Textile article, method for functionalizing a textile article, textile article which can be obtained therefrom, and method for binding a fabric

Abstract

The invention relates to a textile article which has a first polymer and a second polymer, wherein the second polymer is different from the first polymer and covers at least part of the first polymer, the second polymer comprises a siloxane copolymer, and the siloxane copolymer comprises at least one block composed of a plurality of siloxane monomer units and at least one block composed of a plurality of other monomer units, at least one of the other monomer units having a first ionic group, which is a cationic group. The invention further relates to a method for functionalizing a textile article, to a textile article which can be obtained therefrom, and finally to a method for binding a material.

Description

[0001] Textile object, method for functionalizing a textile object and textile object obtainable therefrom and method for binding a fabric

[0002] AREA OF INVENTION

[0003] The present invention relates to a textile article, a method for functionalizing a textile article, and a textile article obtainable therefrom. Furthermore, the present invention relates to a method for binding (and thereby removing) a fabric.

[0004] BACKGROUND

[0005] For the removal of unwanted or harmful substances, such as allergens, peptides, proteins, or bacteria, from the air in living spaces or similar environments, functionalized surfaces, especially ionically functionalized surfaces, such as those found on upholstered furniture, curtains, bedding, or filters, represent a promising approach. It can be particularly advantageous if the fibers, yarns, or foams used for this purpose are themselves ionically functionalized or treated. These materials usually consist of polymers or at least have polymers on their surface.

[0006] The cationic finishing of fibers and textiles, especially those made of cellulose fibers (and other polymers in the form of blended fabrics), during dyeing for the purpose of improved color binding, preferably with acidic dyes, is known. The cationic finishing of textile surfaces for the purpose of improved color binding during washing processes, so-called dye catchers, is also described, for example, in EP 1 775 372 A2 and DE 10 2005 049 015 A1. WO 2015 / 091740 A2 describes the finishing of textiles, preferably polyester (PET), with hydrophilic silanes that also have cationic components, for the purpose of hindering the adhesion of bacteria and the resulting biofilms, thus precisely the opposite of the approach described above. EP 3 192 923 A2 describes a bed textile and a chemical finishing process such that anion-functional polysiloxanes are applied to bed textiles.These are limited to specific amido-functional aminopolydiorganosiloxanes. The purpose of this application is the non-permanent binding of mite fecal allergens to textile surfaces. Various forms of antimicrobial textile finishing are described in WO 2015 / 028852 A1, EP 3 061 864 A1, and WO 2021 / 180930 A1. However, in these inventions, the ionic, preferably cationic, finish is applied directly to the polymer surface of the fiber by chemical reaction (e.g., WO 2015 / 028852 A1) or a mechanical layer build-up is achieved (e.g., WO 2021 / 180930 A1). It is also known to provide polysiloxane block copolymers with cationic groups in the backbone or main chain of the block copolymer (e.g. DE 198 17 776 A1 , US 2010 / 0048795 A1 , US 2021 / 0388163 A1).

[0007] On the other hand, it is desirable if functionalization such as cationic treatment of fibers and textiles does not impair or even cause the loss of other advantageous properties of the fibers and textiles, such as tear resistance, water absorption capacity and / or breathability, but rather imparts additional advantageous properties to the fibers or textiles, such as improved softness in textiles.

[0008] None of the solutions proposed in the prior art to date allow for targeted and adjustable ionic treatment of polymer surfaces of a textile object, let alone without significantly impairing desired properties of the polymer or the textile object, or where additional advantageous properties such as improved softness are imparted to the textile object, such as a textile.

[0009] There may therefore be a need to equip polymer surfaces with ionic functionalities in a targeted and adjustable manner (for example, with regard to number, spacing, mobility, chemical structure and thus interaction capability with the ion carriers of the protein surfaces to be bound) in order to bind unwanted or harmful substances, such as allergens, peptides, proteins, bacteria or the like, and thus render them harmless or remove them from the environment, without significantly impairing the desired properties of the polymer or the textile object, but even giving the textile object, such as a textile, additional advantageous properties such as an improved soft feel in textiles.Furthermore, from an ecological perspective, there is a need for methods to physically bond the aforementioned protein structures to textile objects that are effective in organisms (bacteria, viruses, etc.) without undesirable (ecologically problematic) chemical or biochemical mechanisms. SUMMARY OF THE INVENTION.

[0010] The inventors of the present invention have discovered that a targeted and, as required, adjustable ionic treatment of a polymer surface can be achieved using a siloxane copolymer comprising longer (e.g., with at least 5, in particular with at least 10 monomer units) hydrophobic polysiloxane blocks and longer (e.g., with at least 5, in particular with at least 10 monomer units) hydrophilic blocks with cationic groups. In addition, particularly through at least partial coating and preferably only spot bonding of the polymer surface, it is possible not only to ensure that other advantageous properties of the polymer or the textile object are not significantly impaired, but even to impart additional advantageous properties. It is known, on the one hand, that a siloxane copolymer of a textile provides increased lubricity or...It imparts suppleness and / or an improved soft feel. However, the inventors have discovered that, in addition, a siloxane copolymer comprising longer hydrophobic polysiloxane blocks and longer hydrophilic blocks with cationic groups can advantageously form loops on or at the polymer surface of a textile object. The type of loop formed also depends on the nature, in particular the hydrophilicity / hydrophobicity, of the coated polymer surface. With a rather nonpolar or hydrophobic polymer surface (such as PE, PP, or PET), the hydrophobic polysiloxane blocks adhere to the polymer surface, while the hydrophilic cationic blocks are repelled by the polymer surface and can thereby form a (polar, cationic-group-equipped) loop. With a rather polar orOn hydrophilic polymer surfaces (such as cellulose, wool, polyamides, but also hydrophilized surfaces of PE, PP or PET (for example by means of ionizing radiation or plasma treatment)), the hydrophilic cationic blocks tend to adhere to the polymer surface, while the hydrophobic polysiloxane blocks tend to be repelled by the polymer surface and can form a (hydrophobic) loop.

[0011] Without wishing to be bound to any specific theory, the inventors currently assume that at least partial coating and preferably only point-like bonding to the polymer surface and / or the loop formation described above by a (essentially linear) siloxane copolymer can significantly contribute to a targeted and, as needed, adjustable ionic treatment of a polymer surface. Furthermore, this can ensure that unwanted or harmful substances are not only bound by ionic interactions but can also be trapped sterically or structurally and thus rendered harmless. In addition, the passages within the loops can provide a uniform distribution of ambient media, such as air, water vapor, or water, and thus contribute to the uniform wetting of hydrophilic surfaces, which is particularly beneficial for textile surfaces based on cellulose or polyamides.whose blended fibers contain polypropylene (PP), polyethylene terephthalate (PET), or elastane. The inventors further assume that a three-dimensional structure of the polymer surface, for example, a helical structure of a cellulose chain at least partially covered with a siloxane copolymer as described above, will result in additional degrees of freedom and, to put it simply, a construct with dendrite-like three-dimensional docking sites can be obtained, which is particularly suitable for the reversible binding of protein structures of varying sizes, charge densities, and secondary or tertiary structures. Furthermore, the inventors currently assume that a coating according to the invention, orThe functionalization of fibers and their spinning into yarn, as well as its use in textiles, involves not only the aforementioned smaller loops but also larger cavities. These cavities, figuratively speaking, represent a cage with hydrophilic, cationically functionalized, or hydrophobic walls, and can therefore capture and bind larger unwanted or harmful substances such as viruses or even entire bacteria. Within the tertiary structure of the textile, repulsion and binding reactions (a "ping-pong" effect) with binding proteins can thus occur simultaneously at the microstructure level, for example, within a single thread. This can ultimately force the final binding to a high degree and preferably results in the final stage.

[0012] The present invention relates accordingly to a textile article comprising a first polymer and a second polymer, wherein the second polymer is different from the first polymer and covers (coats) at least a part (of the surface) of the first polymer, wherein the second polymer comprises a siloxane copolymer, the siloxane copolymer comprising at least one (hydrophobic) block of a plurality of siloxane monomer units and at least one (hydrophilic) block of a plurality of further monomer units, wherein at least one of the further monomer units has a first ionic group (as a side chain), the first ionic group being a cationic group. The first ionic group is thus located, in particular, in a side chain of the siloxane copolymer (and not in its main chain or backbone), specifically in the at least one (hydrophilic) block of a plurality of further monomer units.The first ionic group can itself also represent a side chain (i.e., the first ionic group as a side chain) that is (directly) bound to the main chain or backbone of the siloxane copolymer in at least one (hydrophilic) block consisting of a plurality of further monomer units (but not in the main chain or backbone of the siloxane copolymer).

[0013] Furthermore, the present invention relates to a method for functionalizing a textile article, wherein the method comprises providing a textile article comprising a first polymer (at least on one surface of the textile article), optionally with a first binding site (reactive group) on a surface, and at least partially covering (coating) the first polymer with a second polymer, wherein the second polymer comprises a siloxane copolymer, the siloxane copolymer comprising at least one (hydrophobic) block of a plurality of siloxane monomer units and at least one (hydrophilic) block of a plurality of further monomer units. At least one of the further monomer units has a first ionic group (as a side chain or in a side chain), wherein the first ionic group is a cationic group.Additionally or alternatively, the second polymer, in particular at least one of the further monomer units, has a second binding site (reactive group) on a surface, and the process further comprises applying a functionalizing agent comprising a first ionic group, which is a cationic group, and a spacer to the surface of the second (and optionally first) polymer and binding the functionalizing agent to the second (and optionally to the first) binding site, such that the first ionic group is bound to the surface of the second (and optionally first) polymer via the spacer.

[0014] Furthermore, the present invention relates to a textile article obtainable by a method described herein.

[0015] Furthermore, the present invention relates to a method for binding (and thereby removing) an (undesirable / harmful) substance having a second ionic group on a surface, wherein the method comprises bringing the substance into contact with a textile object as described herein, wherein the second ionic group is charged oppositely to the first ionic group (so that the substance is bound to the first ionic group (by means of ionic interaction, physically)).

[0016] Further tasks and advantages of embodiments of the present invention will become apparent from the following detailed description.

[0017] DETAILED DESCRIPTION OF THE INVENTION

[0018] Further details of the present invention and other embodiments thereof are described below. However, the present invention is not limited to the following detailed description, which merely serves to illustrate the teachings of the invention.

[0019] It should be noted that features described in connection with one exemplary embodiment can be combined with any other exemplary embodiment. In particular, features described in connection with one exemplary embodiment of a textile article according to the invention can be combined with any other exemplary embodiment of a textile article according to the invention, as well as with any exemplary embodiment of a method according to the invention, and vice versa, unless expressly stated otherwise.

[0020] When a term is used with an indefinite or definite article, such as "ein," "eine," "eines," "der," "die," and "das" in the singular, this also includes the plural form, and vice versa, unless the context clearly indicates otherwise. The expressions "aufweisen" and "umfassen," as used here, do not only include the meanings "contain" or "include," but can also mean "consist of" and "essentially consist of."

[0021] Unless explicitly stated otherwise, the term “at least partially” or “at least a part (of)”, as used here, can mean at least 1% of it, at least 2% of it, at least 5% of it, at least 10% of it, at least 15% of it, at least 20% of it, at least 25% of it, at least 30% of it, at least 35% of it, at least 40% of it, at least 45% of it, at least 50% of it, at least 55% of it, at least 60% of it, at least 65% of it, at least 70% of it, at least 75% of it, at least 80% of it, at least 85% of it, at least 90% of it, at least 95% of it, at least 98% of it, at least 99% of it, and can also mean 100% of it.

[0022] In a first aspect, the present invention relates to a textile object.

[0023] For the purposes of this application, a “textile article”, which may also be referred to as a “textile” or “textile”, is understood in particular to be an article with a textile structure and includes, in particular, textile raw materials such as fibers or filaments (natural fibers, synthetic fibers, textile fibers) and linear (e.g. yarns, threads, twines), planar (e.g. woven, knitted, crocheted, braided, nonwoven and felt) and spatial textile structures (e.g. garments and the like) produced therefrom.

[0024] The textile object is not particularly restricted as long as it, and in particular a main body thereof, comprises a first polymer, which is present, in particular, at least on one surface of the textile object. The textile object, and in particular its main body, may also comprise two or more types of polymers or may also be composite materials made of a polymer and a non-polymeric substance. The textile object further comprises a second polymer that is different from the first polymer and covers at least part (of the surface) of the first polymer. The second polymer thus constitutes at least a partial coating (of the surface) of the first polymer (the main body). The second polymer comprises a siloxane copolymer, which is, in particular, essentially linear, i.e., little or not at all branched.

[0025] For the purposes of this application, a "polymer" is understood to mean, in particular, a structure with more than 10 monomer units (repeat units). A "copolymer" is understood to mean, in particular, a structure with more than 10 monomer units (repeat units) comprising at least two different types of monomer units. A "siloxane copolymer," which may also be referred to as a "siloxane hybrid polymer," is understood to mean, in particular, a structure with more than 10 monomer units (repeat units) comprising at least two different types of monomer units, at least one of which is a siloxane monomer unit. The different types of monomer units are arranged in blocks. The siloxane copolymer according to the invention is thus a (siloxane) block copolymer in which at least one block consists of siloxane monomer units.In the context of this application, a “siloxane monomer unit” is understood in particular to be a monomer unit with the general formula - [O-SiR2]-, where R may in particular stand for alkyl, alkoxy and / or phenyl.

[0026] According to an exemplary embodiment, the textile article consists of fibers, filaments, yarns (threads) and / or roving. For the purposes of this application, the term "roving" refers in particular to a bundle, strand, or multifilament yarn made of parallel filaments (continuous fibers), which is predominantly used in the manufacture of fiber-reinforced plastics or fiber-reinforced plastics.

[0027] According to an exemplary embodiment, the textile object is a textile fabric (woven, nonwoven, knitted, or laid fabric), a membrane, a filter, a wipe, a mask (e.g., a face covering, medical mask, FFP2 mask), a garment, a mattress cover, a bed cover, bed linen, cushions, a blanket, upholstered furniture, a seat cover (e.g., a seat cover for motor vehicles, trains, or aircraft), a carpet, a curtain, and / or a dressing (such as a wound dressing, bandage, or plaster). For the purposes of this application, the term "textile fabric" refers to a two-dimensional textile product, which may be woven or non-woven.

[0028] According to an exemplary embodiment, the second polymer is covalently bonded (i.e., via covalent bonds) to the first polymer. For this purpose, the second polymer and / or the first polymer (in particular, each on a surface thereof) has binding sites (reactive groups, functional groups) that can form a covalent bond (directly or via a crosslinking agent) with the other polymer, as is apparent to a person skilled in the art based on their general knowledge. A covalent bond between the second polymer and the first polymer offers the advantage of a stable and durable connection between the second and first polymers, which, for example, largely withstands washing in the case of a textile.

[0029] According to an exemplary embodiment, the second polymer is bound to the first polymer only at specific points (i.e., at a few binding sites). This ensures that the desired properties of the first polymer and the textile object are affected as little as possible. Furthermore, by binding or fixing the second polymer to the first at only specific points, the flexibility of the second polymer, and thus its adaptability to certain undesirable or harmful substances, can be increased. In particular, this allows the second polymer to be bound to the first polymer in a particularly advantageous manner, such that the second polymer forms a loop with, on, or at the surface of the first polymer.Such elastic loops made of the second polymer can significantly contribute to a flexible yet targeted and, as needed, adjustable ionic finish of the textile object. Furthermore, they ensure that unwanted or harmful substances are not only bound through ionic interactions but can also be trapped sterically or structurally. In addition, such elastic loops made of the second polymer, which comprises a siloxane copolymer, can create an improved soft feel, for example, in a textile object.

[0030] According to an exemplary embodiment, the first polymer is selected from the group consisting of cellulose, polyamide (both synthetic and natural), polyester, chitosan, polyurethane, polyvinyl halide, epoxy, (functionalized) polyolefin, in particular polyethylene or polypropylene, polyethylene terephthalate, ethylene-vinyl alcohol copolymer (EVOH), and polyacrylonitrile (PAN). Combinations of polymers or copolymers may also be used. Where a polymer is mentioned below, a copolymer is always implied.

[0031] According to an exemplary embodiment, the first polymer has a three-dimensional structure. A three-dimensional structure of the first polymer, at least partially covered with a (essentially linear) siloxane copolymer, can provide further degrees of freedom and possibilities, and, as mentioned above, can result in a construct with dendrite-like three-dimensional docking sites that is particularly suitable for the reversible binding of protein structures of widely varying sizes, charge densities, and secondary or tertiary structures. A helical structure as a three-dimensional structure, such as that found in a cellulose chain, has proven particularly advantageous for this purpose.

[0032] The siloxane copolymer comprises at least one (hydrophobic, nonpolar) block made up of a plurality of siloxane monomer units and at least one (hydrophilic, polar) block made up of a plurality of further monomer units, wherein at least one of the further monomer units has a first ionic group. In particular, the at least one block made up of a plurality of siloxane monomer units is less hydrophilic and / or less polar than the at least one block made up of a plurality of further monomer units. The siloxane copolymer can comprise several blocks, in particular at least 5, in particular at least 10, in particular at least 15, made up of a

[0033] Multiple siloxane monomer units and / or several blocks, in particular at least 5, in particular at least 10, in particular at least 15, from a

[0034] Each block consists of a plurality of further monomer units.

[0035] Each siloxane monomer unit can independently comprise at least 5, in particular at least 10, and in particular at least 15, siloxane monomer units. Each block of a plurality of further monomer units can independently comprise at least 5, in particular at least 10, and in particular at least 15, further monomer units.

[0036] According to an exemplary embodiment, the further monomer units forming the at least one (hydrophilic or polar) block are different from the siloxane monomer units forming the at least one (hydrophobic, nonpolar) block. The siloxane copolymer can also comprise several different (hydrophilic or polar) blocks with several (in particular two or three) different monomer units, preferably with one block consisting of (only) one monomer unit. At least one further monomer unit has a first ionic group. The first polymer can be covalently bonded to at least one further monomer unit. It is possible that one (i.e., one and the same) further monomer unit has both the first ionic group and the first polymer is covalently bonded to it. However, it can be advantageous, for example with regard to the synthesis or…A more flexible application of the siloxane copolymer is possible if a (first) additional monomer unit has the first ionic group and the first polymer is covalently bonded to another (second) additional monomer unit. Additionally or alternatively, the first polymer can also be covalently bonded to a siloxane monomer unit, for example, in the case of a vinylalkoxysiloxane monomer unit.

[0037] According to an exemplary embodiment, a hydrophobic block contains, in addition to a (hydrophobic) siloxane monomer unit, at least one hydrophilic monomer unit, and / or a hydrophilic block contains, in addition to a further (hydrophilic) monomer unit having a first ionic group, at least one hydrophilic monomer unit. In other words, the hydrophobic or hydrophilic blocks can be modified by incorporating sub-blocks with different lipophilicity / hydrophilicity. This can reduce the otherwise very pronounced hydrophobic or hydrophilic properties of the corresponding polymer blocks, thereby improving the emulsifiability or dispersibility of the siloxane copolymer. This can be particularly advantageous in blended textiles such as cellulose / PET, cellulose / IPP, polyamide / PET, or semipolar fibers such as PAN, PVA, or acetate rayon, as the first polymer, in order to optimize the desired results.In a hydrophobic block, this can be achieved, for example, by incorporating poly(oxyethylene) or poly(oxypropylene) copolymer blocks or PEG or PPG diamines (e.g., using commercially available Jeffamine) into the block, preferably as terminal elements. In a hydrophilic block, the distances between the first ionic groups can be increased by using neutral co-monomers, i.e., without charge carriers, thereby reducing the hydrophilicity. Similar effects can also be achieved by substituting lower alkyl groups (C1 to C3) with longer alkyl chains, preferably (C6 to C20). Such substitution is particularly effective for substituents on the quaternary nitrogen atom of the first ionic group, e.g., methyl tetradecylamino instead of dimethylamino. Intermediates for the synthesis of such variants are usually commercially available, and methods for carrying out these variations are familiar to those skilled in the art.

[0038] According to an exemplary embodiment, the at least one siloxane monomer unit is selected from the group consisting of dimethylsiloxane, tetramethyldisiloxane, vinylsiloxane, vinylalkoxysiloxane (alkyoxyvinylsiloxane), and combinations thereof. These siloxane monomer units have proven to be particularly suitable for solving the problem according to the invention.

[0039] According to an exemplary embodiment, one or more further (other) monomer units are selected from the group consisting of vinyl, allyl, methallyl, acrylic, methacryl, and combinations thereof. The terms "vinyl," "allyl," "methallyl," "acrylic," and "methacrylic," as used herein, correspond to their generally accepted meanings. A vinyl can be represented by the general formula "H₂C=CH⁻," an allyl can be represented by the general formula "H₂C=CH-CH₂⁻," a methallyl can be represented by the general formula "H₂C=C(CH₃)-CH₂⁻," an acrylic can be represented by the general formula "H₂C=CH-C(=O)-O⁻," and a methacrylic can be represented by the general formula "H₂C=C(CH₃)-C(=O)-O⁻." A "(meth)acrylic" can comprise an acrylic and / or a methacrylic. These general further monomer units are suitable for solving the problem according to the invention.

[0040] According to an exemplary embodiment, the one or more further (other) monomer unit(s) comprise at least one monomer unit from the group consisting of allyl glycidyl ether, diallyldimethylammonium chloride (DADMAC), and diallylamine. These specific further monomer units have proven to be particularly suitable for solving the problem according to the invention. For example, the secondary amino group of diallylamine can be used for the point-linking of the second polymer to the first polymer.

[0041] According to an exemplary embodiment, the siloxane copolymer comprises a compound as represented by the general formula below:

[0042] A - [(Polysiloxane - C - Polysiloxane) - A - B - (Polycation - D - Polycation) - B] x (hydrophobic block) (hydrophilic block) where:

[0043] Polysiloxane stands for one or more siloxane monomer unit(s);

[0044] Polycation for one or more further monomer unit(s) with a first ionic group;

[0045] A represents a functional group that can form a covalent bond with B, in particular one of the following functional groups: -CH=CH2, -CH2OH, -NH2, -NHR, -NCO, -SH, -CH2, -Halogen, -Glycidyl, -COOH, -Si-O-Alkyl, where R can in particular represent alkyl;

[0046] B represents a functional group that can form a covalent bond with A, in particular one of the following functional groups: -CH=CH2, -CH2OH, -NH2, -Si-O-alkyl;

[0047] C and D represent binding sites that can each bind independently to the first polymer, either directly or via a difunctional crosslinking agent, in particular a diisocyanate, a diamine, a diepoxide, a diaziridine, and / or a dichlorohydrin, wherein at least one of C and D is present and each independently forms 0.01 to 20 mol% of the respective block, preferably wherein C forms 0.1 to 1 mol% of the hydrophobic block and / or D forms 1.0 to 5 mol% of the hydrophilic block. If "A - B" is a reactive group that can itself form a covalent bond with the surface of the first polymer, "A - B" can be used as a binding site for the first polymer either in addition to, or instead of, C and / or D. For example, for A = epoxide and B = secondary amine, "A - B" is: -CH(OH)-CH2NRR.The OH group can react with hydroxyl groups of cellulose to form ethers or bind with -CONH- (the amide group of a polyamide). If necessary, such reactions can be accelerated by catalysis, but can also lead to loosely cross-linked bonds between the second polymer and the first polymer by means of additional cross-linking agents such as isocyanates or aziridines.

[0048] According to an exemplary embodiment, the siloxane copolymer comprises a compound as represented by the general formula below:

[0049] A - [(PS) X - (C) v1 - (PS) y ] - A - B - [(PK) z1 - (D) V2 - (PK) Z2 ] - B where:

[0050] PS for a siloxane monomer unit -SiR 1 R 2 O- with R 1 = Methyl or Phenyl and R 2= Methyl; x and y are independently integers from 10 to 1500, in particular integers from 10 to 500, preferably integers from 20 to 300;

[0051] PK represents a further monomer unit having a first ionic group; z1 and z2 are independently an integer from 100 to 30000, in particular an integer from 250 to 10000, preferably an integer from 20 to 500;

[0052] A represents a functional group that can form a covalent bond with B, in particular one of the following functional groups: -CH=CH2, -CH2OH, -NH2, -NHR, -NCO, -SH, -CH2, -Halogen, -Glycidyl, -COOH, -Si-O-Alkyl, where R can in particular represent alkyl;

[0053] B represents a functional group that can form a covalent bond with A, in particular one of the following functional groups: -CH=CH2, -CH2OH, -NH2, -Si-O-alkyl;

[0054] C and D represent binding sites that can each bind independently of one another directly or via a difunctional crosslinking agent, in particular a diisocyanate, a diamine, a diepoxide, a diaziridine, and / or a dichlorohydrin, to the first polymer, where v1 = 0 to 1, in particular 0 to 1 mol% of the hydrophobic block; v2 = 1 to 5, in particular 1.0 to 5 mol% of the hydrophilic block. According to an exemplary embodiment, the first ionic group is directly bonded (i.e., without a spacer as described below, but directly in the side chain or as a side chain of the at least one further monomer unit) to the at least one further monomer unit. A suitable example of the first ionic group being bonded in a side chain is diallyldimethylammonium chloride (DADMAC) as the further monomer unit.Such direct binding of the first ionic group enables a particularly stable and targeted bond. Furthermore, additional functionalization steps, such as the application and binding of a functionalizing agent, can be omitted.

[0055] According to another exemplary embodiment, the first ionic group is bonded to the second polymer, in particular to the further monomer unit, via a spacer. In the context of this application, the term "spacer" refers to a plurality or chain of atoms arranged between a first ionic group and (a bonding site) a surface of the second (and optionally first) polymer. The spacer ensures that the first ionic group is positioned at a certain distance from the surface of the textile object, a distance which can be precisely adjusted via the length of the spacer. Furthermore, the quantity / number of spacers also allows for precise control of the quantity / number of first ionic groups and thus the charge density or charge distance of the textile object.Furthermore, even with point-like attachment to the first polymer, the mobility of the first ionic group can be maintained, or even expanded, depending on the length of the spacers.

[0056] According to an exemplary embodiment, the second polymer (particularly on one of its surfaces) has binding sites (reactive groups, functional groups) to which (at least on some of them) a first ionic group is bound via a spacer. Additionally, the first polymer (particularly on an uncovered surface) can also have binding sites (reactive groups, functional groups) to which (at least on some of them) another first ionic (cationic) group is bound via another spacer. This second first ionic group can be the same as or different from the first ionic group bound to the second polymer via a spacer. Likewise, the second spacer bound to the first polymer can be the same as or different from the spacer bound to the second polymer.By providing a first ionic group on the second polymer as well as another first ionic group on the first polymer, a wide variety of functionalization combinations can be achieved, which, in addition to binding unwanted or harmful substances, can also serve other purposes, such as coloring.

[0057] According to one exemplary embodiment, the spacer is covalently bonded to (a bonding site on) the surface of the second (and optionally the first) polymer. This enables a particularly strong and durable bond of the spacer, including the first ionic group, to the textile object, thus ensuring stable and permanent functionalization of the textile object. Alternatively, depending on requirements, the spacer can also be bonded to (a bonding site on) the surface of the polymer or the textile object via van der Waals forces and / or hydrogen bonds. This can be particularly advantageous if a less strong or only temporary functionalization of the textile object is desired, or if the textile object, especially its second (and optionally the first) polymer, would be impaired or damaged by covalent bonds (particularly during their formation through chemical reactions).

[0058] According to an exemplary embodiment, the spacer is bonded to the surface of the second (and optionally first) polymer via at least one amide bond, one ether bond, one ester bond, and one urethane bond. This allows for the functionalization of a wide variety of polymer types in diverse ways.

[0059] According to an exemplary embodiment, the spacer comprises a (preferably divalent) group selected from the group consisting of a linear or branched, saturated or unsaturated, substituted or unsubstituted alkylene group; a linear or branched, saturated or unsaturated, substituted or unsubstituted heteroalkylene group; a saturated or unsaturated, substituted or unsubstituted cycloalkylene group; a saturated or unsaturated, substituted or unsubstituted heterocycloalkylene group; a substituted or unsubstituted arylene group; a substituted or unsubstituted heteroarylene group; or a silicon-containing bivalent group.The meanings of the terms "linear," "branched," "saturated," "unsaturated," and "unsubstituted," as used herein, correspond to their respective established meanings as known to a person skilled in the art. The term "substituted," as used herein, means that one or more, in particular 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, hydrogen atoms of the respective groups are substituted by a substituent. Examples of suitable substituents include halogen atoms such as -F, -CI, -Br, -I, -OH; hydroxyalkyl groups (ethers), -SH, thioalkyl groups (thioethers), α0, ester groups, amide groups, nitrile groups, and nitro groups. If two or more substituents are present, they may be the same or different and may be linked together to form a ring. The terms "heteroalkylene group", "heterocycloalkylene group" and "heteroarylene group" stand for an alkylene group, a cycloalkylene group, and a cycloalkylene group, respectively.An arylene group, wherein one or more, in particular 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, carbon atoms are replaced by a heteroatom, such as O, N or S, in particular O and / or N. If more than one heteroatom is contained in a group, these heteroatoms may be the same or different.

[0060] Suitable examples for the alkylene group include C1 to C20 alkylene groups, in particular C2 to C10 alkylene groups, in particular C3 to C8 alkylene groups, and in particular C4 to C6 alkylene groups.

[0061] Suitable examples of the cycloalkylene group include C3 to C20 cycloalkylene groups, in particular C4 to C15 cycloalkylene groups, in particular C5 to C10 cycloalkylene groups, and in particular C6 to C8 cycloalkylene groups.

[0062] Suitable examples of the arylene group include C6 to C20 arylenes, in particular C6 to C16 arylenes, in particular C6 to C14 arylenes, and in particular C6 to C10 arylenes. In particular, the arylene group can be a phenylene group.

[0063] The "silicon-containing bivalent group" can include, in particular, groups containing one or more silicon (Si) atoms and, optionally, one or more of, for example, carbon, oxygen, nitrogen, phosphorus, and / or hydrogen atoms. Suitable examples include [Si-dialkyl]- (or [alkyl-Si-alkyl]-), [alkyl-Si-alkoxy]-, and [Si-dialkoxy]- (or [alkoxy-Si-alkoxy]-). The first ionic group is a cationic (partially positively charged) group. This allows, in particular, the binding of partially negatively charged substances, as is often the case with peptides and proteins. According to the literature, 85% of protein structures have an excess of acidic amino acids and are therefore partially negatively charged. For example, a significant allergen from house dust mite feces, DerP1, has an excess of acidic amino acids and can thus be bound by a cationically functionalized surface.

[0064] Suitable examples of cationic groups include a (primary, secondary, tertiary) amino group, a (quaternary) ammonium group, a guanidino group, an aminocarboxyl group (as in amino acids), an imidazole group, an imidazoline group, a triazole group, a tetrazole group, a creatinine group, a betaine group, a (primary, secondary, tertiary) phosphine group, and a (quaternary) phosphonium group. Different cationic groups can also be combined as primary ionic groups, for example, a permanently charged cationic group, such as an ammonium group, and a pH-dependent charged cationic group, such as a primary amino group.

[0065] According to one exemplary embodiment, the first ionic group is a permanently charged group. In particular, it can be advantageous that the charge state of the first ionic group does not depend on the pH value when, for example, it comes into contact with water. This allows a constant binding capacity to be achieved, regardless of the environmental conditions. A suitable example of a permanently charged (cationic) group is a (quaternary) ammonium group.

[0066] According to another exemplary embodiment, the first ionic group is a pH-dependent (temporarily) charged group; that is, the charge state of the first ionic group depends on the pH value when it comes into contact with, for example, water. This allows the charge state and thus the charge density of the textile object to be adjusted as needed. Suitable examples of a pH-dependent charged (cationic) group include a primary, secondary, or tertiary amino group, as well as a guanidino group.

[0067] According to an exemplary embodiment, the distance of the first ionic group to the surface of the second (or, if applicable, first) polymer or textile object can be specifically adjusted by selecting the spacer, thus accommodating, for example, the folding of peptide structures. The (average) distance of the first ionic group to the surface of the second (or, if applicable, first) polymer or textile object, as well as the (average) molecular length of the spacer, can be calculated, in particular, based on the (known) bond lengths between the atoms in the spacer molecule. The (average) distance of the first ionic group to the surface of the second (or, if applicable, first) polymer or textile object, as well as the (average) molecular length of the spacer, can be determined, for example, using an electron microscope.a transmission electron microscope (TEM) or a high-resolution scanning electron microscope (SEM).

[0068] Suitable examples of spacers and their corresponding lengths are given in the table below: The length of the spacers can be increased if required. Common methods of preparative chemistry, based on polymer-analogous synthesis methods, are suitable for this purpose. Examples include: chain extension by addition and / or condensation reactions, e.g., using native or disguised diisocyanates, dicarbonimides, bis-2-oxazolines, bis-acyl-lactamates, bifunctional silanes and siloxanes, diepoxides, alkylene oxides, and bis-aziridines.

[0069] According to an exemplary embodiment, the spacer has an (average) distance of 1 to 100 nm, in particular 2 to 50 nm, and in particular 5 to 25 nm, to an adjacent spacer, especially the nearest adjacent spacer. The distance between adjacent spacers, and thus the charge density, can be specifically adjusted by selecting the spacer (for example, its steric extent) or by the number of spacers per surface unit. This can be particularly important when binding large protein units and can also take other steric effects into account. The (average) distance of the spacer to an adjacent spacer can be determined, for example, using an electron microscope, such as a transmission electron microscope (TEM) or a high-resolution scanning electron microscope (SEM).

[0070] According to an exemplary embodiment, the surface of the second (or, if applicable, first) polymer or the textile object has binding sites (reactive groups, functional groups), wherein a spacer is bonded to 0.5 to 20%, particularly 1 to 10%, and particularly 2 to 5% of the binding sites. The remaining binding sites can, in this case, be essentially unbound (free), in particular essentially free of spacers and / or ionic groups. This also allows the binding capacity of the functionalized surface to be adjusted as required and makes it particularly suitable for binding larger, sterically demanding molecules.

[0071] According to one exemplary embodiment, a substance having a second ionic group on its surface can be bound to, or be bound to, the first ionic group (by means of ionic interaction, i.e., physically). For this to occur, the second ionic group should be charged oppositely to the first ionic group. Since the first ionic group is a cationic group, the second ionic group should therefore be an anionic or (partially) negatively charged group. According to one exemplary embodiment, the substance is essentially permanently or irreversibly bound to the first ionic group. This is particularly advantageous if the substance is a nuisance or harmful substance that should be bound as permanently as possible and thus removed from the environment.

[0072] According to another exemplary embodiment, the substance is reversibly (latently) bonded to the first ionic group. This is particularly advantageous when only a temporary bonding of the substance to the textile object is desired, for example, when the substance is to be removed again by washing (e.g., a textile).

[0073] For example, the substance can be a pharmaceutical and / or a cosmetically active substance that is intended to be released by the textile object. A textile object according to the invention, for example, a dressing material (such as a wound dressing, bandage, or plaster), can thus be equipped with a pharmaceutically active substance, such as a peptide drug, an anti-inflammatory drug, and / or an antibiotic drug, which can be released in a delayed manner over a longer period if required. Such a delayed release can also be adjusted as needed through targeted functionalization according to the invention.

[0074] According to one exemplary embodiment, a drug substance can be reversibly (latently) or permanently bound to the first ionic group. Examples of such drugs include anionic fungicides and bactericides, such as piroctone, octopirox, ciclopirox, pyrithione, and perillic acid. This may be of particular interest for filters and topical medical applications.

[0075] According to an exemplary embodiment, the substance is selected from the group consisting of peptides, proteins, microorganisms such as bacteria, viruses, yeasts and fungi, metabolic products such as allergens, toxins, enzymes, microorganisms such as mites, and organic material with peptide surface structures such as spores, pollen, skin particles and mite eggs. These are predominantly disruptive or harmful substances that are usually intended to be permanently bound to the textile object or that are intended to be removed again, for example by washing, i.e., they are reversibly bound.

[0076] In a further aspect, the present invention relates to a method for functionalizing a textile object. As a result of the functionalization method, a textile object according to the first aspect, as described above, can be obtained. The method can therefore also be described as a method for manufacturing a (functionalized) textile object.

[0077] The textile object to be functionalized can be, for example, fibers, filaments, yarns (threads) and / or roving, or a textile surface structure (woven fabric, nonwoven, knitted fabric, laid fabric), a membrane, a filter, a wipe, a mask (e.g., a face covering, medical mask, FFP2 mask), a garment, a mattress cover, a bed cover, bed linen, cushions, a blanket, upholstered furniture, a seat cover (e.g., a seat cover for motor vehicles, trains or airplanes), a carpet, a curtain and / or a dressing material (such as a wound dressing, a bandage or a plaster).

[0078] In a first step, a textile object that has a first polymer (at least on one surface of the textile object) is optionally provided with a first binding site (reactive group) on a surface.

[0079] According to an exemplary embodiment, the first polymer located on a surface of the textile object has binding sites or reactive groups. Suitable examples of such polymers include cellulose, ethylene-vinyl alcohol copolymer (EVOH) (with a hydroxyl group (-OH)), polyamides (with an amide group (-CONH-)), polyesters (with an ester group (-COO-)), chitosan (with an amino group (-NH2)), polyurethane (with a urethane group (-NH-COO-)), polyvinyl halides (with a halogen, for example, chlorine (-CI)), epoxides (with, for example, -CH(OH)-CH2-NH-), and polyacrylonitrile (with a nitrile group (-CN)). In these cases, no special surface treatment is required to create binding sites on the surface, but it can nevertheless be carried out, for example, to reinforce or optimize the binding sites or for other reasons.

[0080] According to another exemplary embodiment, the first polymer located on a surface of the textile object inherently has no (suitable) or only a few or only slightly reactive binding sites. Examples of such polymers include polyolefin, in particular polyethylene or polypropylene, and polyethylene terephthalate. According to an exemplary embodiment, providing the textile object with a first binding site on a surface thus involves a surface treatment to form binding sites on the surface of the textile object or the first polymer. According to an exemplary embodiment, the surface treatment is selected from the group consisting of plasma treatment, oxidation treatment, and flame treatment (flame treatment).In particular, plasma treatment, especially using reactive gas or gas mixtures containing, for example, ammonia or hydrazine, enables a wide range of binding sites on polymer surfaces.

[0081] In a further step, the first polymer is at least partially covered or coated with a second polymer, the second polymer comprising a siloxane copolymer. The siloxane copolymer comprises at least one (hydrophobic) block consisting of a plurality of siloxane monomer units and at least one (hydrophilic) block consisting of a plurality of further monomer units. According to one embodiment, at least one of the further monomer units has a first ionic group (as a side chain), wherein the first ionic group is a cationic group. According to another embodiment, the second polymer, in particular at least one of the further monomer units, has a second binding site (reactive group) on a surface. The at least partial covering or coating of the first polymer with the second polymer is not particularly restricted and can be carried out in a manner familiar to a person skilled in the art.Preferably, a chemical reaction takes place, in particular forming covalent bonds between the first and the second polymer. For this purpose, the first polymer and / or the second polymer has suitable binding sites or reactive groups, for example, in one of the further monomer units and / or in a siloxane monomer unit of the siloxane copolymer. Furthermore, preferably, the chemical reaction between the first and the second polymer takes place such that the second polymer binds to the first polymer only at specific points (i.e., at a few binding sites), and in particular such that the second polymer forms a loop with, on, or at the surface of the first polymer. A point-based binding of the second polymer to the first polymer can be achieved, for example, by the siloxane copolymer having relatively few suitable binding sites.The number of reactive groups per chain length (for example, secondary amino groups of diallylamine as one of the monomer components of the siloxane copolymer) is relatively high compared to the number of suitable binding sites or reactive groups on the surface of the first polymer. This allows the polymer chain segments between two reactive groups of the siloxane copolymer to protrude from the first polymer. This protrusion, and the associated loop formation, is further intensified by the fact that the siloxane copolymer comprises at least one (hydrophobic) block consisting of multiple siloxane monomer units and at least one (hydrophilic) block consisting of multiple other monomer units. These monomers exhibit varying affinities for the surface of the first polymer, and depending on the hydrophilicity / hydrophobicity of the first polymer's surface, the hydrophobic blocks tend to protrude more readily.Rather, the hydrophilic blocks of the siloxane copolymer detach from the surface of the first polymer and form corresponding loops on or at the surface of the first polymer.

[0082] According to an exemplary embodiment, the first and / or second binding site, which can also be referred to as a reactive group, is one of the following: a hydroxyl group (-OH), a carboxyl group (-COOH), an amide group (-CONH-), an ester group (-COO-), a carbonyl group (-CO-), in particular a ketone group or an aldehyde group, an amino group (-NH2), a urethane group (-NH-COO-), a halogen, in particular chlorine (-CI) or bromine (-Br), and an epoxide group (oxirane group). Combinations of different binding sites are also possible, especially when different functionalizing agents are to be applied, which can, for example, create different binding options for one or more substances to be removed. For example, the first binding site (on the first polymer) can be different from the second binding site (on the second polymer).

[0083] According to an exemplary embodiment, particularly when the first ionic group is to be bound to the second polymer, especially to the further monomer unit, via a spacer, a functionalizing agent comprising a first ionic group and a spacer is applied to the surface of the second (and optionally first) polymer or the textile object in a further step. Several different functionalizing agents can also be applied. For example, a (first) functionalizing agent comprising the spacer can be applied first, followed by a further (second) functionalizing agent comprising the first ionic group. The first functionalizing agent can be applied to the second (and optionally first) binding site on the surface of the second (and optionally first) polymer or the textile object.first) polymers are bound before the second functionalizing agent is applied, which in turn is bound to the first functionalizing agent (especially to a suitable functional group thereof).

[0084] The application of the functionalizing agent, which is preferably applied dissolved or dispersed in a solvent, is not particularly limited and can be carried out in any suitable manner known to a person skilled in the art. For example, the functionalizing agent can be applied by spraying onto the surface of the polymer or the textile article, or the textile article can be immersed in the functionalizing agent. A foulard process (i.e., a process using a foulard) can also be employed, which is particularly suitable for functionalizing a textile article. A foulard typically comprises a system of two or more rollers and a trough (also called a chassis) for holding a bath of the functionalizing agent.In the foulard process, the textile is typically immersed in the liquor in its widest state, and then the excess absorbed liquor is evenly removed across the entire width of the fabric using rollers. However, the functionalizing agent can also be applied to the surface of the second (and possibly first) polymer or the textile object by vapor deposition (without being dissolved or dispersed in a solvent such as water).

[0085] The functionalizing agent comprises a first ionic group and a spacer. This can be, in particular, a first ionic group or a spacer, as explained in detail above in connection with the first aspect.

[0086] According to an exemplary embodiment, the functionalizing agent further comprises a functional group capable of interacting, and in particular reacting, with the second (and optionally the first) binding site on the surface of the second (and optionally the first) polymer or the textile object. This allows for a (strong) bond between the functionalizing agent and the surface of the second (and optionally the first) polymer or the textile object. In particular, the functional group of the functionalizing agent can advantageously react with the second (and optionally the first) binding site on the surface of the second (and optionally the first) polymer to form a covalent bond.According to an exemplary embodiment, the functional group is selected from the group consisting of a hydroxyl group (-OH), a carboxyl group (-COOH), an amide group (-CONH-), an ester group (-COO-), a carbonyl group (-CO-), in particular a ketone group or an aldehyde group, an amino group (-NH2), a urethane group (-NH-COO-), a halogen, in particular chlorine (-CI) or bromine (-Br), and an epoxide group (oxirane group). The selection of the functional group of the functionalizing agent is made in particular taking into account the nature of the second (and optionally first) binding site on the surface of the second (and optionally first) polymer. For example, if the binding site comprises a hydroxyl group or an amino group, the functional group of the functionalizing agent may in particular comprise a carboxyl group, and vice versa.

[0087] According to an exemplary embodiment, the functionalizing agent is an oligomer and / or a copolymer, in particular a terpolymer. For the purposes of this application, an "oligomer" is understood to mean, in particular, a structure with up to ten monomer units, for example, two to eight monomer units. For the purposes of this application, a "copolymer" is understood to mean a polymer with at least two different monomer units. For the purposes of this application, a "terpolymer" is understood to mean a polymer with (exactly) three different monomer units.

[0088] According to an exemplary embodiment, the functionalizing agent is a terpolymer comprising a first monomer, a second monomer and a third monomer, wherein the first monomer comprises the first ionic group, the second monomer comprises the spacer and the third monomer comprises a functional group capable of interacting, in particular reacting, with the second (and optionally first) binding site on the surface of the second (and optionally first) polymer or the textile object.

[0089] According to an exemplary embodiment, the first monomer is a cationic monomer, the second monomer is a neutral (uncharged) monomer, and the third monomer is an anionic monomer. For a particularly easy-to-produce terpolymer, the first monomer can be a cationic vinyl monomer (e.g., 2-(dimethylamino)ethyl acrylate), the second monomer can be a neutral vinyl monomer (e.g., methyl methacrylate), and the third monomer can be a carboxyl-containing vinyl monomer (e.g., acrylic acid). The third monomer can, for example, bind to a binding site of the polymer, in particular a hydroxyl group, such as a primary hydroxyl group of cellulose, and the first monomer can provide a cationic group as the first ionic group. The length of the spacer can, in turn, be adjusted by the number of second (neutral) monomers.Another advantage of such terpolymers is that they are either readily soluble in water or easily emulsifiable. Suitable examples of the second monomer include acrylates, methacrylates, maleate esters, and styrene. A suitable example of the first monomer is diallyldimethylammonium chloride, which can provide a permanently positively charged first ionic group.

[0090] According to an exemplary embodiment, a substoichiometric amount of functionalizing agent is applied to the second (and optionally the first) binding site. In particular, it can be advantageous for the (molar) ratio of functionalizing agent to the second (and optionally the first) binding site to be in the range of 1:200 to 1:5, particularly from 1:100 to 1:10, and especially from 1:50 to 1:20. This allows the degree of functionalization or the charge density of the polymer surface to be adjusted in a particularly simple manner, for example, so that only 0.5 to 20%, particularly 1 to 10%, and especially 2 to 5% of the second (and optionally the first) binding sites of the spacer are bound, while the remainder of the second (and optionally the first) binding sites are essentially unbound (free).

[0091] According to an exemplary embodiment, particularly when the first ionic group is to be bound to the second polymer, especially to the further monomer unit, via a spacer, the functionalizing agent is bound to the second (and optionally the first) binding site in a further step such that the first ionic group is bound to the surface of the second (and optionally the first) polymer or the textile object via the spacer. In other words, the functionalizing agent is bound to the second (and optionally the first) binding site in such a way that the first ionic group is directed away from the binding site.

[0092] According to an exemplary embodiment, binding the functionalizing agent to the second (and optionally first) binding site comprises a chemical reaction forming a covalent bond (between the functionalizing agent, in particular its functional group, and the second (and optionally first) binding site). According to an exemplary embodiment, binding the functionalizing agent to the second (and optionally first) binding site comprises heating to a temperature in the range of 50 to 220 °C, in particular 100 to 200 °C, in particular 150 to 190 °C, in particular 160 to 180 °C, for a period of 5 s to 5 min, in particular 10 s to 2 min, in particular 15 s to 60 s.

[0093] In another aspect, the present invention relates to a textile object that is obtainable or obtained by a functionalization method as described above.

[0094] In another aspect, the present invention relates to a method for binding (and thereby removing) an (undesirable / harmful) substance.

[0095] The substance can be, in particular, a peptide, protein, microorganism such as bacteria, viruses, yeasts and fungi, metabolic product such as allergens, toxins, enzymes, microorganisms such as mites, organic material with peptide surface structures such as spores, pollen, skin particles and mite eggs.

[0096] The process involves bringing the material into contact with a (functionalized) textile object, as described above, which has a first ionic group. The material has a second ionic group on one surface, which is oppositely charged to the first ionic group. This allows the material to be bonded to the first ionic group (by means of ionic interaction, i.e., physically).

[0097] According to one exemplary embodiment, the substance is reversibly bonded to the first ionic group. This is particularly advantageous when only a temporary bonding of the substance to the textile object is desired, for example, when the substance is to be removed again by washing (e.g., a textile).

[0098] The present invention is further described with reference to the following examples, which, however, serve only to illustrate the teachings of the invention and are in no way intended to limit the scope of the present invention. Examples

[0099] The following describes examples of the synthesis of siloxane copolymers according to the invention, their "hydrophobic siloxane blocks" and "hydrophilic cation blocks," as well as their attachment to a first polymer for its functionalization. The examples are based on synthesis steps familiar to a person skilled in the art, so no detailed synthesis procedures are given; rather, the synthesis routes are merely illustrated by way of example.

[0100] Example 1:

[0101] Hydrophobic siloxane blocks:

[0102] Basic synthesis steps: a) Hydrosylation of tetramethyldisiloxane or homologues thereof:

[0103] Addition of two synthesis building blocks or monomers, each with a vinyl, allyl, acrylic, or methacryl end group, to the terminal -SiH groups of the siloxanes used. This is typically achieved using platinum catalysis (e.g., hexachloroplatinic acid, Karstedt catalysts, Lukvics catalysts). Through this hydrosilation, the desired ligands, such as epoxide, amine, carboxylic acid, or hydroxyl, are bound to the H-siloxanes used, and these then serve as reaction partners with the hydrophilic cation blocks. b) Equilibration is a method for catalytically incorporating units into existing siloxane chains via ring-opening polymerization of cyclic siloxanes, thus leading to targeted siloxane chain elongation. Catalysts for this can be either alkaline (e.g., potassium alkoxide) or acidic (e.g., trifluoromethylbenzenesulfonic acid, perchloric acid, PNCI₂, but also phosphoric and sulfuric acid).This is primarily determined by the existing ligands on the hydrolyzed starting material. Suitable cyclic siloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. Depending on the stoichiometric ratios, catalysts, temperatures, and reaction time, long-chain polysiloxanes can be generated in a targeted manner, while still retaining the reactive ligands at the terminals. c) Incorporation of binding sites onto the first polymer.

[0104] Typically, docking sites (for binding to the first polymer) within the hydrophobic siloxane blocks are avoided to prevent interrupting loop formation. However, if necessary, a compound can be synthesized by combining two or more moderately long siloxane chains with suitable reactants exhibiting two or three functionalities (e.g., dialkanolamine, aminodicarboxylic acid, diaminecarboxylic acid). This compound not only extends the chain but also provides a reactive docking site within the siloxane chain structure. For example, epoxy-terminal siloxanes can be used to produce the desired product via such an intermediate. Both the resulting -OH, -NH-, and the remaining carboxyl group can function as docking sites for the first polymer.

[0105] Alternatively, by incorporating 0.1 - 1.0 mol percent vinyltrialkoxysilane in the hydrosilation stage, a covalent bonding of the point-like docking sites within the polysiloxane chain to the first polymer can be achieved during subsequent hydrolysis.

[0106] Example 2:

[0107] Hydrophilic cation blocks: a) Radical polymerization of vinyl compounds containing at least one cationic element, preferably tertiary or particularly preferably quaternary nitrogen, via a spacer. Examples (mostly commercially available) are cationically substituted (preferably with a quaternary nitrogen atom) acrylic esters, methacrylates, acrylamides, methacrylamides, vinyl ethers, maleates, and copolymers thereof. Besides, for example, tetraalkylammonium ethyl substituents, spacers such as those listed in the table above are also preferred. In these cases, the cations are always located in the side chain, preferably at every second carbon atom. The distance of the cationic side chain can be adjusted by copolymerization with vinyl compounds without cationic substituents. b) Radical polymerization of diallylamines

[0108] This leads, in a known manner, to polydimethylenetetrahydropyrrolidines via ring-closing polymerization, preferably with a quaternary nitrogen atom. Diallyldimethylammonium chloride (DADMAC) can preferably be considered a model substance here. By changing the substituents on the diallylamine, e.g., methyl tetradecyl diallylammonium chloride, highly effective cations are generated along the polymer chain as side chains. c) Addition synthesis using epoxides and amines

[0109] Basic reaction: Polyimines (e.g., polyethyleneimines, polypropyleneimines) react with (mostly commercially available) QIIABS, e.g.:

[0110] Q11AB 342: 3-Chloro-2-Hydroxypropyl-Dimethyl (Lauryl)ammonium chloride; Q11AB 426: 3-Chloro-2-Hydroxypropyl-Dimethyl (Stearyl)ammonium chloride; Q11AB 188: 3-Chloro-2-Hydroxypropyl-Dimethyl Trimethylammonium chloride; Q11AB 151: Epoxypropyl-Trimethylammonium chloride, each in slightly substoichiometric amounts to keep imine groups free for subsequent bonding reactions with siloxane blocks or docking reactions to the first polymer. d) Sol-gel structures, i.e., organic-inorganic hybrid structures with adjustable cation density:

[0111] Varying amounts of tetraalkoxysilane, cationic di- or trialkoxysilane such as trimethoxypropyl dimethyltetradecylammonium chloride (“POLON MF50” from Shin Etsu), and alkyltrialkoxy and / or phenyl alkyldialkoxysilanes are subjected to a common hydrolysis, usually in an alcoholic, acid-catalyzed solution, using stoichiometric amounts of water, leading to reactive silanols whose -OH groups are equally suitable for attachment to -OH terminal siloxane blocks (using diisocyanates) as well as for docking onto the first polymer.

[0112] The high density of such silanol groups therefore leads to a particularly close coupling to the first cellulose-based polymer, so that such sol-gel polymers are optimally coupled with hydrophobic siloxane blocks that have as few docking sites as possible and are thus particularly suitable for loop binding.

[0113] Example 3: Coupling of hydrophobic siloxane blocks according to Example 1 with hydrophilic catonic blocks according to Example 2:

[0114] Depending on the type of terminal reactive groups of both blocks, suitable reactants are available, as is readily known to those skilled in the art. For example: for epoxide terminal groups: diamines, possibly diols; for amine groups: diepoxides, diisocyanates; for carboxyl groups: diaziridines; for vinyl groups: a further polymerization step; for trialkoxysilane groups: co-hydrolysis

[0115] Note on examples 1 - 3:

[0116] Since all polymer reactions follow statistical laws, the predicted end products of the syntheses are not represented in (at best idealized) formula diagrams.

[0117] Accordingly, no purification of the end products is performed, recognizing that they are always a mixture of comparable substances. However, it is generally advisable to remove residual monomers, low-molecular-weight oligomers, unwanted solvent residues, etc., from the obtained end products. This can be achieved, for example, by distillation, ideally under vacuum, at temperatures of 50–150°C.

[0118] Example 4:

[0119] Functionalization of the first polymer

[0120] The synthesis products according to the invention (siloxane copolymer, second polymer) are generally in liquid or low-melting form, optionally also in water-dilutable solvents such as C1 - C4 alcohols or C3 - C4 ketones.

[0121] The final application form, i.e., a partially covalently bonded structure comprising the first and second polymers, is achieved, from an application-technical perspective, through the described fouling process.

[0122] This requires processing the second polymer into an aqueous solution or emulsion. The more balanced the ratio of hydrophobic and hydrophilic structural elements, the easier this task is to accomplish.

[0123] Ideally, this is achieved by mechanically homogenizing the second polymer with deionized water to the desired concentration.

[0124] Otherwise, using a variety of commercially available non-ionic detergents and dispersing agents.

[0125] The concentration is chosen so that in the subsequent fouling step, after impregnation, compression and thermal post-treatment (e.g. heating to a temperature in the range of 50 to 220 °C, in particular 100 to 200 °C, in particular 150 to 190 °C, in particular 160 to 180 °C, for a period of 5 s to 5 min, in particular 10 s to 2 min, in particular 15 s to 60 s) the second polymer bonds with the first polymer.

[0126] The proportions are 0.05–10%, preferably 0.1–5%, and particularly preferably 0.3–3% of the second polymer, based on the textile weight (i.e., of the first polymer). These values ​​are determined gravimetrically.

[0127] This foulard process does not differ from known methods.

[0128] In special cases, the second polymer can also be applied to the textile by spraying, brushing, pouring the solution, or emulsion. Thermal fixing, after an evaporation phase of the solvent, can be carried out as described above.

[0129] Example 5:

[0130] Investigation of the binding of various peptides to functionalized textiles

[0131] Investigations were carried out to determine the binding capacity of functionalized textile samples against various potentially allergenic peptides and / or pathogenic microorganisms (bacteria, fungi). The functionalized textile samples used were a textile article according to the invention, functionalized with a siloxane copolymer in which the cationic group is located in a side chain of the siloxane copolymer, and, as comparative examples, textile samples functionalized with siloxane block copolymers with cationic groups in the backbone of the block copolymer according to the prior art.

[0132] For this purpose, textile samples consisting of 52% TENCEL (cellulose) and 48% cotton, with a basis weight of 280 g / m², were used. 2, in analogy to Example 4, equipped by means of a fouling process with ultimately 0.8 - 1.0% (based on solids / fiber) of an aqueous solution or aqueous emulsion, whereby the following parameters were chosen:

[0133] Impregnation at 50 - 60°C

[0134] Roller compression / dewatering

[0135] Drying at 80°C / fan-assisted drying

[0136] Thermal post-treatment: 20 seconds at 180°C

[0137] Fabric samples of the same size were stirred for 15 minutes at room temperature in aqueous solutions / dispersions of peptides of the same concentration. The samples were then removed from the dispersion, rinsed, and the remaining liquid was analyzed for residual peptide content using an enzyme-linked immunosorbent assay (ELISA). This test method was performed in accordance with DIN 58967-30-1999 and is considered established in the field.

[0138] 1. The following comparison patterns were selected:

[0139] A) From DE 198 17 776 A1

[0140] Example 3 = A3

[0141] Example 5 = A5

[0142] Example 7 = A7

[0143] Example 9 = A9

[0144] B) From US 2010 / 0048795 A1

[0145] Example 3 = B3

[0146] Example 10 = B10

[0147] C) From US 2021 / 0388163 A1

[0148] Composition 1 from Table 2 = C1

[0149] 2. Inventional embodiment (hereinafter referred to as EC)

[0150] General formula:

[0151] A - [(PS) X - (C) v1 - (PS) y ] - A - B - [(PK) z1 - (D) V2 - (PK) Z2 ] - B

[0152] Hydrophobic block:

[0153] A - [(PS) X - (C)vi - (PS) y ] = Bis - Aminopropyl - Dimethyl - Polysiloxane; x + y = approx. 30, (C) vi = O

[0154] Hydrophilic block: statistical copolymer of: B = (glycidyl methacrylate) 1 mol

[0155] (PK)zi + (PK)Z2 = (methyl methacrylate) 40 mol

[0156] Cationic side chain = (Methacrylic acid dimethylaminoethyl ester) 10 mol

[0157] D = (Allylamine) 2 mol

[0158] Bonding of hydrophobic block and amine from D, as well as to textile using diisocyanate (hexamethylene diisocyanate trimer in H2O)

[0159] 3. Selected peptides or microorganisms

[0160] P1 = Mite fecal allergen. The p1

[0161] P2 = Staphylococcus aureus ATCC 6538

[0162] P3 = Klebsiella pneumoniae ATCC 4352

[0163] P4 = Aspergillus niger ATCC 6275

[0164] P5 = Bacitracin (anionic peptide antibiotic)

[0165] The following table shows the binding fraction (wt %) of peptides or microorganisms on the functionalized textile surfaces of the samples examined.

[0166] As can be seen from the above investigation results, by functionalizing a textile surface according to the invention with cationic groups in the side chain of the siloxane copolymer, all of the investigated peptides and microorganisms (bacteria, fungi) are bound significantly better than by functionalizing a textile surface with cationic groups in the backbone of a block copolymer according to the prior art. The present invention has been described with reference to specific embodiments and examples. However, the invention is not limited to these, and various modifications are possible without departing from the scope of the present invention.

Claims

REQUIREMENTS 1. Textile article comprising a first polymer and a second polymer, wherein the second polymer is different from the first polymer and covers at least part of the first polymer, wherein the second polymer comprises a siloxane copolymer, the siloxane copolymer comprising at least one block of a plurality of siloxane monomer units and at least one block of a plurality of further monomer units, wherein at least one of the further monomer units has a first ionic group, the first ionic group being a cationic group.

2. Textile article according to claim 1, wherein the second polymer is covalently bonded to the first polymer, and / or wherein the second polymer is spot-bonded to the first polymer, in particular wherein the second polymer is bonded to the first polymer in such a way that the second polymer forms a loop with, on or at the surface of the first polymer.

3. Textile article according to one of the preceding claims, wherein the first polymer is selected from the group consisting of cellulose, polyamide, polyester, chitosan, polyurethane, polyvinyl halide, epoxy, polyolefin, in particular polyethylene or polypropylene, polyethylene terephthalate, ethylene-vinyl alcohol copolymer and polyacrylonitrile, and / or wherein the first polymer has a three-dimensional structure, in particular a helical structure, and / or wherein a further first cationic group is bonded to the first polymer.

4. Textile article according to any of the preceding claims, wherein the at least one siloxane monomer unit is selected from the group consisting of dimethylsiloxane, tetramethyldisiloxane, vinylsiloxane, vinylalkoxysiloxane and combinations thereof, and / or wherein the one or more further monomer unit(s) is selected from the group consisting of vinyl, allyl, methallyl, acrylic, methacryl and combinations thereof, and / or wherein the one or more further monomer unit(s) comprises at least one monomer unit from the group consisting of allyl glycidyl ether, diallyldimethylammonium chloride (DADMAC) and diallylamine.

5. Textile article according to one of the preceding claims, wherein the cationic group is selected from the group consisting of an amino group, an ammonium group, a guanidino group, an aminocarboxyl group, an imidazole group, an imidazoline group, a triazole group, a tetrazole group, a creatinine group, a betaine group, a phosphine group and a phosphonium group, and / or wherein the first ionic group is a permanently charged group or wherein the first ionic group is a pH-dependent charged group, and / or wherein the first ionic group is a side chain or in a side chain of the siloxane copolymer, in particular of the at least one block consisting of a plurality of further monomer units. 6 Textile article according to one of the preceding claims, wherein the first ionic group is bound to the second polymer, in particular to the further monomer unit, via a spacer.

7. Textile article according to claim 6, wherein the spacer is covalently bonded to the surface of the second polymer, and / or wherein the spacer is bonded to the surface of the second polymer via at least one amide bond, ether bond, ester bond, and urethane bond, and / or wherein the spacer comprises a group selected from the group consisting of a linear or branched, saturated or unsaturated, substituted or unsubstituted alkylene group; a linear or branched, saturated or unsaturated, substituted or unsubstituted heteroalkylene group; a saturated or unsaturated, substituted or unsubstituted cycloalkylene group; a saturated or unsaturated, substituted or unsubstituted heterocycloalkylene group; a substituted or unsubstituted arylene group; a substituted or unsubstituted heteroarylene group;or a silicon-containing bivalent group.; 8. Textile article according to any of the preceding claims, wherein the textile article is selected from the group consisting of fibers, filaments, yarns and roving, and / or wherein the textile article is selected from the group consisting of a textile fabric, membrane, filter, wipe, mask, garment, mattress cover, bed cover, bed linen, cushion, blankets, upholstered furniture, seat cover, carpet, curtain and dressing material, and / or wherein a fabric having a second ionic group on a surface is bonded to the first ionic group, in particular wherein the fabric is reversibly bonded to the first ionic group.

9. Method for functionalizing a textile object, wherein the method comprises the following steps: Providing a textile article comprising a first polymer, optionally with a first bonding site on a surface; at least partially covering the first polymer with a second polymer, wherein the second polymer comprises a siloxane copolymer, the siloxane copolymer comprising at least one block of a plurality of siloxane monomer units and at least one block of a plurality of further monomer units, wherein at least one of the further monomer units comprises a first ionic group, the first ionic group being a cationic group;and / or wherein the second polymer, in particular at least one of the further monomer units, has a second binding site on a surface and the process further comprises applying a functionalizing agent comprising a first ionic group, which is a cationic group, and a spacer to the surface of the second polymer and binding the functionalizing agent to the second binding site, such that the first ionic group is bound to the surface of the second polymer via the spacer.

10. Method according to claim 9, wherein the provision of the textile article with a first bonding site on a surface includes a surface treatment, in particular wherein the surface treatment is selected from the group consisting of plasma treatment, oxidation treatment and flame treatment, and / or wherein the first and / or second bonding site is selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an ester group, a carbonyl group, in particular a ketone group or an aldehyde group, an amino group, a urethane group, a halogen, in particular chlorine or bromine, an epoxy group and a nitrile group.

11. Method according to claim 9 or 10, wherein the functionalizing agent further comprises a functional group capable of interacting, in particular reacting, with the second binding site on the surface of the second polymer, in particular wherein the functional group is selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an ester group, a carbonyl group, in particular a ketone group or an aldehyde group, an amino group, a urethane group, a halogen, in particular chlorine or bromine, and an epoxide group, and / or wherein the functionalizing agent is an oligomer and / or a copolymer, in particular a terpolymer.

12. A method according to any one of claims 9 to 11, wherein a substoichiometric amount of functionalizing agent is applied to the second binding site, and / or wherein the binding of the functionalizing agent to the second binding site comprises a chemical reaction forming a covalent bond, wherein the textile article is selected from the group consisting of fibers, filaments, yarns, and roving, and / or wherein the textile article is selected from the group consisting of a textile fabric, membrane, filter, wipe, mask, garment, mattress cover, bed linen, cushion, blanket, upholstered furniture, seat cover, carpet, curtain, and dressing material.

13. Textile article obtainable by a method according to any one of claims 9 to 12.

14. Method for binding a substance having a second ionic group on a surface, the method comprising: Bringing the material into contact with a textile object according to one of claims 1 to 8 and 13, wherein the second ionic group is charged oppositely to the first ionic group.

15. The method of claim 14, wherein the substance is reversibly bonded to the first ionic group, and / or wherein the substance is selected from the group consisting of peptides, proteins, microorganisms such as bacteria, viruses, yeasts and fungi, metabolic products such as allergens, toxins, enzymes, microorganisms such as mites, organic material with peptide surface structures such as spores, pollen, skin particles and mite eggs.

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