Object, method for functionalizing an object and object which can be obtained therefrom, and method for binding a peptide, and use of an object for binding a peptide

Abstract

The invention relates to an object which has a polymer, wherein a first ionic group is bound to the surface of the polymer or the object via a spacer. The invention additionally relates to a method for functionalizing an object and to an object which can be obtained therefrom. Finally, the invention relates to a method for binding a substance and to the use of an object for binding a substance.

Description

[0001]Our reference: W 1756 WO --------------------------------------------------------------------------------------- Object, method for functionalizing an object and object obtainable therefrom, method for binding a substance and use of an object for binding a substance --------------------------------------------------------------------------------------- FIELD OF THE INVENTION The present invention relates to an object, a method for functionalizing an object and an object obtainable therefrom. Furthermore, the present invention relates to a method for binding (and thereby removing) a substance and the use of an object for binding a substance. BACKGROUND For removing unwanted or harmful substances, such as allergens, peptides, proteins or bacteria, from the air in living spaces or the like.Functionalized surfaces, in particular ionically functionalized surfaces, of upholstered furniture, curtains or bed linen, for example, represent a promising approach. In particular, it can be advantageous if the fibers, yarns or foams used for this purpose are themselves ionically functionalized or finished. These usually consist of polymers or at least have polymers on their surface. The cationic finishing of fibers and textiles, in particular of cellulose fibers (and other polymers in the form of blended fabrics), during dyeing for the purpose of better color binding, preferably of acidic dyes, is known. The cationic finishing of textile surfaces for the purpose of preferential color binding during washing processes, so-called dye catchers, is also described, for example, in EP 1775372 A2 and DE 102005049 015 A1.WO 2015 / 091740 A2 describes the finishing of textiles, preferably polyester (PET), with hydrophilic silanes that also contain cationic components to impede the adhesion of bacteria and the resulting biofilms—the exact opposite of the approach described above. EP 3192923 A2 describes a bed textile and a method for chemical finishing, in which 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 the textile surfaces. Various forms of antimicrobial treatment of textiles are described in WO 2015 / 028852 A1, EP 3 061864 A1 and WO 2021 / 180930 A1.However, none of the solutions proposed to date in the prior art enable a targeted and adjustable ionic treatment of polymer surfaces as needed. Therefore, there may be a need to equip polymer surfaces with ionic functionalities in a targeted and adjustable manner as needed in order to bind undesirable or harmful substances, such as allergens, peptides, proteins, bacteria, or the like, and thus render them harmless or remove them from the environment. SUMMARY OF THE INVENTION The inventors of the present invention have discovered that a targeted and adjustable ionic treatment of a polymer surface can be achieved by means of a spacer with a variably adjustable length and quantity (charge density) between an ionic functionality and the polymer surface.The present invention accordingly relates to an article comprising a polymer (at least on one surface of the article), Our reference W 1756 WO page 3 / 37, wherein a first ionic group is bound (immobilized) to a surface of the polymer or of the article via a spacer. Furthermore, the present invention relates to a method for functionalizing an article, wherein the method comprises providing an article comprising a polymer (at least on one surface of the article) with a binding site (reactive group) on a surface, applying a functionalizing agent comprising a first ionic group and a spacer to the surface of the polymer or of the article, and binding the functionalizing agent to the binding site, such that the first ionic group is bound (immobilized) to the surface of the polymer or of the article via the spacer.of the article. Furthermore, the present invention relates to an article obtainable by a method described herein. 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, the method comprising bringing the substance into contact with an article as described herein, wherein the second ionic group is charged oppositely to the first ionic group (so that the substance is physically bound to the first ionic group (by means of ionic interaction)).Furthermore, the present invention relates to the use of an article as described herein for binding (and thereby removing) an (undesirable / harmful) substance having a second ionic group on a surface, wherein the second ionic group is oppositely charged to the first ionic group (so that the substance is physically bound to the first ionic group (by means of ionic interaction)). Further objects and advantages of embodiments of the present invention will become apparent from the following detailed description and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a functionalization of a cellulosic fiber fabric with a cationic functionalizing agent according to an exemplary embodiment.Figure 2 illustrates reactive epoxides or chlorohydrins suitable for the cationic functionalization of a cellulosic fiber fabric with a cationic spacer according to another exemplary embodiment. Figure 3 illustrates functionalization of a cellulosic fiber fabric with a cationic functionalizing agent according to another exemplary embodiment. DETAILED DESCRIPTION OF THE INVENTION Further details of the present invention and further embodiments thereof are described below. However, the present invention is not limited to the following detailed description, but rather serves merely to illustrate the teachings of the invention. It should be noted that features described in connection with an exemplary embodiment can be combined with any other exemplary embodiment.In particular, our reference W 1756 WO page 5 / 37, features described in connection with an exemplary embodiment of an object according to the invention can be combined with any other exemplary embodiment of an object according to the invention, as well as with any exemplary embodiment of a method according to the invention, as well as with any exemplary embodiment of a use according to the invention, and vice versa, unless expressly stated otherwise. When a term is referred to with an indefinite or definite article, such as “a”, “an”, “an”, “the”, “the” and “that”, in the singular, this also includes the term in the plural and vice versa, unless the context clearly specifies otherwise. The expressions “have” or “have”."Comprise," as used herein, includes not only the meaning of "contain" or "include," but can also mean "consist of" and "consist essentially of." In a first aspect, the present invention relates to an article. The article is not particularly limited as long as it comprises a polymer, in particular at least on one surface of the article. The article can also consist (essentially) of the polymer. Of course, the article can also comprise two or more types of polymers or can also relate to composite materials made of a polymer and a non-polymeric substance. In the context of the present application, a "polymer" is understood in particular to mean a structure with more than 10 monomer units (repeating units). According to an exemplary embodiment, the article comprises fibers, filaments, yarns (threads), roving, films, and / or a foam.In the context of the present application, the term "roving" is understood in particular to mean a bundle, strand or multifilament yarn made of parallel arranged filaments (continuous fibers) Our reference W 1756 WO page 6 / 37, which is predominantly used in the production of fiber-reinforced plastics or fiber-reinforced plastics. According to an exemplary embodiment, the article is a textile fabric (woven, nonwoven, knitted, non-woven), a membrane, a filter, a wipe, a mask (e.g. a mouth and nose covering, medical mask, FFP2 mask), a mattress cover, a duvet cover, bed linen, upholstery, 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).The term “textile fabric” in the context of the present application is understood to mean a two- or three-dimensional textile product, which can in particular be woven or non-woven. According to an exemplary embodiment, the polymer is selected from the group consisting of cellulose, polyamide (both synthetic and natural), polyester, polyketone, chitosan, polyurethane, polyvinyl halide, epoxy, polyolefin, in particular polyethylene or polypropylene, polyethylene terephthalate, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer (EVOH) and polyacrylonitrile (PAN). These polymers have proven to be particularly suitable for finishing with ionic groups. Combinations of polymers or copolymers can also be used. Whenever a polymer is mentioned below, a copolymer is always also understood to be included. According to an exemplary embodiment, a polymer is located at least on oron a surface of the object. According to an exemplary embodiment, the surface of the object or of the polymer has binding sites (reactive groups, Our reference W 1756 WO page 7 / 37 functional groups) to which (at least some of them) a first ionic group is bonded via a spacer. The term “spacer,” which can also be referred to as “spacer,” is understood in the context of the present application to mean a plurality or chain of atoms arranged between a first ionic group and (a binding site) of a surface of the object or of the polymer. The spacer ensures that the first ionic group is positioned at a certain distance from the surface of the object, which distance can be specifically adjusted via the length of the spacer.In addition, the amount / number of first ionic groups and thus the charge density or the charge spacing of the object can be specifically adjusted via the amount / number of spacers. According to an exemplary embodiment, the spacer is covalently bound to (a binding site on) the surface of the polymer or the object. This enables a particularly strong and permanent bond of the spacer, including the first ionic group, to the object, thus providing stable and permanent functionalization of the object. Alternatively, however, the spacer can also be bound to (a binding site on) the surface of the polymer or the object via van der Waals forces and / or hydrogen bonds, as required. This can be particularly advantageous if a less strong oronly temporary functionalization of the article is desired or if the article, in particular its polymer, would be impaired or damaged by covalent bonds (in particular when they are formed by a chemical reaction). According to an exemplary embodiment, the spacer is bound to the surface of the polymer or Our reference W 1756 WO page 8 / 37 of the article via at least one of an amide bond, an ether bond, an ester bond and a urethane bond. In this way, a wide variety of polymers can be functionalized in a variety of ways. According to an exemplary embodiment, the spacer comprises a (preferably divalent orA (bivalent) 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 one of ordinary skill in the art.The term "substituted" as used herein means that one or more, especially 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, -Cl, -Br, -I; -OH, hydroxyalkyl groups (ethers), -SH, thioalkyl groups (thioethers), =O, ester groups, amide groups, nitrile groups, and nitro groups. When two or more substituents are present, they may be the same or different and may be bonded together to form a ring. The terms “heteroalkylene group”, “heterocycloalkylene group” and “heteroarylene group” stand for an alkylene group, a cycloalkylene group or 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. Suitable examples of the alkylene group include C1 to C20 alkylene groups, in particular C2 to C10 alkylene groups, in particular C3 to C8 alkylene groups, in particular C4 to C6 alkylene groups. 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, in particular C6 to C8 cycloalkylene groups. Suitable examples of the arylene group include C6 to C20 arylene groups, in particular C6 to C16 arylene groups, in particular C6 to C14 arylene groups, in particular C6 to C10 arylene groups. In particular, the arylene group can be a phenylene group.The "silicon-containing bivalent group" can in particular include groups containing one or more silicon (Si) atoms and optionally further one or more of, for example, C, O, N, P, and / or H atoms. Suitable examples include -[Si-dialkyl]- (or -[alkyl-Si-alkyl]-), -[alkyl-Si-alkoxy]-, and -[Si-dialkoxy]- (or -[alkoxy-Si-alkoxy]-). According to an exemplary embodiment, the first ionic group is a cationic ((partially) positively charged) group. This allows, in particular, partially negatively charged substances to be bound, as is often the case with peptides and proteins. According to literature, 85% of protein structures have an excess of acidic amino acids, i.e., they are partially negatively charged. For example, a major allergen from house dust mite faeces, DerP1, contains an excess of acidic amino acids and can thus be bound by a cationically functionalized surface.Our reference W 1756 WO Page 10 / 37 Suitable examples of the cationic group include a (primary, secondary, tertiary) amino group, in particular a primary amino group, a (quaternary) ammonium group, a guanidino group, an imidazole group, a triazole group, a tetrazole group, a creatinine group, a (primary, secondary, tertiary) phosphine group (phosphine group), and a (quaternary) phosphonium group. Different cationic groups can also be combined as first 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. According to another exemplary embodiment, the first ionic group is an anionic ((partially) negatively charged) group.This opens up another, particularly complementary, field of application to a cationic group, thus achieving particularly great versatility. Suitable examples of the anionic group include a carboxyl group, a sulfonate group, a sulfate group, a phosphonate group, and a phosphate group. Here, too, different anionic groups can be combined as the first ionic groups. According to an exemplary embodiment, the ionic group is a permanently charged group. In particular, it can be advantageous that the charge state of the ionic group does not depend on the pH value, for example, when it comes into contact with water. This allows a constant binding capacity to be achieved, regardless of the ambient conditions. A suitable example of a permanently charged (cationic) group is a (quaternary) ammonium group.Our reference W 1756 WO Page 11 / 37 According to another exemplary embodiment, the ionic group is a pH-dependent (temporarily) charged group, i.e., the charge state of the ionic group depends on the pH value when it comes into contact with water, for example. This allows the charge state and thus the charge density of the object to be adjusted as needed. A suitable example of a pH-dependent charged (cationic) group is a primary amino group. According to an exemplary embodiment, the ionic group has an (average, median) distance from the surface of the polymer or the article in the range from 0.3 to 5 nm, in particular from 0.5 to 4 nm, in particular from 0.8 to 2.5 nm, in particular from 1 to 2 nm. For this purpose, the spacer preferably has an (average, median) molecular length of 0.3 to 5 nm, in particular from 0.5 to 4 nm, in particular from 0.8 to 2.5 nm, in particular from 1 to 2 nm.The distance of the ionic group from the surface of the polymer or object can be specifically adjusted by the choice of spacer, which, for example, can take folding into account in peptide structures. The (average, median) distance of the ionic group from the surface of the polymer or object, as well as the (average, median) 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, median) distance of the ionic group from the surface of the polymer or object, as well as the (average, median) molecular length of the spacer, can be confirmed, for example, using an electron microscope, e.g., a transmission electron microscope (TEM) or a high-resolution scanning electron microscope (SEM).Suitable examples of spacers and their corresponding lengths are given in the table below: Our symbol W 1756 WO Page 12 / 37 Length [pm] a) Spacers with cationic end groups -[CH2–O-CH2]–(N. + R1R2R3) 440 -[CH2–O-CH2-CH2]–(N + R1R2R3) 590 -[CH2–O-CO–CH(NH2)-CH2]–(N + R1R2R3) 740 -[CH2–O-CH2-CH(OH)-CH2]–(N + R1R2R3) 740 -[CH2–O-SO2-CH2-CH2]–(N + R1R2R3) 780 -[CH2–O–Si(=O)–(CH2)3]–(N + R1R2R3) 930 -[CH2-O-CO-CH2-CH2-CO-O-CH2]–(N + R1R2R3) 1180 -[CH2-O-CO-(CH2)5]-(N + R1R2R3) 1200 -[CH2-O-CO-CH(NH2)-(CH2)4]–(N + R1R2R3) 1200 -[CH2-O-CO-CH(NH2)-(CH2)3-NH-C(=NH)]–(N + R1R2R3) 1340 -[CH2-O-CH2-CH2-SO2-CH2-CH2-O-CH2-CH2]–(N + R1R2R3) 1540 -[CH2-O-CO-CH2-CH2-(CH(COOCH3)-CH2)x-CH2-CH2-COOCH2- 1950 (x=1) CH2]–(N + R1R2R3) 4720 (x=10) -[CH2-O-CO-NH-(CH2)6-NH-CO-O-CH2-CH2]–(N +R1R2R3) 2200 -[CH2-O-Si(=O)-(CH2)3-NH-CO-NH-CH2-CH2-(O-CH2-CH2)x- 2550 (x=1) CH2-CH2]–(N +R1R2R3) 4000 (x=5) 6200 (x=10) b) Spacers with anionic end groups -[CH2–O-CH2]–(COO-) 440 -[CH2-O-CH2-CH2]–(COO-) 590 -[CH2-O-CH2-NH-CO-CH2-CH2-S-CH2]–(COO-) 1400 The length of the spacers can be increased if necessary. Common methods of preparative chemistry, similar to polymer-analogous synthesis methods, are suitable for this purpose. Examples of such reactions include: chain extension by addition and / or condensation reactions, e.g., using native or capped diisocyanates, bis-2-oxazolines, bis-acyl-lactamates, bifunctional silanes and siloxanes, diepoxides, and alkylene oxides. According to an exemplary embodiment, the spacer has an (average, mediated) distance of 1 to 100 nm, in particular 2 to 50 nm, in particular 5 to 25 nm, from an adjacent spacer, in particular the nearest adjacent spacer.The distance between adjacent spacers and thus the charge density can be specifically adjusted by the choice of spacer (e.g. its steric extension) or by the amount of spacer per surface unit, which can be particularly important for the binding of large protein units and can also take other steric effects into account. The (average, mediated) distance of the spacer to a neighboring spacer can be determined, for example, using an electron microscope, e.g. a transmission electron microscope (TEM) or a high-resolution scanning electron microscope (SEM). According to an exemplary embodiment, the surface has binding sites (reactive groups, functional groups), with a spacer being bound to 0.5 to 20%, in particular 1 to 10%, in particular 2 to 5%, of the binding sites.In this case, the remainder of the binding sites can 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. According to an exemplary embodiment, a substance having a second ionic group on a surface can be bound or bonded to the first ionic group (by means of ionic interaction, i.e. physically). For this purpose, the second ionic group should be charged oppositely to the first ionic group. If the first ionic group is a cationic group, the second ionic group should therefore be an anionic or (partially) negatively charged group.If the first ionic group is an anionic group, the second ionic group should therefore be a cationic or (partially) positively 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 disruptive or harmful substance that should be bound as permanently as possible and thus removed from the environment. According to another exemplary embodiment, the substance is reversibly (latently) bound to the first ionic group. This is particularly advantageous if only a temporary binding of the substance to the object is desired. For example, the substance can be a pharmaceutical and / or a cosmetically active substance that is to be released again from the object.An article according to the invention, for example a dressing material (such as a wound dressing, a bandage, or a plaster), can thus be provided 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 of time if required. Such delayed release can also be adjusted as needed by targeted functionalization according to the invention. According to an exemplary embodiment, a drug can be reversibly (latently) or permanently (permanently) bound to the first ionic group. Exemplary drugs for this purpose include anionic fungicides and bactericides, such as piroctone, octopirox, ciclopirox, pyrithione, and perillic acid. This can be of particular interest for filter and medical topical applications.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 object. In a further aspect, the present invention relates to a method for functionalizing an object. As a result of the functionalization method, in particular, an object according to the first aspect, as described above, can be obtained. The method can therefore also be referred to as a method for producing a (functionalized) object.The article to be functionalised can be, for example, fibres, filaments, yarns (threads), roving, films and / or a foam or a textile fabric (woven, nonwoven, knitted, scrim), a membrane, a filter, a wipe, a mask (e.g. a mouth and nose covering, medical mask, FFP2 mask), a mattress cover, a duvet cover, bed linen, upholstery, 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 material (such as a wound dressing, a bandage or a plaster). Our symbol W 1756 WO Page 16 / 37 In a first step, an article which has a polymer (at least on one surface of the article) is provided with a binding site (reactive group) on a surface.According to an exemplary embodiment, the polymer located on a surface of the article already has binding sites or reactive groups. Suitable examples of such polymers include cellulose, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer (EVOH) (each with a hydroxyl group (-OH)), polyamides (with an amide group (-CONH-)), polyesters (with an ester group (-COO-)), polyketones (with a ketone group (-CO)-), chitosan (with an amino group (-NH2)), polyurethane (with a urethane group (-NH-COO-)), polyvinyl halides (with a halogen, for example, chlorine (-Cl)), 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 can still be carried out, for example, to reinforce or optimize the binding sites or for other reasons.According to another exemplary embodiment, the polymer located on a surface of the article inherently has no (suitable) or only a few or only slightly reactive bonding sites. Examples of such polymers include polyolefin, in particular polyethylene or polypropylene, polyethylene terephthalate, and polystyrene. According to an exemplary embodiment, providing the article with a bonding site on a surface thus includes a surface treatment to form bonding sites on the surface of the article or the polymer. According to an exemplary embodiment, the surface treatment is selected from the group consisting of plasma treatment, oxidation treatment, and flame treatment (flaming).In particular, plasma treatment, especially using reactive gas or gas mixtures containing, for example, ammonia or hydrazine, enables a broad spectrum of bonding sites on polymer surfaces. According to an exemplary embodiment, the bonding site, which can also be referred to as a reactive group, is one 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 (-Cl) or bromine (-Br), and an epoxy group (oxirane group).Combinations of different binding sites are also possible, especially if different functionalizing agents are to be applied, which can, for example, create different binding options for one or more substances to be removed. In a further step, a functionalizing agent comprising a first ionic group and a spacer is applied to the surface of the polymer or the object. Several different functionalizing agents can also be applied. For example, a (first) functionalizing agent comprising the spacer can be applied first, followed by another (second) functionalizing agent comprising the first ionic group.In this case, the first functionalizing agent can be bound to the binding site on the surface of the article before the second functionalizing agent is applied, which in turn is bound to the first functionalizing agent (in particular to a suitable functional group thereof). 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 as is 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 article, or the article can be immersed in the functionalizing agent. A padding process (i.e. a process using a padder) can also be used, in particular for the functionalization of a textile article.A padder typically comprises a system of two or more rollers and a trough (also referred to as a chassis) for holding a liquor containing the functionalizing agent. In the padder process, the textile material is typically immersed in the liquor in a wide state, and the excess liquor is then removed evenly across the entire width of the fabric using rollers. However, the functionalizing agent can also be applied to the surface of the polymer or article by vapor deposition (without being dissolved or dispersed in a solvent). The functionalizing agent has a first ionic group and a spacer. This can in particular be a first ionic group or a spacer, as explained in detail above in connection with the first aspect.According to an exemplary embodiment, the functionalizing agent further comprises a functional group capable of interacting, in particular reacting, with the binding site on the surface of the polymer or the object. This makes it possible to achieve a (firm) bond between the functionalizing agent and the surface of the polymer or the object. In particular, the functional group of the functionalizing agent can advantageously react with the binding site on the surface of the polymer to form a covalent bond.Our reference W 1756 WO Page 19 / 37 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 (-Cl) or bromine (-Br), and an epoxy group (oxirane group). The selection of the functional group of the functionalizing agent is made in particular taking into account the type of binding site on the surface of the polymer. If, for example, the binding site comprises a hydroxyl group or an amino group, the functional group of the functionalizing agent can in particular comprise a carboxyl group and vice versa.According to an exemplary embodiment, the functionalizing agent is selected from the group consisting of betaine, choline, taurine, caprolactam, laurolactam, alkoxysilanes, lysine, arginine, ornithine, histidine, creatinine, and succinylcholine betaine. These functionalizing agents have proven particularly suitable for implementing the inventive functionalization of a polymer surface, in particular for functionalizing a polymer surface, for example made of cellulose, with a cationic group. According to an exemplary embodiment, the functionalizing agent is an oligomer and / or a copolymer, in particular a terpolymer. In the context of the present application, an "oligomer" is understood in particular to mean a structure with up to ten monomer units, for example, from two to eight monomer units.In the context of the present application, a “copolymer” is understood to mean an oligomer or a polymer with at least two different monomer units. In the context of the present application, a “terpolymer” is understood to mean an oligomer or a polymer with (exactly) three different monomer units. Our reference W 1756 WO Page 20 / 37 According to an exemplary embodiment, the functionalizing agent is a terpolymer which comprises 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 which is able to interact, in particular react, with the binding site on the surface of the polymer or of the article.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-prepare 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, for example, 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.A further advantage of such terpolymers is that they are either readily soluble in water or easily emulsifiable. Suitable further examples of the second monomer include acrylates, methacrylates, maleic esters and styrene. A suitable further example of the first monomer is diallyldimethylammonium chloride, with which a permanently positively charged first ionic group can be provided. According to an exemplary embodiment, a substoichiometric amount of functionalizing agent is applied in relation to the binding site. In particular, it can be advantageous for the (molar) ratio of functionalizing agent to binding site to be in the range from 1:200 to 1:5, Our reference W 1756 WO page 21 / 37 in particular from 1:100 to 1:10, in particular from 1:50 to 1:20. In this way, the degree of functionalization orthe charge density of the polymer surface can be adjusted, for example so that the spacer is bound to only 0.5 to 20%, in particular 1 to 10%, in particular 2 to 5%, of the binding sites, while the rest of the binding sites are essentially unbound (free). In a further step, the functionalizing agent is bound to the binding site in such a way that the first ionic group is bound to the surface of the polymer or the object via the spacer. In other words, the functionalizing agent is bound to the binding site in such a way that the first ionic group is directed away from the binding site. According to an exemplary embodiment, the binding of the functionalizing agent to the binding site comprises a chemical reaction with the formation of a covalent bond (between the functionalizing agent, in particular its functional group, and the binding site).According to an exemplary embodiment, binding the functionalizing agent to the binding site comprises heating to a temperature in the range from 50 to 220 °C, in particular from 100 to 200 °C, in particular from 150 to 190 °C, in particular from 160 to 180 °C, over a period of time from 5 s to 5 min, in particular from 10 s to 2 min, in particular from 15 s to 60 s. In a further aspect, the present invention relates to an article which is obtainable or is obtained by a process for functionalization as described above. Our reference W 1756 WO Page 22 / 37 In a further aspect, the present invention relates to a process for binding (and thereby removing) an (undesirable / harmful) substance.The substance can be, in particular, a peptide, protein, microorganism such as bacteria, viruses, yeasts, and fungi, a metabolic product such as allergens, toxins, enzymes, microorganisms such as mites, or organic material with peptide surface structures such as spores, pollen, skin particles, and mite eggs. The method comprises bringing the substance into contact with a (functionalized) object, as described above, which has a first ionic group. The substance has a second ionic group on a surface that is oppositely charged to the first ionic group. This allows the substance to be bound to the first ionic group (by means of ionic interaction, i.e., physically). According to an exemplary embodiment, the substance is reversibly bound to the first ionic group.This is particularly advantageous if only a temporary binding of the substance to the object is desired. According to another exemplary embodiment, the substance is permanently or irreversibly bound to the first ionic group. This is particularly advantageous if the substance is a disruptive or harmful substance that is to be bound as permanently as possible and thus removed from the environment. In a further aspect, the present invention relates to the use of a (functionalized) object, as described above, for binding (and thereby removing) an (undesirable / harmful) substance that has a second ionic group on a surface, wherein the second ionic group is charged oppositely to the first ionic group (so that the substance is physically bound to the first ionic group (by means of ionic interaction)).According to one exemplary embodiment, the substance is reversibly bound to the first ionic group. According to another exemplary embodiment, the substance is permanently or irreversibly bound to the first ionic group. The substance can be, in particular, a peptide, protein, microorganism, such as bacteria, viruses, yeasts, and fungi, a metabolic product, such as allergens, toxins, enzymes, microorganisms, such as mites, or organic material with peptide surface structures, such as spores, pollen, skin particles, and mite eggs. The present invention is further described with reference to the following examples, which, however, serve merely to clarify the teachings of the invention and are not intended to limit the scope of the present invention in any way.Examples Application to organic fibers and textiles is based on impregnation using aqueous baths and application liquors that contain the bondable agents either dissolved or dispersed, possibly simultaneously with other finishing agents. Such processes are industrially established under the term "padding." The substrate is passed through the bath (liquor), completely impregnated, and then the liquor excess is reduced to a defined level by several pairs of rollers. This is usually immediately followed by a drying / fixing process, Our Mark W 1756 WO Page 24 / 37 followed by final geometric deformation (stretching, ironing, etc.). This method can be further modified, as various exhaustion, spray, or foam application processes demonstrate. The basic steps remain the same: impregnation – removal of excess – thermal fixing and drying – finishing.Application to smooth (film) surfaces is comparable: spray – thermally fix – remove unbound excess (rinse) – dry. Comparative Example 1 The teaching from EP 3192 923 allows the conclusion that mite fecal allergens (DerP1) are positively (+) charged, thus binding to anionic (-) surfaces through electrostatic interactions. In contrast, the allergen-binding effect of the textile is attributed to an "amido-functional aminopolydiorganosiloxane compound," i.e., a compound with a moderate cationic charge. Accordingly, the textile should be loaded with large quantities (30-200 g / l liquor = 3-20%). This represents a large stoichiometric excess compared to the reactive OH groups of the (presumed) cellulose textile. Nevertheless, only a maximum of 75% of the allergens are adequately fixed. Only further additives increase the fixation rate.Example 1 A blended fabric made of 55% TENCEL (cellulose fiber produced using the Lyocell process by LENZING AG) and 45% cotton, with a basis weight of 150g / m. 2 (150g / m 2 = ~ 1 mol cellulose / glucose per m 2) absorbed 42% liquor during padding and subsequent roller squeezing. The liquor contained 1.2% of the active ingredient (of an aqueous preparation adjusted to pH 10 with NaOH): Our reference W 1756 WO Page 25 / 37 2-[2-(2-chloroethyl)sulfonyl]ethoxyethanamine·HCl Cl-CH2-CH2-SO2-CH2-CH2-O-CH2-CH2-NH2·HCl (C6H15Cl2NO3S) MG: 252.15 CAS: 98231-71-1 Spacer length: Cell-O- to -NH2: 1400 pm = 1.4 nm The concentration corresponds to: 100 g textile + 42 g liquor corresponds to (0.5 g active ingredient) 150 g textile + 63 g liquor corresponds to (0.75 g active ingredient) or every 30th primary OH group of the cellulose is substituted. The squeezed textile was then dried at 180-200°C for 10-15 seconds (IR radiator with ventilation). Using ELISA (Enzyme-Linked Immunosorbent Assay), the DerP1 absorption was quantified at over 99%.Example 2 This example shows that even a small spacer extension and a slight increase in basicity leads to a remarkable increase in absorption capacity towards anionic peptides. TENCEL C (LENZING AG) is a lyocell fiber with a cellulose core and an integrated (outer) layer of chitosan. Unlike cellulose, chitosan has an amino group (-CH2NH2) instead of the primary hydroxy group (-CH2OH) and is therefore significantly cation-active. This manifests itself in an antimicrobial, antiviral, and (also) fungicidal effect based on charge exchange. Our trademark W 1756 WO Page 26 / 37 Fabrics (textiles) made from TENCEL C are preferably used for sportswear, sock yarn, etc. The further functionalization according to the invention significantly increases the bonding capacity: A fabric made from TENCEL C (50%) and VISCOSE-MODAL (50%) with a basis weight of 80g / m. 2is padded. Liquor: Contains 6% of a 50% technical cyanamide solution (SKW-Cyanamid L500) adjusted to a pH of 9.5 using acetic acid and maintained at this level during padding. Temperature: 70-85°C. Pressed to 35% w / w liquor content, dried at 150°C. The formation of guanyl groups is 13C NMR and FT-IR confirmed this. Elemental analysis shows that the nitrogen content of the fabric increases from 0.41% (corresponding to approximately 9.5% chitosan content of the TENCEL C portion) to 0.52%, which suggests that every fifth -CH2NH2 group from chitosan has been converted to -CH2-NH-C(=NH)-NH2. At the same time, this substitution increases the spacer length by approximately 300 pm, thus becoming more mobile. Likewise, the basicity increases, and thus the electrical (+) potential for the fixation of anion-active proteins. This manifests itself in the increased immobilization of coat proteins from Pseudomonas aeruginosa and Escherichia coli. Example 3 Anionically modified cellulose fibers The basis is the 43% solution of 3-(1-carboxyethyl)-thio-N-hydroxymethyl-propionic acid amide (Na salt): (Na)HOOC-CH(CH3)-S-CH2- CH2-CO-NH-CH2OH Spacer length: 1400 pm = 1.4 nm Our reference W 1756 WO page 27 / 37 which is obtained according to example 4 of EP 0189373.Cellulose fiber fabric or nonwoven can be padded according to stoichiometric requirements with an approximately 10-20% aqueous solution adjusted to pH 3 using hydrochloric acid, and the N-hydroxymethyl group can be condensed to the primary hydroxyl group of the glucose unit in the polymer chain at a temperature ≥ 130°C (preferably 180-200°C). The degree of substitution can thus be adjusted according to the invention (e.g., every OH group, every 2nd, 3rd, 4th, 5th, ..., 10th). The anionically modified cellulose can be used to ionically bind cationic antimicrobial agents. Preferred are: gentamicin, erythromycin, gramicidins, kanamycin, neomycin, streptomycin, tetracyclines, tyrothricin, paromomycin, quinolones, floxacins, penicillins, cephems, and macrolides. Fungicides, acaricides, etc. are also used. Applications: dressings, wound treatment, dermatology. Also filters for operating rooms, masks, etc.Examples 4 to 10 A cellulose fiber fabric that has been anionically treated (statistically) at every tenth primary hydroxyl group according to Example 3 is cationically treated in a subsequent padding process. This occurs by neutralizing the carboxyl groups with an excess of polycationically treated polymers, particularly their free amino / imino groups. The following were tried: Example 4: Polyethylenimine (Luprasol, BASF) MW ~ 25,000 Example 5: Polylysine (CAS 25104 – 18 – 1) MW > 4700 Our reference W 1756 WO Page 28 / 37 Example 6: Polyarginine (CAS 26982 – 20 -7) MW > 5000 Example 7: Polyvinylimidazole (CAS 25232 – 42 – 2) MW › 10,000 Example 8: Copolymer of DADMAC with diallylamine (10:1) Example 9: Condensate of dicyandiamide / formaldehyde / ammonium chloride) 1:3:1 (molar ratios) Example 10: Copolymer of vinylpyrrolidone and vinylimidazole (LUV / QUANT FC550, BASF) If the drying / fixing after the 2ndIf the padding process remains below 80–100°C, the predicted salts are formed. These are therefore not wash-resistant, but highly active against anionic peptide structures (viruses, bacteria, mites) and are therefore particularly suitable for dressing materials or filters. If the drying process is increased to above 150°C, preferably 180°C, intramolecular condensation occurs to form amides, which are subsequently wash-resistant (and thus suitable for textile finishing). This applies to Examples 4, 5, 6, 8, and 9, as these amines contain free NH2 groups (not in Examples 7 and 10!). Figure 1 illustrates the functionalization of a cellulose fiber fabric with a cationic functionalizing agent according to Example 4 (polyethyleneimine (PEI)). The amino groups present in Examples 4 and 5 after drying and fixing can be converted into guanidyl residues in a further reaction step using cyanamide, analogous to Example 2.This increases the ion density and thus the basicity (see Figure 1, Process 4: Increasing the ion density). It should also be noted that the amide formation from -COOH (spacer) and -NH2 (cat. polymer) is easier to carry out than a condensation of COOH with -NH- as is the case in Examples 7 and 10. In this case, a drying time of > 180°C, preferably 200°C / 2 min, is necessary. Our reference W 1756 WO Page 29 / 37 It should also be noted that in steps 2 and 3, parallel chains to the cellulose are formed, which are held at a distance by spacers. It can be assumed that in the usual helix formation of cellulose, these parallel structures are also wound and the (still unbound) cationic centers intended for absorption remain evenly positioned. (Preliminary remark) Particularly suitable as cationic functionalizing agents are so-called "Quabs™," which, as reactive epoxides or chlorohydrins, covalently couple to cellulose in a strongly alkaline environment, as shown in Figure 2. This modification of cellulose fibers is well known in the art and is widely used for color fixation in dyeing processes with acidic dyes (-SO3H groups). A new application is their use as cationic centers for the absorption of anionic protein surfaces. This is already possible with R = C1 – C6. With R = > C6, preferably C8 – C20, and particularly preferably C12 – C18, a pronounced antimicrobial effect is also exerted, which, in addition to the absorption of bacteria (immobilization), can also lead to the lysis of the coat proteins and thus to the death of the microorganisms.Examples 11 – 13 Cellulose fabrics or nonwovens are reacted with a 0.1 – 5.0% QUAB™ solution (depending on the desired degree of functionalization and adequate liquor absorption) in a padding process at pH 8.5 – 11.5, at > 50°C, preferably > 80°C. After squeezing, the fabric is washed at a pH-neutral temperature of 20-35°C (measured in wash water) and dried. Due to the rapid chemical reaction, already in the liquor, subsequent fixation at elevated temperatures is unnecessary. Our reference W 1756 WO Page 30 / 37 Figure 3 shows a corresponding cellulose fiber fabric functionalized with QUAB™. Example 11 QUAB™ 188. X) R = CH3 (Methyl) - Example 12 QUAB™ 342 X) R = CH12 (Lauryl) - Example 13 QUAB™ 426 X)R = CH18 (Stearyl) - x) Supplier: QUAB-Chemicals Protein binding results using the example of DER p1 (ELISA test) Test Degree of substitution / stat. absorption 11a 1:6 94.6% 11b 1:10 88.9% 12 1:10 95.0% 13 1:10 96.5% The immobilization of bacteria, e.g. Pseudomonas aeruginosa, or fungi, e.g. Aspergillus niger, can be confirmed by testing in accordance with DIN EN ISO 20743 and DIN EN 14119. The present invention has been described using specific embodiments and examples. However, the invention is not limited thereto and various modifications are possible without departing from the scope of the present invention.

Claims

Our reference W 1756 WO Page 31 / 37 CLAIMS 1. An article comprising a polymer, wherein a first ionic group is bonded to a surface of the polymer via a spacer, characterized in that the first ionic group has a distance from the surface of the polymer in the range of 0.3 to 5 nm, so that a peptide or a protein having a second ionic group oppositely charged to the first ionic group can be physically bonded to the first ionic group.

2. An article according to claim 1, wherein the first ionic group is a cationic group.

3. An article according to claim 2, wherein the cationic group is selected from the group consisting of an amino group, an ammonium group, a guanidino group, an imidazole group, a triazole group, a tetrazole group, a creatinine group, a phosphine group, and a phosphonium group. 4.The article of claim 1, wherein the first ionic group is an anionic group.

5. The article of claim 4, wherein the anionic group is selected from the group consisting of a carboxyl group, a sulfonate group, a sulfate group, a phosphonate group, and a phosphate group.

6. The article of any one of the preceding claims, wherein the ionic group is a permanently charged group.

7. The article of any one of claims 1 to 5, wherein the ionic group is a pH-dependent charged group. Our reference W 1756 WO Page 32 / 37 8. An article according to any one of the preceding claims, wherein the spacer is covalently bonded to the surface of the polymer.

9. An article according to claim 8, wherein the spacer is bonded to the surface of the polymer via at least one of an amide bond, an ether bond, an ester bond, and a urethane bond. 10.An article according to any one of the preceding claims, 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 divalent group.

11. An article according to any one of the preceding claims, wherein the spacer has a distance of 1 to 100 nm, in particular 2 to 50 nm, from an adjacent spacer. 12.An article according to any one of the preceding claims, wherein the surface has bonding sites, with the spacer being bonded to 1 to 10% of the bonding sites.

13. An article according to any one of the preceding claims, wherein the polymer is selected from the group consisting of cellulose, polyamide, polyester, polyketone, chitosan, polyurethane, polyvinyl halide, epoxy, polyolefin, in particular polyethylene or polypropylene, polyethylene terephthalate. Our reference W 1756 WO page 33 / 37 polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer and polyacrylonitrile.

14. Article according to one of the preceding claims, wherein the article is selected from the group consisting of fibers, filaments, yarns, roving, films and foam.

15. Article according to one of claims 1 to 13, wherein the article is selected from the group consisting of a textile fabric, membrane, filter, wipe, mask, mattress cover, duvet cover, bed linen, upholstery, blankets, upholstered furniture, seat cover, carpet, curtain and dressing material.

16. Article according to one of the preceding claims, wherein the peptide or the protein is reversibly bound to the first ionic group.

17. Article according to one of the preceding claims, wherein the peptide or the protein is a pharmaceutical and / or a cosmetically active substance.

18. Article according to claim 17, wherein the peptide orthe protein is a peptide drug, an anti-inflammatory drug, and / or an antibiotic drug.

19. A method for functionalizing an article, the method comprising the following steps: providing an article comprising a polymer with a binding site on a surface; applying a functionalizing agent comprising a first ionic group and a spacer to the surface of the polymer; binding the functionalizing agent to the binding site such that the first ionic group is bound to the surface of the polymer via the spacer. Our reference W 1756 WO page 34 / 37, characterized in that the first ionic group is at a distance from the surface of the polymer in the range of 0.3 to 5 nm, so that a peptide or a protein having a second ionic group oppositely charged to the first ionic group can be physically bound to the first ionic group.

20. The method according to claim 19, wherein providing the article with a binding site on a surface includes a surface treatment.

21. The method according to claim 20, wherein the surface treatment is selected from the group consisting of plasma treatment, oxidation treatment, and flame treatment. 22.The method according to any one of claims 19 to 21, wherein the binding 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.

23. The method according to any one of claims 19 to 22, wherein the functionalizing agent further comprises a functional group capable of interacting, in particular reacting, with the binding site on the surface of the polymer. 24.The method of claim 23, 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. Our reference W 1756 WO page 35 / 37 25. The method according to any one of claims 19 to 24, wherein the functionalizing agent is selected from the group consisting of betaine, choline, taurine, caprolactam, laurolactam, alkoxysilanes, lysine, arginine, ornithine, histidine, creatinine and succinylcholine betaine.

26. The method according to any one of claims 19 to 25, wherein the functionalizing agent is an oligomer and / or a copolymer, in particular a terpolymer.

27. The method according to claim 26, wherein 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 binding site on the surface of the polymer. 28.The method of claim 27, wherein the first monomer is a cationic monomer, the second monomer is a neutral monomer, and the third monomer is an anionic monomer.

29. The method of any one of claims 19 to 28, wherein a substoichiometric amount of functionalizing agent is applied with respect to the binding site.

30. The method of any one of claims 19 to 29, wherein binding the functionalizing agent to the binding site comprises a chemical reaction to form a covalent bond.

31. The method of claim 30, wherein binding the functionalizing agent to the binding site comprises heating to a. Our reference W 1756 WO page 36 / 37 temperature in the range of 50 to 220°C over a period of 5 s to 5 min.

32. The method according to any one of claims 19 to 31, wherein the article is selected from the group consisting of fibers, filaments, yarns, roving, films and foam.

33. The method according to any one of claims 19 to 31, wherein the article is selected from the group consisting of a textile fabric, membrane, filter, wipe, mask, mattress cover, duvet cover, bed linen, upholstery, blankets, upholstered furniture, seat cover, carpet, curtain and dressing material.

34. A method for binding a peptide or a protein having a second ionic group to a surface, the method comprising: contacting the peptide or protein with an article according to any one of claims 1 to 18, wherein the second ionic group is oppositely charged to the first ionic group. 35.The method of claim 34, wherein the peptide or protein is reversibly bound to the first ionic group.

36. Use of an article according to any one of claims 1 to 18 for binding a peptide or protein having a second ionic group on a surface, wherein the second ionic group is oppositely charged to the first ionic group.

37. Use according to claim 36, wherein the peptide or protein is reversibly bound to the first ionic group.

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