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 for example a water-repellent or waterproof surface, such as outdoor clothing articles, are currently becoming predominant made by equipping with fluorine-containing chemicals.
• fluorine-containing chemicals Often perfluorinated or polyfluorinated organic compounds, also known as "fluorocarbons" are used for this purpose.
• fluorocarbons are very durable and can accumulate in the environment and in the human body - whereby a risk to the environment and the health of living organisms can not be excluded - are sought in the art alternatives that have similar advantageous surface properties, the aforementioned disadvantages however avoid it.
• a plasma is a partially ionized gas, which is often referred to as the "fourth state of matter of matter".
• Phenomena such as lightning or northern lights (aurora borealis) are naturally occurring plasmas. Technically, they can be generated by applying electric fields. Plasmas are interesting because of their physical and chemical properties. In them, highly excited particles and radicals are generated. These can trigger chemical reactions that are not possible under normal conditions. In this case, the temperature of the workpieces to be treated with a plasma can be kept very low.
• the document DE 101 11 427 A1 teaches a method and apparatus for cleaning and treating textiles in low pressure plasma.
• the document EP 695 622 A2 describes a method and apparatus for plasma modification of porous articles, for example textiles.
• WO 2016/193486 A1 discloses a method for applying a halogen-free, water-repellent nano-coating to textiles by means of a low-pressure plasma polymerization method.
• Impregnating agents which contain non-fluorinated silicones and at least one cationic polymer.
• the textile articles produced by said process should preferably also after demanding use - such as the professional or industrial Use, for example, as workwear - maintained with increased demands on abrasion resistance and surface equipment resistance.
• a further specific object of the present invention was to provide an environmentally friendly process which reduces or at least largely and ideally avoids the use of long-lived, at best only slowly degradable in the environment, chemicals such as fluorocarbons or alkylphenol ethoxylates.
• An important aspect of this specific task has also been to produce by the 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) degradable and thus at least partially or ideally fully compostable, and Accordingly, suitable for biological circulation.
• Textile articles made by the process of the present invention are suitable for demanding use such as professional or industrial use its increased requirements for abrasion resistance and resistance of the surface finish, for example, for use as workwear and / or for industrial washing processes, since the textile articles long retain their advantageous properties 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, weather-resistant, easy-to-clean and / or difficult or hardly adhering (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, in particular 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.
• the plasma cleaning is often preceded by subsequent further plasma treatment steps and is usually carried out in low-pressure plasma.
• a universally applicable low-pressure plasma system is therefore often equipped so that the essential cleaning operations, in particular a cleaning in oxygen plasma performed can be.
• Such a low-pressure plasma system used for cleaning processes is also referred to as a "plasma cleaner".
• Plasma activation is most commonly used to increase the surface tension of nonpolar substrates (i.e., 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, which increases the surface tension and / or the wettability of the substrate surface becomes.
• plasma activation no polymerizable monomers are used because direct coating of the substrate surface with polymer films is not the goal.
• Plasma activation is typically performed for shorter periods, such as in the range of less than 10 minutes.
• the quality of plasma activation can be e.g. be assessed or tested by known contact angle measurement. In this method, the contact angle of a drop of a test liquid to the activated surface is measured. The better the activation, the flatter the drop is on the surface.
• Plasma etching is understood to mean material-removing plasma-assisted etching processes on solids.
• 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, perfluorinated hydrocarbons (perfluorocarbons, PFCs) such as tetrafluoromethane (CF 4 ), hexafluoroethane (C 2 F 6 ), perfluoropropane (C 3 F 8 ), perfluorobutadiene (C 4 F 6 ), unsaturated PFCs, perfluorinated aromatics as well as 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 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.
• 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 manufactured or provided in step (a) After only wet-chemical treatment as in step (c) but without prior plasma treatment in step (b).
• "comparatively durable hydrophobicized” means that the plasma-treated hydrophobicized textile surface resulting after step (c) also after five washing and drying cycles (preferably carried out according to the standard ISO 6330: 2000 (E), conditions: washing machine type A / front loader; Washing program 5A "Normal” at 40 ⁇ 3 ° C, drying in a tumble dryer) has a higher value determined in accordance with the AATCC TM22-2014 standard than that treated under the same conditions for comparative purposes (ie also after five washing and drying cycles) ) corresponding textile surface of the article produced or provided in step (a) after only wet-chemical treatment as in step (c), but without prior plasma treatment in step (b).
• the wet-chemical treatment in step (c) of the 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 with both the hydrophobing agent and with water, preferably simultaneously.
• 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. Combinations of preferred materials thus again give preferred materials or combinations of materials.
• 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 natural (and therefore biodegradable) material, preferably selected from the group consisting cotton, wool, silk, cellulose and cellulose regenerate; and at least one synthetic material selected from the group of biodegradable synthetic polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as mixtures of the aforementioned materials
• the textile articles produced by the process according to the invention are advantageously at least partially and, depending on the other constituents of the textile article such as the hydrophobing agent, ideally completely biologically (ie by biological mechanisms such as the action of microorganisms) degradable and thus at least partially and ideally completely 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 almost completely biologically (ie by biological mechanisms such as the action of microorganisms).
• the textile surface of the article produced or provided in step (a) comprises one or more materials selected from the group consisting of at least one natural (and therefore biodegradable) material selected from the group consisting of cellulose and cellulose regenerate ; and at least one synthetic material selected from the group of biodegradable synthetic polymers consisting of substituted polyesters, unsubstituted polyesters, substituted polyamides and unsubstituted polyamides, as well as mixtures of the aforementioned materials
• the products prepared by the process according to the invention are not only advantageously at least partially and, ideally, almost completely biodegradable and thus at least partially and ideally completely compostable, but they are additionally also suitable for meeting particularly high demands on their mechanical strength and the longevity or durability of the hydrophobic or water-repellent or waterproof properties. This variant of the method according to the invention is therefore particularly preferred.
• Cellulose to be used as natural material in step (a) of the method according to the invention is preferably obtained from the wood of trees and / or from plant fibers, preferably from hemp, flax, bamboo, banana and / or ramie.
• 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.
• Regenerated fibers are fibers made from naturally occurring, renewable resources through chemical processes. These are mainly cellulose derivatives of wood.
• 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, modal fibers achieve 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 regenerated cellulose fiber, which is produced by the known direct solvent process. It is used in particular for the production of textiles and nonwovens ("nonwovens"). Lyocell fibers have high dry and wet strength, are soft and absorb moisture very well. Textiles made from this fabric regularly have a smooth and cool handle with a flowing case, have a low tendency to wrinkle and can be washed and chemically cleaned.
• Cupro also referred to as copper silk or copper fiber
• Cuprofibers are mainly processed into 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).
• Synthetic material which can be used in step (a) of the process according to the invention also comprises elastomers, preferably biodegradable elastomers.
• biodegradable substituted or unsubstituted polyesters to be used in step (a) of the process of the invention include copolyesters of aromatic and aliphatic monomers, preferably copolyesters comprising as monomers terephthalic acid and alkanediols, preferably selected from the group consisting of ethanediol, 1,3-propanediol and 1,4-butanediol, and comprising or not comprising other monomers.
• biodegradable substituted or unsubstituted polyesters which are particularly preferred for use in accordance with the invention are polybutylene adipate terephthalate (“PBAT”), Ecoflex® (BASF) and infinito® (Lauffenmühle GmbH & Co. KG).
• PBAT polybutylene adipate terephthalate
• Ecoflex® Ecoflex®
• infinito® Lauffenmühle GmbH & Co. KG
• Preferred polyamides useful in step (a) of the process of the invention are polyamide-imides 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 of the backbone are those 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).
• 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.
• the aforesaid materials for example cellulose or cellulose regenerate
• the types of textile surfaces for example woven or knitted fabrics
• inventive method may preferably be combined, and such combinations, in particular combinations of preferred materials with preferred types of textile surfaces, yield preferred variants of inventive method.
• 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, get a few organic or no organic solvents into the environment, without elaborate filtering 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 at least substantially chemically 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 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 comprise further monomeric units which can be co-polymerized with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic acid esters contain.
• homopolymers and copolymers are formed from monomers of acrylic acid, acrylic acid esters, methacrylic acid and methacrylic acid esters, wherein (depending on the requirements of the case) further with acrylic acid, acrylic acid esters, methacrylic acid and / or methacrylic esters co-polymerizable monomers are integrated or 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, especially preferably in the range of 7: 1 to 1: 7, used in relation to the one or more cationic polymers.
• the aqueous hydrophobing agent in step (c) of the process according to the invention preferably contains the modified polydimethylsiloxane in a total amount in the range from 0.1% by weight to 20% by weight, particularly preferably in the range from 0.2% by weight to 15 Wt .-% and particularly preferably in the range of 0.3 wt .-% to 10 wt .-%, based on the total weight of the aqueous hydrophobing agent.
• the aqueous hydrophobing agent in step (c) of the process according to the invention preferably contains the one or more cationic polymers in a total amount in the range from 0.05% by weight to 15% by weight, particularly preferably in the range from 0.1% by weight. % to 10 wt.%, and more preferably in the range of 0.15 wt.% to 5 wt.%, based on the total weight of the aqueous hydrophobing agent.
• the modified polydimethylsiloxane useful in step (c) of the process of the invention comprises one or more polydimethylsiloxanes selected from the group consisting of aminoalkyl-polydimethylsiloxane, amidoaminoalkyl-polydimethylsiloxane, alkylaminoalkyl-polydimethylsiloxane, alkylamidoaminoalkyl-polydimethylsiloxane, polyoxyalkylene-polydimethylsiloxane and alkyl polyoxyalkylene polydimethylsiloxane.
• modified polydimethylsiloxanes which are preferably also used in step (c) of the process according to the invention, are in particular in the document WO 2010/139466 disclosed.
• the aforementioned modified polydimethylsiloxanes can be used individually or in combination with one another.
• the cationic polymers 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 incorporation 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 in particular in the document WO 2010/139466 disclosed.
• the aforementioned cationic polymers can be used individually or in combination with one another.
• 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.
• Preferred chitosan derivatives to be used in the process of the present invention 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.
• the chain length and / or the degree of deacetylation of the polysaccharide (chitin or chitosan) can be changed. Due to the free amino groups formed by the deacetylation, chitosan in acidic solution is a polycation with a high charge density.
• a chitosan having a degree of deacetylation of> 75% preference is given to a chitosan having a degree of deacetylation of> 75%, particularly preferably having a degree of deacetylation of> 85% and very particularly preferably having a degree of deacetylation of> 90%.
• the molecular weight of the chitosan used in step (c) of the process according to the invention is preferably in the range of 10,000 daltons to 5,000,000 daltons, more preferably in the range of 100,000 daltons to 2,000,000 daltons, and most preferably in the range of 150,000 daltons up 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 in particular in the document WO 2010/139466 disclosed.
• polyamides and “polypeptides” (i.e., in each case a natural or synthetic polymer linked by peptide bonds between amino acids) are used interchangeably and used differently 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 in particular in the document WO 2010/139466 disclosed.
• a low pressure plasma is typically generated between two or more electrodes by high frequency electromagnetic fields, at a pressure substantially lower than the atmospheric pressure of the earth. Due to the large (mean) free path length of excited particles generated in this way, the expansion of the plasma can go beyond the effective range of the high-frequency field and also capture the entire volume of a plasma chamber.
• 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 method according to the invention or a preferred method according to the invention is therefore preferred, wherein the pressure ranges given above for step (b) as being preferred or particularly preferred for the low-pressure plasma treatment, preferably the low-pressure plasma activation, are 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, indicated ranges of the time duration.
• the plasma treatment, preferably the low-pressure plasma treatment, particularly preferably the low-pressure plasma activation, in step (b) of the process according to the invention is carried out in the presence of a reactive gas and / or (preferably "and") an inert gas.
• a reactive gas preferably a reactive gas
• an inert gas preferably a reactive gas
• noble gases or mixtures thereof are preferably used.
• one or more oxygen-containing compounds which at least intermediately release molecular oxygen for example, precursors or precursors of oxygen
• molecular oxygen for example, precursors or precursors of oxygen
• a preferred process according to the invention or one described above or below is therefore preferred, the low-pressure plasma treatment being carried out with at least one oxygen-containing compound selected from the group consisting of O, O 2 , O 3 , NO, N 2 O and CO 2 such that preferably oxygen-containing functional groups (preferably -OH, -CO, -CHO or -COOH) are produced 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 their covalent bonding to the textile surface can be performed by suitable physical or physicochemical methods, for example by Fourier transform infrared spectroscopy (FT-IR spectroscopy) or by X-ray photoelectron spectroscopy for the chemical analysis (ESCA).
• FT-IR spectroscopy Fourier transform infrared spectroscopy
• ESA X-ray photoelectron spectroscopy for the chemical analysis
• 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 process according to the invention or one described above or below as being preferred wherein the aforementioned mixture (before the transition to the plasma state) has a proportion of O 2 in the range from 70% by volume to 90% by volume and a proportion inert gas, preferably He and / or Ar, in the range from 10% to 30% by volume.
• 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).
• variants of the method according to the invention are preferred, wherein in step (b) a low pressure plasma treatment, preferably a low pressure plasma activation, at a pressure in the range of 1 Pa (0.01 mbar) to 0.5 kPa (5 mbar) and for a duration in the range of 30 sec to 5 min.
• 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 for a duration in the range of 1 min to 3 min.
• the electrode density preferably being in the range indicated above, a particularly effective and uniform activation and subsequent hydrophobicization of the textile surface is achieved.
• step (b) of the method according to the invention If the low-pressure plasma treatment is carried out in a plasma treatment chamber at a power in the abovementioned range or with a plasma generation source at a power in the above-mentioned range in step (b) of the method according to the invention, particularly good results with respect to the activation of the textile surface or the following Hydrophobing and their longevity achieved.
• 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.
• 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 hydrophobized 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, prior to wet-chemical hydrophobing of the textile surface.
• Example 1 Providing an article with a textile surface
• each fabric used in the Examples given below was provided which consisted of 100% individual filaments of a biodegradable synthetic polymer (a copolyester comprising as monomers terephthalic acid and ethanediol and other monomers).
• 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
• 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).
• the following parameters were set: Frequency: 13.56 MHz Duration of treatment: 2 min Power (plasma source): 9 kW Print: 0.3 mbar (30 Pa)
• the tissue so plasma-treated was designated "G-tO-pbh”.
• compositions indicated below were abbreviated in a manner known per se from aqueous hydrophobing agents which can be used in the process according to the invention (step (c)) (hereinafter also abbreviated to "HPM") comprising modified polydimethylsiloxane (hereinafter also referred to as "PDMS”) ) manufactured.
• HPM aqueous hydrophobing agents which can be used in the process according to the invention
• 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.
• an emulsifier-containing dispersion (about 35% by weight active content) of an acrylate-styrene copolymer having 25-45% by weight of amino-functional monomers and a molecular weight between 50,000 and 500,000 g / used mol (Da).
• Example 4 Wet-chemical treatment of a textile surface
• a plasma-treated fabric "G-to-pbh” prepared as described above (see Example 2) was prepared in a manner known per se in a padding machine (also known as “padding machine” or “padding mangle") with the same method as described above (see Example 3) impregnated aqueous hydrophobing agent HPM3 (concentration: 300 g / L), wherein the following parameters were set: Print: 300 kPa (3 bar) Temperature: 21 ° C Feed speed: 2 m / min
• the wet-chemically treated (impregnated) fabric was dried for 2 min at 120 ° C on a tenter.
• the dried fabric was then treated for 1 min on a tenter 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-hydr".
• a non-plasma-treated fabric "G-to" provided as described above was impregnated in a padding machine with the hydrophobizing agent HPM3 prepared as described above in the same way as described in Example 4.1, then likewise dried and fixed.
• the thus prepared, non-plasma-treated hydrophobized fabric was designated "G-to-hydr" and used as comparison fabric prepared according to the invention.
• 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 contact surface. The smaller this interaction, the larger the contact angle becomes. From the determination of the contact angle certain properties of the surface of a solid can be determined, for. B. the surface energy.
• the surface In the special case of using water as a liquid, the surface is described as hydrophilic at low contact angles (about 0 °), as hydrophobic at angles of 90 ° and as superhydrophobic at even larger angles. The latter is also called the lotus effect at very high angles (about 160 °) and corresponds to an extremely low wettability.
• 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
• 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 ").
• Example 6b Durability of the hydrophobing against abrasion
• 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.
• the degree of water resistance of a hydrophobicized fabric article made by the process of this invention was determined and compared to an article made (impregnated) by a known prior art process.

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• 2017
  • 2017-10-16 EP EP17196664.1A patent/EP3470573A1/de not_active Withdrawn
• 2018
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  • 2018-10-15 WO PCT/EP2018/078096 patent/WO2019076823A1/de not_active Ceased
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• 2021
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