Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, e.g. by ultrasonic waves, corona discharge, irradiation, electric currents or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
  • D06M10/02—Sonic or ultrasonic waves; Corona discharge
  • D06M10/025—Corona discharge or low temperature plasma
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
  • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
  • D06M23/02—Processes in which the treating agent is releasably affixed or incorporated into a dispensing means
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
  • D06M15/03—Polysaccharides or derivatives thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
  • D06M15/15—Proteins or derivatives thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
  • D06M2200/12—Hydrophobic properties

Definitions

• the present invention relates to a method for producing a textile article having a hydrophobicized textile surface, comprising the steps of: plasma-treating a textile surface, resulting in a plasma-treated textile surface and subsequently wet-chemically treating the plasma-treated textile surface or a textile surface produced therefrom in further steps a hydrophobing agent, so that a plasma-treated hydrophobicized textile surface results.
• the invention also relates to a producible by the process according to the invention textile article.
• the invention also relates to the use of a low-pressure plasma process for the preliminary treatment of a textile surface of an article before the wet-chemical hydrophobing of the textile surface.
• Textile articles having a hydrophobized surface such as a water-repellent or waterproof surface, such as outdoor clothing articles, are currently manufactured predominantly by incorporation with fluorochemicals.
• fluorochemicals perfluorinated or polyfluorinated organic compounds, also known as “fluorocarbons”
• fluorocarbons are used for this purpose, however, since such fluorocarbons are very long-lived and can be used in the conversion process. far and can accumulate in the human body - a hazard to the environment and the health of living organisms can not be excluded - are sought in the art alternatives, which have similar advantageous surface properties, but avoid the aforementioned disadvantages.
• a plasma is a partially ionized gas, which is often referred to as the "fourth state of aggregation of matter.”
• Phenomena such as lightning or northern lights (aurora borealis) are naturally occurring plasmas, which can be technically created by applying electric fields.
• plasmas are interesting in that they generate highly excited particles and radicals, which can trigger chemical reactions that are not possible under normal conditions, and the temperature of the workpieces to be treated with a plasma can be kept very low
• Document DE 101 1 1 427 A1 teaches a method and a device for cleaning and treating textiles in low-pressure plasma.
• the document EP 695 622 A2 describes a method and a device for the plasma modification of porous objects, for example textiles.
• the document WO 2016/193486 A1 specifies a method for applying a halogen-free, water-repellent nano-coating to textiles by means of a low-pressure plasma polymerization method.
• WO 2010/139466 A1 discloses impregnating active ingredients which contain non-fluorinated silicones and at least one cationic polymer.
• the document JP S62 104975 A describes a method for producing a water-repellent fabric, which comprises the application of a liquid containing organopolysiloxanes and / or fluorine compounds to a fabric, a low-temperature plasma treatment and a repeated application of the liquid.
• the document JP S60 194183 A describes a permanently coated synthetic or natural fabric comprising a silicone rubber film formed on a base fabric.
• the textile articles produced by said process should retain the hydrophobic, in particular water-repellent or waterproof, surface properties preferably also after demanding use - such as professional or industrial use, for example as workwear - with increased demands on abrasion resistance and surface finish resistance.
• Another specific object of the present invention was to provide an environmentally friendly process which reduces or at least largely largely and ideally avoids the use of long-lived, in the best case only slowly degradable, chemicals such as fluorocarbons or alkylphenol ethoxylates.
• An important aspect of this specific task was also to produce, by said environmentally friendly method, textile articles which are at least partially and ideally fully biodegradable (ie by biological mechanisms such as the action of microorganisms) and thus at least partially or ideally fully compostable are and are therefore suitable for biological recycling.
• step (b) plasma-treating the textile surface produced or provided in step (a) to give a plasma-treated textile surface, (c) wet-chemically treating the plasma-treated textile surface resulting from step (b) or a textile surface produced therefrom in further steps Hydrophobizing agent, so that a plasma-treated hydrophobêt textile surface results.
• the method according to the invention can be textile products with robust, durable water-repellent or waterproof properties produced in an environmentally friendly manner, even with reduced use or extensive or complete avoidance of long-lived, in the environment at best only slowly degradable chemicals such as fluorocarbons or Alkylphenolethoxylate.
• Textile articles produced by the process according to the invention are suitable for demanding use such as professional or industrial use with its increased demands on abrasion resistance and resistance of the surface finish, for example for use as workwear and / or for industrial washing processes, since the textile Products retain their advantageous properties for a long time even under these demanding conditions.
• the textile articles produced by the process according to the invention have further advantageous surface properties, for example, they may additionally be dirt-repellent, weatherproof, easy to clean and / or difficult or hardly adhesive (bead-off effect).
• Another advantage of the textile articles produced by the process according to the invention is their suitability for a refreshment of the hydrophobization or impregnation or a post-hydrophobicization or post-impregnation, if, for example, after prolonged use of the textile article its water-repellent or waterproof property should subside
• a textile article produced by the process according to the invention can again be given improved hydrophobic or water-repellent or water-tight properties by renewed wet-chemical treatment according to step (c) described above, for example by washing in the washing machine.
• plasma treatment generally refers to all plasma processes which can be used for the surface treatment, in particular for the surface treatment of textile articles, especially plasma cleaning, plasma activation, plasma etching and plasma coating.
• the plasma treatment may include one or more of the aforementioned plasma processes, which will be explained in more detail below.
• Plasma cleaning is often preceded by subsequent plasma treatment steps and is usually carried out in low-pressure plasma.
• a universally applicable low-pressure plasma system is therefore often equipped so that the essential cleaning processes, in particular a cleaning in oxygen plasma, can be performed.
• Such a low pressure plasma system used for cleaning processes is also referred to as a "plasma cleaner.”
• Plasma activation (or plasma activation) is most commonly used to increase the surface tension of nonpolar substrates (ie, materials to be processed by plasma activation)
• oxygen radicals are usually generated in the oxygen plasma (ie using oxygen or oxygen-forming compounds, usually gases), which can form bonds to the surface structures of a substrate due to their high reactivity, as a result of which the surface tension and / or the wettability of the substrate surface
• no polymerizable monomers are used since direct targeting of the substrate surface with polymer films is not the objective, and plasma activation is typically performed for shorter periods, such as less than 10 minutes.
• the quality of plasma activation can be e.g. be assessed or tested by known
• Plasma etching is understood to mean material-removing plasma-assisted etching processes on solids.
• parts of the surface of a substrate are removed by chemical reaction with a process gas.
• the high reactivity of the excited atoms and molecules and in particular of the radicals is used.
• the most important criterion in the selection of the etching gas is its ability to form a readily volatile reaction product with the solid to be etched.
• the etching rate is very different (selective) on different substrates.
• Suitable organic etching gases are, for example, perfluorocarbons (perfluorocarbons, PFCs) such as tetrafluoromethane (CF4), hexafluoroethane (C2F6), perfluoropropane (C3F8), perfluorobutadiene (C4F6), unsaturated PFCs, perfluorinated aromatics and perfluorinated heteroaromatics.
• Suitable inorganic etching gases for example, sulfur hexafluoride, nitrogen (III) fluoride, boron trichloride, chlorine, hydrogen chloride or hydrogen bromide.
• Oxygen is usually not used as an etching gas, if a high material removal with significant change of physical or mechanical surface properties is to be achieved (usually at high energy input). Mixtures of different etching-active gases are common. Plasma etching is usually carried out for longer periods, for example in the range of 15 to 120 minutes.
• plasma coating usually in low-pressure plasma, polymerizable monomers are introduced into a plasma chamber, which then polymerize under the influence of the plasma.
• the achieved with plasma polymerization layer thicknesses are usually in the range of micrometers.
• the process technology for plasma coating is considerably more complex than, for example, for plasma activation.
• the plasma treatment preferably comprises a plasma cleaning and / or a plasma activation, particularly preferably the plasma activation.
• a process according to the invention is preferably where the plasma-treated (preferably plasma-cleaned and / or plasma-activated) resulting from step (c) is a hydrophobicized textile surface
• step (a) the article manufactured or provided in step (a) and / or
• step (b) the plasma-treated (preferably plasma-cleaned and / or plasma-activated) textile surface resulting in step (b), and / or
• step (b) the article produced or provided in step (a) after only wet-chemical treatment as in step (c) but without prior plasma treatment in step (b), and / or - Has a comparatively more durable hydrophobic than the corresponding textile surface of the article produced or provided in step (a) after only wet-chemical treatment as in step (c), but without prior plasma treatment in step (b).
• “Comparatively hydrophobic” means preferably that after step (c) resulting plasma-treated hydrophobic textile surface has a higher value (in cm) for the according to the standard ISO 81 1-1981 / DIN EN 2081 1: 1992-08 (water column above the textile surface, ie above / facing the plasma-treated textile surface or above / facing the plasma-treated, hydrophobized surface) measured water column, as the corresponding textile surface of or in step (a) manufactured or provided article, which no corresponding treatment according to has undergone steps (b) and (c) and / or of an article produced in step (b) which has not undergone any corresponding treatment according to step (c) and / or of one in step (a) produced or provided article after only wet-chemical treatment as in step (c), but without previous plasma treatment in Schr itt (b).
• the textile surface of an article produced or provided in step (a) can be treated wet-chemically, in particular for the purpose of comparison with a process according to the invention and the textile surfaces resulting from a process according to the invention, directly, that is without prior plasma treatment. If the wet-chemical treatment of an article produced or provided in a step (a) for the purpose of a comparison is the same as in a step (c) according to the invention, a textile surface is obtained which can be assessed directly for its hydrophobicity.
• a comparative study is given below in Example 6 (see Table 3, Values "A: Moisture Repellency Initial").
• “Comparatively more durable hydrophobicized” means preferably that the plasma-treated hydrophobicized textile surface resulting after step (c) has a higher value (in standard values according to the standard specification) determined according to the spray test of the AATCC TM22-2014 standard than that under the same conditions treated corresponding textile surface of the article produced or provided in step (a) after only wet-chemical treatment as in step (c), but without prior plasma treatment in step (b) (c) the resulting plasma-treated hydrophobicized textile surface, even after five washing and drying cycles (preferably carried out in accordance with standard ISO 6330: 2000 (E), conditions: washing machine type A / front loader, washing program 5A "normal” at 40 ⁇ 3 ° C; drying in the tumble dryer) even higher, according to the standard AATCC TM22 -2014 has a value corresponding to the textile surface of the article produced or provided in step (a) after treatment under the same conditions (ie also present after five washing and drying cycles) after only wet-chemical treatment as in step (c), however,
• the wet-chemical treatment in step (c) of the process according to the invention is preferably an aqueous wet-chemical treatment, i. a wet-chemical treatment, wherein the plasma-treated textile surface is contacted both with the hydrophobizing agent and with water, preferably simultaneously.
• step (a) Also preferred is a process according to the invention or one described above or below, wherein the textile surface of the article produced or provided in step (a)
• first material preferably a natural material, preferably selected from the group consisting of cotton, wool, silk, cellulose and cellulose regenerate and mixtures thereof, particularly preferably selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof
• second material hereinafter meant in the sense of a "second material group”
• synthetic material preferably selected from the group consisting of polyesters, polyamides, polyamideimides, polypropylene, polyacrylonitrile and polyacrylic thacrylate and mixtures thereof
• synthetic polymers preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof;
• - is selected from the group consisting of woven, knitted, crocheted, braided, stitchbonded, felted, nonwoven, nonwovens, textile hoses, ropes, fibers, threads, yarns, rovings and mixtures thereof; preferably selected from the group consisting of woven fabrics, knitted fabrics, knitted fabrics, nonwoven fabrics, nonwoven fabrics and mixtures thereof.
• the one or more materials comprised of the textile surface of the article made or provided in step (a) of the method of the invention may be used singly or in combination.
• one or more materials may be employed from a first material (ie, selected from the material group of a first material or group as defined above), or one or more materials may be selected from a second material (ie, selected from the material group a second material or a second material group as defined above) or a mixture or combination of one or more materials of a first material (ie selected from the material group of a first material or a first material group as defined above) with one or more materials from a second material (ie selected from the material group of a second material or a second material group as defined above) can be used.
• Combinations of preferred materials again result in preferred materials or combinations of materials.
• the textile surface of the article produced or provided in step (a) comprises at least one second material selected from the group (preferably a second material group) consisting of polyesters, polyamides, polyamide-imides, polypropylene, polyacrylonitrile and polyacrylmethacrylate and their mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably the biodegradable synthetic see polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof.
• the textile surface of the article produced or provided in step (a) comprises only a second material selected from the group (ie one or more materials selected from a second material group) consisting of polyesters, polyamides, polyamide-imides, Polypropylene, polyacrylonitrile and polyacrylmethacrylate and mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof.
• the textile surface of the article manufactured or provided in step (a) does not comprise a first material (preferably natural material), i. no material which is preferably selected from the group (preferably a first material group) consisting of cotton, wool, silk, cellulose and cellulose regenerate and their mixtures.
• the textile surface of the article produced or provided in step (a) comprises one or more materials which - as indicated above - are selected from the group consisting of at least one first material (as defined above), preferably a natural one (and therefore biologically degradable) material, preferably selected from the group (preferably a first material group) consisting of cotton, wool, silk, cellulose and cellulose regenerate; and at least one second material (as defined above), preferably a synthetic material, which is selected from the group (preferably a second material material).
• first material as defined above
• a natural one (and therefore biologically degradable) material preferably selected from the group (preferably a first material group) consisting of cotton, wool, silk, cellulose and cellulose regenerate
• second material preferably a synthetic material, which is selected from the group (preferably a second material material).
• the textile articles produced by the process according to the invention are advantageously at least partially and in the ideal case completely biodegradable (ie by biological mechanisms such as the action of microorganisms) and thus at least partially and ideally fully compostable and thus suitable for biological circulation , This variant of the method according to the invention is therefore preferred.
• Biodegradable in the context of the present invention means that a textile article, a material, or a substance with this property is compostable and preferably within a period in the range of 12 to 36 months, particularly preferably in the range of 18 to 30 months, and preferably at a temperature in the range of 40 ° C to 80 ° C, more preferably in the range of 50 ° C to 75 ° C, at least predominantly (ie> 90 wt .-%, preferably> 95 wt .-%, of the starting material are biodegraded under the conditions specified herein) and, ideally, are degraded substantially completely biologically (ie by biological mechanisms such as the action of microorganisms), provided that the textile surface of the article produced or provided in step (a) comprises one or more materials which are selected from the group consisting of at least a first material (as defined above), preferably a natural (and therefore biodegradable) material selected from the group (preferably a first group of materials) consisting of cellulose and cellulose regenerate; and
• the textile surface of the article produced or provided in step (a) comprises one or more materials which are selected from the group consisting of
• a second material selected from the group (preferably a second material group) consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; preferably the second material is selected from the group (preferably a second material group) of the copolyesters which contain as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1, 3-propanediol and 1, 4-butanediol, particularly preferably ethanediol) and which preferably comprise at least one further monomer; such as
• the textile surface comprises one or more materials, at least one of which is selected from the group consisting of a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein the second material is preferably selected from the group of copolyesters which contain as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1,3-propanediol and 1,4-butanediol, more preferably etanethiol) and which preferably comprise at least one further monomer which is different from the abovementioned monomers (terephthalic acid or one or more alkanediols);
• cellulose is preferably obtained from the wood of trees and / or plant fibers, preferably hemp, flax, bamboo, banana and / or ramie.
• cellulose regenerate preferably comprises regenerated fibers
• Regenerated fibers are fibers which are produced from naturally occurring, renewable raw materials via chemical processes, in particular cellulose derivatives of wood.
• cellulose (cellulose) or cellulose regenerates which can be used in step (a) of the process according to the invention preferably comprise the materials (or the fibers from the materials) viscose, modal, lyocell and cupro, particularly preferably lyocell.
• Viscose fibers are chemical fibers (regenerated fibers) which are produced industrially by means of the known viscose process, a widespread wet spinning process.
• the starting material of the viscose process is cellulose, predominantly in the form of wood, in which the high-purity cellulose is extracted by various methods.
• Modal fibers like viscose fibers, are also 100 percent cellulose but, unlike other regenerated fibers, are made primarily from beech wood. The starting material is debarked and then crushed to separate from lignin into pieces beech wood. By modifying the manufacturing process can be achieved at Modal fibers have higher fiber strength and improved fiber properties than other pulp fibers. In addition, the modal fiber has a higher moisture absorption and dries quickly.
• Lyocell is a per se known, cellulose-made, industrially produced cellulose regenerated fiber, which is produced according to the per se known direct solvent process. It is used in particular for the production of textiles and non-wovens Lyocell fibers have high dry and wet strength, are soft and absorb moisture very well, and textiles made from them regularly have a smooth and cool feel fluently, have a low tendency to crack, and can be washed and chemically cleaned.
• Cupro also referred to as copper silk or copper fiber
• Cuprofibers are mainly processed into textile lining materials because they are breathable, hygroscopic and do not accumulate static. In addition, the fabrics have a silky soft feel and are smooth and shiny. Cupro can be washed and ironed, but is not iron free. Cupro is usually prepared by the copper oxide-ammonia process (cuoxam process).
• step (a) of the method according to the invention usable second, preferably synthetic, material also comprises elastomers, preferably biodegradable elastomers.
• Particularly preferred synthetic polymers to be used as second material in step (a) of the process according to the invention include substituted and / or unsubstituted polyesters and particularly preferably comprise copolyesters of aromatic and aliphatic monomers.
• These particularly preferred copolyesters of aromatic and aliphatic monomers preferably comprise as monomers terephthalic acid and one or more alkanediols, preferably selected from the group consisting of ethanediol, 1,3-propanediol and 1,4-butanediol.
• step (a) as a second, preferably synthetic material to be used polyester as monomers terephthalic acid and one or more alkanediols (preferably an alkanediol, ie an alkanediol of a variety) selected from the group consisting of ethanediol, 1,3-propanediol and 1,4-butanediol (preferably ethanediol), and preferably comprise at least one other monomer.
• alkanediols preferably an alkanediol, ie an alkanediol of a variety
• inventive particularly Preferred biodegradable substituted or unsubstituted polyesters or fibers of such biodegradable substituted or unsubstituted polyesters are polybutylene adipate terephthalate ("PBAT"), Ecoflex® (BASF) and infinito® (Lauffenmühle GmbH & Co. KG)
• PBAT polybutylene adipate terephthalate
• Ecoflex® Ecoflex®
• infinito® Lauffenmühle GmbH & Co. KG
• Polyamides useful in the process of the invention are polyamideimides and aramides (the latter are also referred to as "aromatic polyamides”), preferably as defined by the US Federal Trade Commission, according to which aramids are those polyamides having aromatic groups in the backbone in which at least 85% of the amide groups are bonded directly to two aromatic rings.
• a particularly preferred biodegradable polyamide to be used in step (a) of the process according to the invention is polyamide 6 which is known per se.
• An example of a particularly preferred biodegradable polyamide according to the invention is Amni Soul Eco® (Rhodia / Solvay).
• the above-mentioned variants of the textile surface of the article produced or provided in step (a) can be used individually or in combination (together). For example, filaments, fibers or yarns of one or more of the above materials may be used singly or in combination.
• threads of at least one synthetic material and / or threads of at least one natural material can be spun individually or together into yarns, or such different threads can each be processed individually or together to form a nonwoven, fabric or fabric, for example, joined, woven or knitted , become.
• step (a) of the process according to the invention whose textile surface is selected from the group consisting of woven and knitted fabrics.
• the plasma treatment of woven and knitted fabrics in step (b) of the process according to the invention can be carried out particularly efficiently and effectively.
• Textile fabrics or knitted fabrics produced by the process according to the invention can be further processed directly into ready-made textile articles, for example into textile articles for everyday use, such as outdoor clothing.
• the aforesaid materials for example cellulose or cellulose regenerate and / or one or more synthetic polymers as defined above
• the types of textile surfaces eg woven or knitted fabrics mentioned above may preferably be combined and such combinations, in particular combinations of preferred Materials with preferred types of textile surfaces yield preferred variants of the method of the invention.
• the textile surface of the article produced or provided in step (a) comprises a woven knitted fabric, knitted fabric, braided knit, felt, nonwoven fabric and / or a woven fabric textile hose, preferably a woven fabric and / or a knitted fabric, particularly preferably comprises a fabric, which or which
• step (c) Also preferred is a process according to the invention or one described above or below as being preferred, wherein the water repellent used in step (c)
• an aqueous hydrophobing agent which preferably comprises modified polydimethylsiloxane, and / or does not comprise fluorine-containing organic compounds.
• An aqueous hydrophobing agent allows the process to be carried out as an aqueous (i.e., at least in the presence of water) process, ideally without the presence of organic solvents. In this way, a few organic see or no organic solvents into the environment, without elaborate filter or retention measures would be required or there are few organic or no organic solvent residues that could affect the environment or would have to be disposed of consuming.
• Polydimethylsiloxanes are known to be at most slightly toxic and chemically at least largely inert, so that their use in the process according to the invention can at least largely and ideally exclude completely damage to living organisms.
• the water repellent is preferably an aqueous hydrophobing agent which - modified polydimethylsiloxane, preferably modified polydimethylsiloxane, wherein one or more methyl groups are replaced by substituents with basic functional groups, alkyl groups and / or polyether groups , comprises; and additionally - comprising one or more cationic polymers selected from
• Polyacrylates preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, me- thacrylic acid, methacrylic acid esters and optionally further monomers copolymerizable with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters, preferably styrene;
• Polyurethanes preferably polyurethanes of the polyester type and / or of the polycarbonate type, which are preferably formed by polycondensation of dialcohols or polyalcohols with diisocyanates and / or polyisocyanates;
• Polyesters which are preferably formed by polycondensation of dialcohols or polyalcohols with dicarboxylic acids and / or polycarboxylic acids;
• Polypeptides which are preferably formed by polycondensation of amino acids
• Polyamides which are preferably formed by polycondensation of amino acids
• biopolymers preferably polypeptides or polyamides, which are each preferably formed by polycondensation of amino acids
• Polysaccharides preferably selected from the group consisting of chitin and chitosan (for modifications and the like see below).
• the polyacrylates which can be used in step (c) of the process according to the invention which are preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, methacrylic acid and methacrylic acid esters, may optionally be combined with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters.
• the homopolymers and copolymers are formed from monomers of acrylic acid, acrylic esters, methacrylic acid and methacrylic acid esters, wherein (depending on the requirements of the individual case) further monomers co-polymerizable with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic esters are integrated or are not integrated.
• the modified polydimethylsiloxane in the aqueous hydrophobing agent in step (c) of the process according to the invention in a weight ratio in the range of 1:20 to 20: 1, preferably in the range of 1:10 to 10: 1, particularly preferably in the range of 7: 1 to 1: 7, relative to the one or more cationic polymers used.
• the aqueous hydrophobing agent in step (c) of the process according to the invention preferably contains the modified polydimethylsiloxane in a total amount in the range from 0.1% by weight to 20% by weight, particularly preferably in the range from 0.2% by weight to 15 Wt .-% and particularly preferably in the range of 0.3 wt .-% to 10 wt .-%, based on the total weight of the aqueous hydrophobing agent.
• the aqueous hydrophobing agent in step (c) of the process according to the invention preferably contains the one or more cationic polymers in a total amount in the range from 0.05% by weight to 15% by weight, particularly preferably in the range from 0.1% by weight.
• the modified polydimethylsiloxane usable in step (c) of the process according to the invention comprises one or more polydimethylsiloxanes which are selected from the group consisting of aminoalkyl-polydimethylsiloxane, amidoaminoalkyl-polydimethylsiloxane, alkylaminoalkyl-polydimethylsiloxane, alkylamidoaminoalkylpolydimethylsiloxane , Polyoxyalkylene-polydimethylsiloxane and alkyl-polyoxyalkylene-polydimethylsiloxane. Examples of such modified polydimethylsiloxanes which are preferably also used in step (c) of the process according to the
• the aforementioned modified polydimethylsiloxanes can be used individually or in combination with one another.
• the cationic polymers which can be used in step (c) of the process according to the invention are preferably homopolymers or copolymers comprising, as constituents of the side chains of the corresponding monomers, uncharged basic groups, preferably primary, secondary or tertiary amino groups, which contain cationic groups by uptake of H + ions can form. Examples of such cationic polymers which are preferably used in step (c) of the process according to the invention are disclosed in particular in document WO 2010/139466.
• polysaccharide comprises modified and unmodified polysaccharides, preferably modified chitin and modified and unmodified chitosan, wherein differences may be present in terms of molecular weights, degrees of deacetylation and polysaccharide derivatives suitable according to the invention, preferably chitosan derivatives
• Preferable chitosan derivatives include chitosan succinate (N-succinyl chitosan), chitosan propionate (N-propionyl chitosan) and chitosan adipate (N-adipyl chitosan).
• Cationic polymers which are preferably used in the process according to the invention specified above are the biopolymers chitin and / or chitosan and their derivatives, preferably chitosan and its derivatives. If more deacetylated than acetylated 2-amino-2-deoxy-.beta.-D-glucopyranose units are present in the total biopolymer molecule (> 50% deacetylated units), this is described in the present text, in accordance with the usual understanding in the art, referred to as chitosan.
• chitin If there are more acetylated than deacetylated 2-amino-2-deoxy- ⁇ -D-glucopyranose units in the total biopolymer molecule ( ⁇ 50% deacetylated units), this will be understood in the present text, in accordance with the usual understanding in the art, referred to as chitin.
• the degree of the resulting deacetylation in chitin or chitosan may vary. To improve the solubility in aqueous solutions and / or to reduce the viscosity, the chain length and / or the degree of deacetylation of the polysaccharide (chitin or chitosan) can be changed.
• chitosan in acidic solution is a polycation with a high charge density.
• the molecular weight of the chitosan used in step (c) of the process according to the invention is preferably in the range of 10,000 daltons to 5,000,000 daltons, more preferably in the range of 100,000 daltons to 2,000,000 daltons, and most preferably in the range of 150,000 daltons to 1,000,000 daltons.
• Examples of chitosan types which can be used or preferably used in step (c) of the process according to the invention are disclosed in particular in document WO 2010/139466.
• the modified polydimethylsiloxane is a modified polydimethylsiloxane
• methyl groups are each replaced by a substituent with a basic functional group, preferably in each case by an aminoalkyl group or an amido-aminoalkyl group, and which preferably comprises terminal methoxy groups; and / or (preferably "and")
• the one or more cationic polymers are selected from the
• Polyacrylates which are functionalized by cationic groups or basic groups, preferably by amino groups, wherein the functionalization is preferably effected by appropriately substituted or functionalized (meth) acrylic acid esters; preferably styrene-acrylate copolymers which are functionalized by basic groups, preferably by amino groups;
• Polyesters which are functionalized by cationic groups or basic groups, preferably by amino groups;
• Polypeptides comprising one or more basic amino acids, preferably selected from the group consisting of lysine, arginine, histidine, citrulline and ornithine, and
• Chitosan preferably with a degree of deacetylation> 75%; wherein preferably at least one of the one or more cationic polymers is selected from the group consisting of - polyacrylates, preferably styrene-acrylate copolymers, which are functionalized by cationic groups or basic groups, preferably by basic groups, more preferably by amino groups, and
• Chitosan preferably with a degree of deacetylation> 75%.
• a substitution for example a side chain of a molecule, with a functional group (which may also be specified in detail in individual cases) is generally referred to as “functionalization.”
• the terms “substituted” and “functionalized” are also used herein (
• polyamides” and “polypeptides” ie in each case a natural or synthetic polymer linked by peptide bonds between amino acids) are used interchangeably and differ only depending on the material context Usually the term “polypeptide” is used in connection with corresponding natural polymers.
• aqueous, fluorine-free hydrophobing agents which are preferably used in step (c) of the process according to the invention are disclosed in particular in document WO 2010/139466. Also preferred is a process according to the invention or one described above or below as being preferred, wherein the plasma treatment in step (b) is a low-pressure plasma treatment, preferably a low-pressure plasma activation, or
• a low pressure plasma treatment preferably a low pressure plasma activation, and at least one further plasma treatment step.
• the at least one further plasma treatment step preferably comprises a plasma cleaning, particularly preferably a plasma cleaning of the textile surface produced or provided in step (a), before a plasma activation of said textile surface is carried out.
• the plasma activation is thus followed by the plasma activation, preferably the low-pressure plasma activation.
• the low-pressure plasma treatment being carried out at a pressure in the range from 1 Pa (0.01 mbar) to 20 kPa (200 mbar), preferably at a pressure in the region of 1 Pa (0.01 mbar) to 0.5 kPa (5 mbar), more preferably at a pressure in the range of 10 Pa to 50 Pa (0.1 mbar to 0.5 mbar).
• a process according to the invention or a preferred process according to the invention is therefore preferred, the pressure ranges specified above for step (b) being preferred or particularly preferred for the low-pressure plasma treatment, preferably the low-pressure plasma activation, being combined with those described below for step (b). as preferred or as particularly preferred for the low-pressure plasma treatment, preferably the low-pressure plasma activation, specified ranges of the time duration.
• step (b) Preference is given to a method according to the invention or one described above or below as being preferred, wherein the low-pressure plasma treatment (step (b)) is carried out at a temperature in the range from 10 ° C to 50 ° C, preferably from 15 ° C to 40 ° C ,
• a plasma method in particular a low-pressure plasma method or low-pressure plasma activation method
• step (b) of the process according to the invention is carried out at temperatures below the specified temperature range or preferred temperature range, for example, undesirable side reactions may occur, if step (b) of the process according to the invention occurs at temperatures above the specified temperature range or above If, for example, the deposition rate of components of the gas or gas mixture forming the plasma is undesirably reduced, the desired effect of the plasma treatment may be undesirably reduced can be compromised.
• the plasma treatment preferably the low-pressure plasma treatment, particularly preferably the low-pressure plasma activation, in step (b) of the method according to the invention
• the inert gas is preferably used in the presence of a reactive gas and / or (preferably "and") an inert gas.
• the inert gases used are preferably noble gases or mixtures thereof.
• the reactive gas used is preferably one or more oxygen-containing compounds which at least temporarily release molecular oxygen (at least under the conditions of low-pressure plasma activation, for example precursors or precursors of oxygen) or make it available.
• a preferred process according to the invention or one described above or below is preferred, wherein the low-pressure plasma treatment is carried out with at least one oxygen-containing compound selected from the group consisting of O, O 2, O 3, NO, N 2 O and CO 2 such that Preferably, oxygen-containing functional groups (preferably -OH, -CO, -CHO or -COOH) are formed on the textile surface which are preferably covalently bonded to the textile surface.
• oxygen-containing functional groups preferably -OH, -CO, -CHO or -COOH
• the detection of the production of such oxygen-containing functional groups on or the detection of their covalent bonding to the textile surface can be performed by suitable physical or physico-chemical methods, for example by Fourier transform infrared spectroscopy (FT-IR spectroscopy) or by X-ray photoelectron spectroscopy for chemical analysis (ESCA). Accordingly, a preferred process according to the invention or one described above or below, according to the invention, wherein the at least one oxygen-containing compound is particularly preferred
• - O2 molecular oxygen
• / or (preferably "and") - is present in admixture with at least one inert gas, preferably selected from the group consisting of He, Ar, Ne and Xe, and / or is present in a mixture, preferably a gas mixture, which comprises O 2 and at least one inert gas selected from the group consisting of He and Ar, wherein preferably the mixture (preferably said gas mixture, which is O 2 and at least one inert gas selected from the group consisting of He and Ar) comprises at least 99% by volume of O 2 and at least one inert gas selected from the group consisting of He and Ar, and more preferably contains at least 99% by volume of O 2 and Ar.
• the plasma treatment preferably the low-pressure plasma treatment, particularly preferably the low-pressure plasma activation, in step (b) of the inventive method with a gas or gas mixture is performed, which (before the transition to the plasma state) in addition to the or the oxygen-containing gases not more than 1% by volume of other gaseous constituents.
• a gas or gas mixture is performed, which (before the transition to the plasma state) in addition to the or the oxygen-containing gases not more than 1% by volume of other gaseous constituents.
• a process according to the invention or one described above or below as being preferred wherein the aforementioned mixture (preferably said gas mixture comprising O 2 and at least one inert gas selected from the group consisting of He and Ar) (before the transition into the plasma state) contains a proportion of O 2 in the range of 70% by volume to 90% by volume and a proportion of inert gas, preferably of He and / or Ar, in the range from 10% by volume to 30% by volume ,
• a gas mixture of this preferred composition gives very good or even best results in terms of preparatory plasma activation of a textile surface by the method according to the invention, so that also very good or even the best results with respect to the moisture-repellent properties of the inventive Process produced plasma-treated hydrophobized textile surface and the durability of these moisture-repellent properties result (see, for example, below the results of Example 6, Table 3 or Example 7, Table 4).
• step (a) comprises one or more materials selected from the group consisting of
• a first material preferably a natural material, selected from the group consisting of cotton, wool, silk, cellulose and cellulose regenerate and mixtures thereof; particularly preferably selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof;
• a second material preferably a synthetic material selected from the group consisting of polyesters, polyamides, polyamide-imides, polypropylene, polyacrylonitrile and polyacrylmethacrylate and mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; such as
• the textile surface comprises one or more materials, at least one of which is selected from the group consisting of a second material preferably a synthetic material, preferably selected from the group consisting of polyesters, polyamides, polyamide-imides, polypropylene, polyacrylonitrile and polyacrylic methacrylate and their mixtures thereof; particularly preferably selected from the group of synthetic polymers, preferably biodegradable synthetic polymers, consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; the plasma treatment in step (b) a low-pressure plasma treatment, preferably a low-pressure plasma activation, wherein the low-pressure plasma treatment is carried out with at least one oxygen-containing compound selected from the group consisting of O, O 2, O 3, NO, N 2 O and CO 2, so that preferably oxygen-containing functional groups are produced on the textile surface, which are preferably covalently bonded to the textile surface, and the hydrophobizing agent used in step
• Polyacrylates preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters and optionally further monomers co-polymerizable with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters, preferably styrene;
• Polyurethanes preferably polyester-type and / or polycarbonate-type polyurethanes
• Polysaccharides preferably selected from the group consisting of chitin and chitosan.
• step (a) comprises one or more materials which are selected from the group consisting of
• a first material selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof;
• a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein preferably the second material is selected from the group of Copoly lyester which as monomers terephthalic acid and one or more alkanediols
• ethanediol 1, 3-propanediol and 1, 4-butanediol, more preferably ethanediol
• ethanediol 1, 3-propanediol and 1, 4-butanediol, more preferably ethanediol
• at least one other monomer which of the aforementioned monomers terephthalic acid or a several alkanediols
• the textile surface comprises one or more materials, at least one of which is selected from the group consisting of a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein the second material is preferably selected from the group of copolyesters which contain as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1,3-propanediol and 1,4-butanediol, more preferably etanethiol) and which preferably comprise at least one further monomer which is different from the abovementioned monomers (terephthalic acid or one or more alkanediols); the plasma treatment in step (b)
• a low-pressure plasma treatment preferably a low-pressure plasma activation, which is carried out in the presence of a gas mixture comprising O 2 and at least one inert gas selected from the group consisting of He and Ar, preferably wherein said gas mixture is at least 99% by volume at O2 and at least one inert gas selected from the group consisting of He and Ar, and particularly preferably said gas mixture contains at least 99 vol .-% of O2 and Ar
• the hydrophobizing agent used in step (c) is an aqueous hydrophobing agent comprising modified polydimethylsiloxane, preferably modified polydimethylsiloxane wherein one or more methyl groups are replaced by substituents having basic functional groups, alkyl groups and / or polyether groups; and additionally comprises one or more cationic polymers selected from the group consisting of
• Polyacrylates preferably selected from the group consisting of homopolymers and copolymers of acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters and optionally further, with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic esters co-polymerizable monomers, preferably styrene;
• Polyurethanes preferably polyester-type and / or polycarbonate-type polyurethanes
• Polysaccharides preferably selected from the group consisting of chitin and chitosan.
• step (b) Also preferred is a process according to the invention or a process described above or below as being preferred, wherein in step (b)
• the low-pressure plasma treatment is carried out for a duration in the range from 10 seconds to 10 minutes, preferably in the range from 30 seconds to 5 minutes, particularly preferably in the range from 1 minute to 3 minutes; and or
• the low-pressure plasma is generated at a frequency in the range of 10 MHz to 18 MHz, preferably in the range of 1 1 MHz to 15 MHz, and or
• the low-pressure plasma is generated with electrodes, wherein the electrode density preferably in the range of 1 to 10 electrodes / m 2 , more preferably in the range of 2 to 5 electrodes / m 2 , most preferably in the range of 2.5 to 4 electrodes / m 2 , based on the textile surface produced or provided in step (a); and or
• step (b) of the process according to the invention may preferably be combined and in combination give particularly preferred process conditions for carrying out step (b).
• a low pressure plasma treatment preferably a low pressure plasma activation, at a pressure in the range of 1 Pa (0.01 mbar) to 0.5 kPa (5 mbar) and for a duration in the range of 30 sec to 5 min.
• step (b) a low-pressure plasma treatment, preferably a low-pressure plasma activation, at a pressure in the range of 10 Pa to 50 Pa (0.1 mbar to 0.5 mbar) and a duration in the range of 1 min to 3 min is performed.
• a low-pressure plasma treatment preferably a low-pressure plasma activation
• a pressure in the range of 10 Pa to 50 Pa 0.1 mbar to 0.5 mbar
• a duration in the range of 1 min to 3 min is performed.
• the electrode density preferably being in the above-mentioned range, a particularly effective and uniform (homogeneous) activation and subsequent hydrophobicization of the textile surface is achieved.
• step (b) of the method according to the invention the low-pressure plasma treatment is carried out in a plasma treatment chamber at a power in the above-mentioned range or with a plasma generation source at a power in the above-mentioned range, particularly good results with respect to the activation of the textile surface the subsequent hydrophobing and their longevity achieved.
• step (c) comprises one or more or all of the following measures: Impregnating, preferably full bath impregnating, particularly preferably by means of padding, the plasma-treated textile surface resulting in step (b) or a textile surface produced therefrom in further steps,
• Fixing absorbed hydrophobing agent on the textile surface wherein the wet-chemical treatment preferably comprises a full bath impregnation, particularly preferably a full bath impregnation by padding, in step (b) resulting plasma-treated textile surface or a textile surface produced therefrom in further steps, preferably thereafter drying and / or fixing absorbed hydrophobing agent on the textile surface takes place.
• the wet-chemical treatment preferably comprises a full bath impregnation, particularly preferably a full bath impregnation by padding, in step (b) resulting plasma-treated textile surface or a textile surface produced therefrom in further steps, preferably thereafter drying and / or fixing absorbed hydrophobing agent on the textile surface takes place.
• the impregnation in the course of the abovementioned wet-chemical treatment in step (c) of the process according to the invention can be carried out by any suitable method for this purpose, for example by spraying, dipping, pressure impregnation, kiss-and-roll, Wash-in impregnation, for example in the washing machine, full bath impregnation (preferred) or by a combination of several of the aforementioned methods.
• the impregnation is preferably carried out according to the invention by full bath impregnation, particularly preferably by padding, preferably when the wet chemical treatment is an aqueous wet chemical treatment.
• the plasma-treated hydrophobicized textile surface obtained in step (c) of the process according to the invention is most effectively brought into contact with the hydrophobizing agent, resulting in a particularly completely and permanently hydrophobicized textile surface.
• step (c) Also preferred is a preferred process according to the invention or one described above or below, wherein the wet-chemical treatment in step (c)
• an aqueous wet-chemical treatment (as explained above), which comprises impregnating (as explained above), preferably full bath impregnation, in particular preferably by means of padding, comprising the plasma-treated textile surface or a textile surface produced therefrom in step (b) with an aqueous hydrophobing agent comprising modified polydimethylsiloxane, the modified polydimethylsiloxane being present in a concentration in the range of 200 g / L to 400 g / L, preferably in the range of 250 g / L to 350 g / L, based on the total amount of aqueous liquid used in the wet-chemical treatment in step (c) is used.
• step (c) in particular on a textile surface of an article prepared or provided in step (a) as described above, which comprises one or more materials which are selected from the group consisting of a first material selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof
• step (c) in particular on a textile surface of an article prepared or provided in step (a) as described above, which comprises one or more materials which are selected from the group consisting of a first material selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof
• the wet-chemical treatment in step (c) is an aqueous wet-chemical treatment and a full bath impregnation, preferably by means of padding, of the plasma-treated textile surface resulting in step (b) or the textile surface produced therefrom in further steps, wherein the full bath impregnation, preferably the padding, is carried out at a pressure in the range from 100 kPa to 500 kPa, preferably in the range from 200 kPa to 400 kPa and / or at a speed of passage of the textile surface (length dimension of the textile surface) through the full bath serving for the impregnation in the range of 0.5 m / min to 5 m / min, preferably in the range of 1 m / min to 3 m / min, and / or (preferably "and") at a temperature in the range of 15 ° C to 35 ° C, preferably in the range of 18 ° C
• Treating in step (c) is an aqueous wet-chemical treatment and comprises drying absorbed hydrophobing agent on the textile surface, wherein the drying is carried out at a temperature in the range of 100 ° C to 140 ° C, preferably in the range of 1 10 ° C up to 130 ° C, and / or (preferably "and")
• the wet-chemical treatment in step (c) is an aqueous wet-chemical treatment and comprises fixing absorbed hydrophobizing agent on the textile surface, wherein the fixing is carried out at a temperature in the range of 120 ° C to 190 ° C, preferably in the range of 140 ° C to 180 ° C, more preferably in the range of 150 ° C to 170 ° C, and / or (preferably "and")
• the measures specified above for the wet-chemical treatment in step (c) of the process according to the invention or as (particularly) preferred, including drying and fixing, are preferably combined with one another, which results in particularly preferred variants of the process according to the invention which are particularly effective and / or permanently hydrophobicized textile surfaces.
• Such particularly permanently hydrophobicized textile surfaces retain their advantageous, in particular water-repellent or watertight, properties particularly long and are particularly resistant to mechanical stress, for example by abrasion or washing or drying operations.
• the present invention also relates to a textile article comprising a hydrophobicized textile surface, producible by a method according to the invention, preferably preparable by a method according to the invention described above as being preferred.
• the textile article according to the invention is preferably selected from the group consisting of weatherproof clothing; Outdoor clothing, functional clothing; Work clothing, preferably for outdoor use; Ponchos; ponchos; Tarpaulins for motor vehicles or construction; awnings; Sunroofs; Umbrellas; Umbrellas; Tarpaulins; Tents and transport containers, preferably suitcases, carrier bags, sports bags, rucksacks and panniers.
• the present invention also relates to the use of a low-pressure plasma process for the preliminary treatment of a textile surface of an article, before the wet-chemical hydrophobing of the textile surface.
• a first material selected from the group consisting of cellulose and cellulose regenerate and mixtures thereof;
• a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein the second material is preferably selected from the group of copolyesters which as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1, 3-propanediol and 1, 4-butanediol, particularly preferred Ethanediol) and which preferably comprise at least one other monomer other than the aforementioned monomers (terephthalic acid or one or more alkanediols); such as
• the textile surface comprises one or more materials, of which at least one is selected from the group consisting of
• a second material selected from the group consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides and mixtures thereof; wherein preferably the second material is selected from the group of copolyesters which comprise as monomers terephthalic acid and one or more alkanediols (preferably selected from the group consisting of ethanediol, 1, 3-propanediol and 1, 4-butanediol, more preferably ethanediol) and which preferably comprise at least one other monomer which is one of the abovementioned monomers
• Example 1 Providing an article with a textile surface
• a fabric was used (provided) consisting of 100% individual filaments of a biodegradable synthetic polymer (a copolyester comprising Monomeric terephthalic acid and ethanediol and at least one other monomer).
• the weight per unit area of the fabric was about 150 g / m 2 and the thread density was about 100 warp threads / cm and about 50 weft threads / cm.
• Example 2 Plasma treatment of a textile surface 2.1 Plasma treatment with a gas mixture
• a sample of the tissue provided above was subjected to low pressure plasma activation in a Nano Plasmacoater BAG with plasma chamber (about 11 m 3 ) and a plurality of electrodes (electrode density about 3.5 electrodes / m 2 tissue ), with the following parameters being set:
• Process gas / inert gas ratio 20 vol.% Ar / 80 vol.% O2.
• the tissue thus plasma-treated was designated "G-tO-pbh (Ar / O 2)".
• Example 1 Another sample of the fabric provided above (see Example 1) was subjected to just as low-pressure plasma activation as described above under 2.1, but only the inert gas argon, but not the process gas molecular oxygen was used (100 vol .-% argon ).
• the tissue so plasma-treated was designated "G-tO-pbh (Ar)".
• Example 2 Another sample of the tissue provided above (see Example 1) was subjected to just as low-pressure plasma activation as described above under 2.1, but only the process gas molecular oxygen, but not the inert gas argon was used (100 vol .-% O2 ).
• compositions stated below (see Table 1) of aqueous water repellents (hereinafter abbreviated to "HPM”) which can be used in the process according to the invention (step (c)) comprising modified polydimethylsiloxane (hereinafter also referred to as “ Abbreviated "PDMS”).
• HPM aqueous water repellents
• PDMS modified polydimethylsiloxane
• chitosan As chitosan, a chitosan having a degree of deacetylation of 95% and a molecular weight of 300,000 to 500,000 g / mol (Da) was used in each case.
• the amino-functionalized (styrene) acrylate copolymer was in each case an emulsifier-containing dispersion (about 35% by weight of active content) of an acrylate-styrene copolymer having 25-45% by weight of amino-functional monomers and a molecular weight of between 50,000 and 500,000 g / mol (Da).
• Table 1 Compositions of water repellents
• Example 4 Wet-chemical treatment of a textile surface
• a plasma-treated fabric "G-to-pbh (Ar / O 2)" prepared as described above (see Example 2.1) was prepared in a manner known per se in a padding machine (also known as “padding machine” or “Padding-Mangle ”) was impregnated with the aqueous hydrophobing agent HPM3 (concentration: 300 g / L) prepared as described above (see Example 3), the following parameters being set:
• the wet-chemically treated (impregnated) fabric was dried for 2 min at 120 ° C on a tenter.
• the dried tissue was then treated for a further 1 minute on a spreader frame at 180 ° C.
• the hydrophobized fabric which had been plasma-treated in this way corresponded to an article produced according to the invention having a hydrophobicized textile surface and was designated "G-tO-pbh (Ar / O 2) -hydr".
• a non-plasma-treated fabric "G-to" provided as described above was impregnated in a padding machine with the hydrophobing agent HPM3 prepared as described above in otherwise identical manner as described in Example 4.1, then likewise dried and fixed.
• the non-plasma-treated hydrophobized fabric produced in this way was designated "G-to-hydr” and used as comparison fabric produced according to the invention.
• Example 5 Determination of the Contact Angle
• the contact angle ⁇ of gas-circulated liquids on a solid surface denotes the angle at the phase boundary of gaseous, liquid and solid phases.
• the size of the contact angle between liquid and solid depends on the interaction between the substances at the interface. The smaller this interaction, the larger the contact angle becomes.
• certain properties of the surface of a solid can be determined, for. B. the surface energy.
• the surface is described as hydrophilic at low contact angles (about 0 °), as hydrophobic at angles of 90 ° and as superhydrophobic at even larger angles. The latter is also called the lotus effect at very high angles (about 160 °) and corresponds to an extremely low wettability.
• the contact angle can be changed.
• the contact angle ⁇ can be measured with a contact angle goniometer.
• the durability of the hydrophobization (moisture repellency) of a textile surface which can be achieved by the process according to the invention was determined and compared with that of a non-inventively produced textile surface.
• Example 6a Durability of the Hydrophobing versus Wash-Dry Cycles
• G-tO-pbh (Ar / O 2 ) -hydr, G-tO-pbh (Ar) -hydr and G-to-O- were prepared with the fabrics provided or prepared as indicated above.
• This spray test is used to determine the water-repellent properties of textile surfaces with or without equipment.
• the tensioned textile surface is wetted under controlled conditions with water, whereby a moisture pattern on the textile surface is formed, the expansion of which depends on the relative water repellency of the considered textile surface.
• Evaluation of the test result as "moisture rejection level” is made by comparing the resulting moisture pattern with corresponding reference standard patterns on a scale of 0 ("full humidification of the entire upper and lower surfaces") to 100 ("no sticking or moistening, too only the upper surface ").
• a (impregnated) textile surface produced by the process according to the invention has better, more durable and more resistant hydrophobic (ie water-repellent or water-repellent) properties than a fabricated (impregnated) fabric according to a known process of the prior art ) textile surface.
• Example 7 Determination of the extent of hydrophobing (water column) The degree of water resistance of a hydrophobbed textile surface article produced by the method of the present invention was determined and compared with an article made (impregnated) by a known prior art method ,
• G-tO-pbh (Ar / O 2 ) -hydr G-tO-pbh (Ar) -hydr and G-to-pbh (0 2 ) -hydr (each according to the invention) were prepared with the tissues provided or prepared above ) and G-to-hydr (comparative) a test to determine the resistance against the penetration of water according to the standard ISO 81 1: 1981-10 / DIN EN 2081 1: 1992-08 (water column above the textile surface, ie above / facing the plasma-treated textile surface or above / facing the plasma-treated, hydrophobic surface) carried out ("hydrostatic pressure test").
• the water resistance is given by this test as the resistance of each considered textile surface against a water column.
• the height of the water column in cm which leads to the permeability of the textile surface to water according to the test conditions of the above-mentioned standard, is given as a measure of the water resistance of the textile surface.
• the results of this experiment are given below in Table 4, once for the corresponding fabrics after their preparation or manufacture (see column A: “Initial”, ie without prior washing and drying treatment) and once for the same fabrics, but after every five Washing and drying cycles (see column B: "After 5 W / T cycles").
• washing and drying cycles were carried out according to the standard ISO 6330: 2000 (E) (washing machine type A / front loader, washing program 5A "normal” at 40 ⁇ 3 ° C; standard detergent without phosphates, ballast 2 kg; Tumble dryer at 65 ° C for 30 min.):

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Physics & Mathematics (AREA)
• Plasma & Fusion (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Priority Applications (9)

Applications Claiming Priority (2)

Publications (1)

Family

ID=60186016

Family Applications (1)

Country Status (12)

Cited By (3)

Families Citing this family (3)

Citations (10)

• 2017
  • 2017-10-16 EP EP17196664.1A patent/EP3470573A1/de not_active Withdrawn
• 2018
  • 2018-10-15 WO PCT/EP2018/078096 patent/WO2019076823A1/de not_active Ceased
  • 2018-10-15 PT PT187830484T patent/PT3697958T/pt unknown
  • 2018-10-15 PL PL18783048T patent/PL3697958T3/pl unknown
  • 2018-10-15 DK DK18783048.4T patent/DK3697958T3/da active
  • 2018-10-15 RS RS20210468A patent/RS61750B1/sr unknown
  • 2018-10-15 LT LTEP18783048.4T patent/LT3697958T/lt unknown
  • 2018-10-15 HU HUE18783048A patent/HUE054827T2/hu unknown
  • 2018-10-15 SI SI201830248T patent/SI3697958T1/sl unknown
  • 2018-10-15 HR HRP20210558TT patent/HRP20210558T1/hr unknown
  • 2018-10-15 EP EP18783048.4A patent/EP3697958B1/de active Active
  • 2018-10-15 ES ES18783048T patent/ES2868050T3/es active Active
• 2021
  • 2021-05-20 CY CY20211100440T patent/CY1124169T1/el unknown

Patent Citations (10)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events