washing and drying cycles (see column B: "After 5 W/T cycles"). The washing and drying cycles were carried out in accordance with the ISO 6330:2000 (E) standard (type A/front-loading washing machine; Washing program 5A "Normal" at 40 ± 3 °C; standard phosphate-free detergent, ballast: 2 kg; tumble drying at 65 °C, 30 minutes).

Example 6b: Durability of hydrophobization in relation to abrasion

In order to test the durability of the hydrophobic properties of the fabric in relation to abrasion, a water spray test was carried out in the same way as stated in the previous part of the text (see Example 6a), according to the AATCC standard TM22-2014, on the fabrics G-tO-pbh (Ar/O2)-hydr (produced according to the invention) and G-tO-hydr (for comparison), after the abrasion test was carried out on the same two fabrics in accordance with the ASTM standard D4966-98 (2004) ("Martindale" abrasion test method; conditions: abrasive: wool; applied pressure (weight) of abrasive: 12 kPa; number of abrasion cycles: 2000). The results of this test were evaluated in the manner indicated in the previous part of the text (see Example 6a) and are listed below in Table 3 (see column "C: Degree of moisture rejection after abrasion test (Martindale)").

T l R z l i r k n m n k ilnim r in m

From the values listed in Table 3, it can be seen that the plasma-treated hydrophobized (impregnated) textile surface of the product produced using the method performed in accordance with the invention repels moisture better after production (i.e. it is proportionally more hydrophobic) than the textile surface produced according to the same process, but not previously treated with plasma, which was impregnated only by wet chemical treatment (see column "A").

Also, from the values listed in Table 3, it can be seen that the difference in the moisture repellency properties becomes even greater if the corresponding values are compared after five washing and drying cycles (i.e. after mechanical, chemical and thermal effects on the fabric): while the moisture repellency properties of the textile surface of the product with a hydrophobized textile surface produced by the process according to the invention are almost unchanged (the best result for the product G-tO-pbh (Ar/O2)-hydr; reference standard sample 90 instead 100), the moisture repellency properties of the textile surface used for comparison (G-tO-hydr) significantly deteriorated after previous exposures to the fabric (see column "B").

Also, from the values listed in Table 3, it can be seen that the plasma-treated hydrophobized (impregnated) textile surface of the object (G-tO-pbh (Ar/O2)-hydr) produced using the process performed in accordance with the invention has a better abrasion resistance than the textile surface (G-tO-hydr) produced according to the same process, but not previously treated with plasma, which was impregnated only by wet chemical treatment (see column "C").

From this result it can be concluded that the (impregnated) textile surface produced by the process according to the invention has a better, more permanent and more resistant hydrophobic (ie here:

1

water-repellent or water-resistant) properties from a textile surface produced (impregnated) in accordance with procedures known from the current state of the art.

Example 7: Determination of degree of hydrophobicity (water column)

The degree of water resistance of a product with a hydrophobized textile surface produced by a process according to the invention was determined and compared with the degree of water resistance of a product produced (impregnated) in accordance with a process known from the current state of the art.

For this purpose, the fabrics mentioned in the previous part of the text, G-tO-pbh (Ar/O2)-hydr, (produced in accordance with the invention) G-tO-pbh (Ar)-hydr (not produced in accordance with the invention) and G-tO-pbh (O2)-hydr (not produced in accordance with the invention) and G-tO-hydr (used for comparison), were subjected to a test to determine the resistance to water penetration according to the standard ISO 811: 1981-10 / DIN EN 20811: 1992-08 (height of the water column above the textile surface, i.e. the column above/facing the plasma-treated textile surface, i.e. above/facing the plasma-treated textile surface or above/facing the plasma-treated surface that has been hydrophobized) ("hydrostatic pressure test"). According to this test, water resistance is stated as the resistance of the textile surface to the water column. The height of that water column in centimeters, 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 testing are listed below in Table 4, first for the respective fabrics after their acquisition or manufacture (see column A: "Initial", i.e. without washing and drying pre-treatment), and then for the same fabrics, but after five washing and drying cycles (see column B: "After 5 W/T cycles"). The washing and drying cycles are carried out in accordance with the ISO 6330: 2000 (E) standard (washing machine type A/with front loading; Washing program 5A "Normal" at 40 ± 3 °C; standard phosphate-free detergent, ballast: 2 kg; tumble drying at 65 °C, 30 minutes):

T l 4 R z l i i i i n k ilnih rin hi r i kim rii k m

The values in Table 4 listed in parentheses (column A) were obtained in a separate series of measurements. The values in Table 4 not listed in parentheses (column A) were also obtained in a subsequent separate series of measurements.

From the values given in table 4, it can be seen that the plasma-treated hydrophobized (impregnated) textile surfaces of objects with a hydrophobized textile surface produced by the process according to the invention already had a significantly higher water resistance (i.e. they were comparatively more hydrophobic) than that after the same process with only a wet chemically impregnated textile surface, but without prior plasma treatment. The best result was achieved with the article G-tO-pbh (Ar / O2)-hydr (see column A).

2

Claims (15)

Also, from the values listed in Table 4, it can be seen that the difference in water resistance becomes even greater in favor of the preferred embodiments if the corresponding values are compared after five washing and drying cycles (i.e. after mechanical, chemical and thermal action on the fabric): while the water resistance properties of the textile surface of the product with a hydrophobized textile surface produced by the process according to the invention (low-pressure plasma treatment with at least one oxygen-containing compound) changed relatively little, the resistance properties on water of the textile surface used for comparison (G-tO-hydr) was significantly worsened by the previous stress (see column B). The best value for remaining water resistance after five washing and drying cycles was obtained for the product G-tO-pbh (Ar/O2)-hydr. Patent claims 1. The procedure for the production of textile items with a hydrophobic textile surface, which includes the following steps: (a) the production of objects with a textile surface or the placement of a textile surface on an object, (b) plasma treatment of the textile surface produced or placed on the object in step (a), so as to obtain the plasma treated textile surface, (c) Wet chemical treatment of the plasma treated textile surface obtained as a result of step (b) or the textile surface produced therefrom by means of a hydrophobizing agent, so as to obtain as a result of the process a plasma treated hydrophobic textile surface, the plasma treatment specified in step (b) - processing with low-pressure plasma or - low-pressure plasma treatment and at least one further step of plasma treatment wherein the low-pressure plasma treatment is performed using at least one oxygen-containing compound selected from the group consisting of O, O2, O3, NO, N2O and CO2 wherein at least one compound containing O2 and at least one inert gas selected from the group consisting of He and Ar are present in the gas mixture, where in the mixture of gases O2 has a share ranging from 70% volume to 90% volume, while the share of inert is in the range from 10% volume to 30% volume. 2. A method according to any of the preceding claims, wherein the textile surface of the object which is produced or on which the textile surface is placed in step (a) comprises one or more materials selected from the group consisting of - the first material, primarily a natural material, for which it is advantageous to be selected from the group consisting of cotton, wool, silk, cellulose and regenerated cellulose, as well as their mixtures; it is particularly advantageous for that material to be selected from the group consisting of cellulose and regenerated cellulose, as well as their mixtures; - another material, primarily a synthetic material, for which it is preferable to be selected from the group consisting of polyester, polyamide, polyamide-imide, polypropylene, polyacrylonitrile and polyacryl-methacrylate, as well as their mixtures, whereby it is particularly desirable that this material be selected from the group of synthetic polymers, primarily biodegradable synthetic polymers, which consists of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures; as well as - mixtures of these materials. 3. The method according to any of the previous requirements, primarily according to claim 2, wherein the textile surface of the object that is produced or on which the textile surface is placed in step (a) contains one or more materials that are selected from the group consisting of: - the first material, selected from the group consisting of cellulose and regenerated cellulose, as well as their mixtures; - another material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures; as well as - mixtures of these materials; whereby the textile surface primarily contains one or more materials, at least one of which is selected from the group they comprise - another material, selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures. 4. A method according to any one of the preceding claims, wherein the textile surface of the article which is produced or on which the textile surface is placed in step (a) is - selected from the group consisting of woven, knitted, knitted, twisted, stitched, felted or textile composite materials, non-woven textiles, textile hoses, ropes, fibers, threads, yarns, trenches and their mixtures, whereby it is primarily selected from the group consisting of woven, knitted, knitted materials, textile composite materials, non-woven textile materials, as well as mixtures of these materials; and/or contains fabric, knitted fabric, knitted fabric, braid, stitched fabric, felted fabric, non-woven materials and/or textile tubes, preferably fabric and/or knitted fabric, wherein it is particularly advantageous to contain fabric, which - has a weight per unit area in the range of 20 g/m<2> to 500 g/m<2>, primarily in the range of 100 g/m<2> to 200 g/m<2> and/or - has a thread density ranging from 80 to 120 threads/cm warp, and 40 to 80 threads/cm weft. 5. A method according to any of the preceding claims, preferably according to claim 3, wherein the hydrophobizing agent used in step (c) 4 - a water-based hydrophobization agent that primarily contains modified polydimethylsiloxane and/or - does not contain organic compounds containing fluorine and/or wherein the hydrophobizing agent is a water-based hydrophobizing agent that it contains - 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 - one or more cationic polymers selected from the group they comprise - polyacrylates, primarily selected from the group consisting of homopolymers and copolymers of acrylic acid, esters of acrylic acid, methacrylic acid, esters of methacrylic acid, and optionally also other monomers that can be copolymerized with acrylic acid, esters of acrylic acid, methacrylic acid and/or esters of methacrylic acid, and primarily styrene; - polyurethanes, primarily polyester-type and/or polycarbonate-type polyurethanes; - polyester, - polypeptides, - polyamides and - Polysaccharides, which are preferably selected from the group consisting of chitin and chitosan, and/or wherein the hydrophobizing agent is a water-based hydrophobizing agent containing modified polydimethylsiloxane, wherein - it is a modified polydimethylsiloxane in which they are - one or more methyl groups replaced by a substituent containing a basic functional group, wherein each of these substituted methyl groups is preferably replaced by an aminoalkyl group or an amido-aminoalkyl group and which primarily contains terminally placed methoxy groups; and or - whereby one or more additionally contained cationic polymers are selected from the group they comprise - polyacrylates that are functionalized with cationic groups or basic groups, primarily amino groups, where it is primarily styrene acrylate-copolymer functionalized with basic groups, primarily amino groups; - polyurethanes functionalized with cationic groups or basic groups, primarily amino groups; - polyesters that are functionalized by means of cationic groups or basic groups, primarily with amino groups; - polypeptides containing one or more essential amino acids, primarily selected from the group consisting of lysine, arginine, histidine, citrulline and ornithine, and - chitosan, primarily with a degree of deacetylation that is greater than 75%; whereby it is preferable that at least one of the cationic polymers - of which there may be more - is selected from the group they comprise - polyacrylates, preferably styrene acrylate copolymers, which are functionalized by means of cationic groups or basic groups, primarily by means of basic groups, and it is particularly desirable that they be functionalized by amino groups, and - chitosan, primarily with a degree of deacetylation that is greater than 75%. 6. A method according to any one of the preceding claims, wherein the plasma treatment in step (b) - implies activation with low-pressure plasma or - involves activation with low-pressure plasma and at least one additional further step of plasma processing and/or the low-pressure plasma treatment is carried out under a pressure in the range of 1 Pa to 20 kPa, whereby it is advantageous for the pressure to be in the range of 1 Pa to 0.5 kPa, and particularly preferably in the range of 10 Pa to 50 Pa. 7. The method according to claim 6, wherein the low-pressure plasma treatment is performed using at least one oxygen-containing compound, which is selected from the group consisting of O, O2, O3, NO, N2O and CO2, in order to create functional groups on the textile surface that contain oxygen and which will primarily be bound by covalent bonds to the surface of the textile. 8. The method according to claim 7, wherein the at least one compound is an oxygen-containing compound - present in the gas mixture containing O2 and at least one other inert gas selected from the group consisting of He and Ar, wherein said mixture of gases containing O2 and at least one other inert gas selected from the group consisting of He and Ar contains at least 99% by volume of O2 and at least one inert gas selected from the group consisting of He and Ar, wherein it is particularly advantageous for the mixture to contain at least 99% by volume of O2 and Ar, wherein it is preferable that in the mixture of gases O2 has a proportion ranging from 70% by volume to 90% by volume and a proportion of He and/or Ar in the range of 10% by volume to 30% by volume. 9. Procedure in accordance with any of the previous requirements, whereby the textile surface of the article which is manufactured or placed on that textile surface in step (a) contains one or more materials which are selected from the group consisting of - the first material, for which it is preferable to be selected from the group consisting of cotton, wool, silk, cellulose and regenerated cellulose, as well as their mixtures, where it is particularly desirable that this material is selected from the group consisting of cellulose and regenerated cellulose, as well as their mixtures; - another material, for which it is preferable to be selected from the group consisting of polyester, polyamide, polyamide-imide, polypropylene, polyacrylonitrile and polyacrylmethacrylate, as well as their mixtures, whereby it is particularly preferable that this material is selected from the group of synthetic polymers, preferably biodegradable synthetic polymers, which consists of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixture; as well as - mixture of dry materials; wherein the plasma treatment in step (b) - low-pressure plasma treatment, primarily low-pressure plasma activation, whereby this low-pressure plasma treatment is carried out using at least one oxygen-containing compound selected from the group consisting of O, O2, O3, NO, N2O and CO2, in order to create functional groups on the textile surface that contain oxygen and which will preferably be bound by covalent bonds to the surface of the textile, and the hydrophobizing agent used in step (c) is a water-based hydrophobizing agent containing a modified polydimethylsiloxane, preferably a modified polydimethylsiloxane in which one or more methyl groups are replaced by substituents with basic functional groups, alkyl groups and/or polyether groups; and additionally contains one or more cationic polymers selected from the group they comprise - polyacrylates, primarily selected from the group consisting of homopolymers and copolymers of acrylic acid, esters of acrylic acid, methacrylic acid, esters of methacrylic acid, and optionally also other monomers that can be copolymerized with acrylic acid, esters of acrylic acid, methacrylic acid and/or esters of methacrylic acid, and primarily styrene; - polyurethanes, preferably polyester-type and/or polycarbonate-type polyurethanes; - polyester, - polypeptides, - polyamides and - polysaccharides, which are preferably selected from the group consisting of chitin and chitosan. 10. Procedure in accordance with any of the previous requirements, primarily in accordance with requirement 9, whereby the textile surface of the article which is manufactured or placed on that textile surface in step (a) contains one or more materials which are selected from the group consisting of - the first material, selected from the group consisting of cellulose and regenerated cellulose and their mixtures; - another material, selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures; as well as - mixtures thereof; where it is advantageous for the surface of the textile to contain one or more materials, at least one of which is selected from the group they comprise another material, selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as their mixtures; wherein the plasma treatment in step (b) - low-pressure plasma treatment, which is preferably activated by low-pressure plasma, which is carried out in the presence of a gas mixture containing O2 and at least one other inert gas selected from the group consisting of He and Ar, wherein it is preferable that said gas mixture contains at least 99% by volume of O2 and at least one other inert gas selected from the group consisting of He and Ar, where it is particularly desirable that the mentioned mixture of gases contains at least 99% by volume of O2 and Ar, and the hydrophobizing agent used in step (c) is a water-based hydrophobizing agent containing a modified polydimethylsiloxane, preferably a modified polydimethylsiloxane in which one or more methyl groups are replaced by substituents with basic functional groups, alkyl groups and/or polyether groups; and additionally contains one or more cationic polymers selected from the group they comprise - polyacrylates, preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, esters of acrylic acid, methacrylic acid, esters of methacrylic acid, and optionally additionally other monomers that can be copolymerized with acrylic acid, esters of acrylic acid, methacrylic acid and/or esters of methacrylic acid, primarily styrene; - polyurethanes, primarily polyester-type and/or polycarbonate-type polyurethanes; - polyesters, - polypeptides, - polyamides and - polysaccharides, which are preferably selected from the group consisting of chitin and chitosan. 11. The procedure according to any of the requirements from 6 to 10, wherein in step b) - treatment with low-pressure plasma is performed for a duration of 10 seconds to 10 minutes, primarily for a duration of 30 seconds to 5 minutes, and especially preferably for a duration of 1 minute to 3 minutes; and/or - low-pressure plasma is created at a frequency ranging from 10 MHz to 18 MHz, primarily in the range from 11 MHz to 15 MHz, and/or - low-pressure plasma is created using electrodes, where it is preferable that the density of electrodes is in the range of 1 to 10 electrodes/m<2>, particularly advantageously in the range of 2 to 5 electrodes/m<2>, and in the ideal case it is particularly favorable that this density is in the range of 2.5 to 4 electrodes/m<2>, in relation to the surface of the textile that was produced or placed in step (a); and/or - that the low-pressure plasma treatment is performed using a plasma production system that operates at a power ranging 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, and in the perfect case particularly advantageously in the range from 5 kW to 10 kW, and/or - that the low-temperature plasma treatment is performed in a plasma treatment chamber at a power ranging 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>. 12. A process according to any of the preceding claims, wherein the wet chemical treatment in step (c) contains one, or more measures, or all of the following measures: - impregnation of the surface of the textile resulting from the plasma treatment from step (b) or the textile surface produced from it in further steps, preferably impregnation by complete immersion in a bath, particularly advantageously using coatings, - drying of the absorbed agent for hydrophobization on the surface of the textile, - fixing of the absorbed agent for hydrophobization on the surface of the textile, wherein it is advantageous that the wet chemical treatment of the textile surface resulting from the plasma treatment from step (b) or the textile surface produced from it in further steps includes impregnation by complete immersion in a bath, and especially preferably impregnation by means of coatings, whereby it is advantageous that the drying and/or solidification of the absorbed hydrophobization agent takes place on the surface of the textile afterwards. 13. A method according to any one of the preceding claims, wherein the hydrophobized textile surface that has been treated with the plasma of step (c) - relatively more hydrophobic than the textile surface - products produced or equipped with a textile surface in step (a) and/or - textile surface which is the result of plasma treatment in step (b), and/or - an object that has been produced or on which a textile surface has been placed in step (a) after only wet chemical treatment has been performed in the manner described in step (c), but without the prior plasma treatment described in step (b), and/or - relatively more permanently hydrophobic than the corresponding textile surface of the object which was produced or on which the textile surface was placed in step (a) after performing only wet chemical treatment in the manner described in step (c), but without the prior plasma treatment described in step (b). 14. A textile product, which contains a hydrophobized textile surface, and which can be produced by carrying out a procedure in accordance with any of the preceding requirements. 15. Carrying out a procedure with a low-pressure plasma for the preparatory treatment of the textile surface of the object, before the wet chemical hydrophobization of the surface of the textile, wherein the low-pressure plasma treatment is performed using at least one oxygen-containing compound selected from the group consisting of O, O2, O3, NO, N2O and CO2, wherein at least one oxygen-containing compound is present in the gas mixture containing O2 and at least one more inert gas selected from the group consisting of He and Ar, wherein the gas mixture has a volume fraction of O2 ranging from 70% by volume to 90% by volume and an inert gas volume fraction ranging from 10% by volume to 30% by volume. Published and printed by: Institute for Intellectual Property, Belgrade, Kneginje Ljubice 5 4