Biocides and adhesive bonds thereof

Abstract

The invention provides an aqueous solution having a diamine component, wherein the diamine component consists of at least 75 to 100% by weight of 5-N-formylamino-2-pyrrolidone-N '-n-dodecylpropane-1, 3-diamine (also referred to as Py-C12) or at least 35% by weight of 5-N-formylamino-2-pyrrolidone-N'-n-tetradecylpropane-1, 3-diamine (also referred to as Py-C14), based on the total weight of the diamine in the aqueous solution, the solution is used to attach the diamine to a material, wherein the solution has a pH of 8 or less and does not contain a solubilizing agent. These solutions are particularly suitable for use as biocides. In a related aspect, the present invention provides a method for attaching a diamine component according to the present invention to a material.

Description

[0001] The present invention provides aqueous solutions having a diamine component, in particular 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (also known as Py-C12) and / or 5-N-formylamino-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine (also known as Py-C14), which are preferably used to attach Py-C12 and / or Py-C14 to a material, wherein the pH of the solution is 8 or less, and wherein the solution does not contain a solubilizing agent. Preferably, Py-C12 and / or Py-C14 are attached to the material by curing the diamine. These solutions are particularly suitable for use as biocides. In a related aspect, the present invention provides methods for attaching Py-C12 and / or Py-C14 to a material. Background Art

[0002] Derivatives of propylene diamine have long been used for disinfection purposes. Commercially available diamines with biocidal activity include "C12", i.e., N-dodecyl-1,3-diaminopropane (C 15 H 34 N2; molecular weight 242.45; CAS 5538-95-4) and "bis-C12", i.e. N'-(3-aminopropyl)-N'-dodecyl-1,3-diaminopropane (C 18 H 41 N3; molecular weight 299.54; CAS 2372-82-9).

[0003] Furthermore, biocides of the N,N'-alkyl-1-ω-diamine type are important active ingredients in preparations and dressings for microbial control.

[0004] One outstanding biocide is alkaline glucoprotamine (Glucoprotamin). By definition, glucoprotamine (CAS 164907-72-6) is "the reaction product of glutamic acid with N-(C12-14-alkyl)propylenediamine". The latter is usually used in the synthesis of glucoprotamine in the form of cocopropylene-1,3-diamine and is a mixture of various acyclic N-alkylpropylene-1,3-diamines and N-alkylamines. The main difference is the chain length of the N-alkyl residue. The conversion with L-glutamic acid is achieved by a thermal condensation process, which produces glucoprotamine, which is a complex mixture of different condensation products as well as unreacted components of the cocopropylene-1,3-diamine starting material. Glucoprotamine also contains Py-C12 and Py-C14 and is characterized by good solubility in water. Waxy alkaline protamine is readily soluble, with a solubility of 440 g / L in water (i.e., 44% (w / v) in a 33% aqueous solution at pH 9.2). In contrast, Py-C12 (free base) is only slightly soluble in water, with a solubility of 33 mg / L (i.e., 0.0033% (w / v) at pH 9.5).

[0005] The good water solubility of the protamine containing Py-C12 and Py-C14 is attributed to the additional components in the protamine acting as solubilizers.

[0006] Generally speaking, the presence of additional substances such as solubilizers in biocidal products limits their practical use because the additional substances are often potentially hazardous and costly.

[0007] It was therefore an object of the present invention to provide solutions comprising Py-C12 and / or Py-C14 which are in particular free of solubilizers.

[0008] Furthermore, biocides are often associated with negative environmental toxicological potential. Therefore, their immobilization is very important but technically challenging.

[0009] The available techniques can be distinguished by the way in which immobilization is achieved, ie on the one hand by covalent binding (coupling) and on the other hand by adhesive interactions depending on effects such as ionic binding or van der Waals forces.

[0010] For 5-oxo-pyrrolidine-2-carboxylic acid derivatives such as Py-C12 and Py-C14, the possibility of immobilization by coupling (ie covalent binding) via its heterocycle oxo-pyrrolidine has been proposed (see WO 2016 / 016168 A1 and WO 2016 / 016167 A1).

[0011] Adhesion immobilization techniques (ie based on non-covalent interactions) may offer an alternative approach, but these methods often suffer from unintentional and uncontrolled leaching.

[0012] In particular, depending on their substitution pattern, N,N′-alkyl-1-ω-diamines display different physical characteristics related to their solubility in aqueous and non-aqueous media and to their adhesion behavior to surfaces.

[0013] Furthermore, depending on the specific desired use of the diamines, their physical and chemical properties can be very important. In particular, solubility is a frequently observed problem, and for many applications the liquid phase (state of matter) is crucial. On the one hand, the liquid phase and fluid parameters are important for technical process management. On the other hand, good solubility can lead to problems with leaching or undesired washing out.

[0014] This can lead to serious problems, for example because many N,N'-alkyl-1-ω-diamines are toxic or ecotoxic chemicals, so their release into soil or water should be avoided or at least minimized. Therefore, washing off such substances when in contact with water is a problem, for example in outdoor applications, and causes costs and efforts involving, for example, plant infrastructure and wastewater management.

[0015] Therefore, there is a need for the possibility to combine desired properties such as biocidal activity with physical parameters such as adhesion to various materials, which ultimately allow use in specific applications.

[0016] Therefore, it is another object of the present invention to provide a method by which Py-C12 and / or Py-C14 can be easily and durably attached to a material. The material thus obtained can be used in a variety of applications and provides beneficial properties. SUMMARY OF THE INVENTION

[0018] It has now been surprisingly found that changes in pH, temperature and / or salt concentration allow reversible modulation of the species state of Py-C12 and Py-C14 in an aqueous environment.

[0019] Based on this discovery, it is now possible to provide an aqueous solution having a diamine component, wherein the diamine component consists of at least 75-100 wt % Py-C12 based on the total weight of the diamines in the aqueous solution or at least 35 wt % Py-C14 based on the total weight of the diamines in the aqueous solution, which does not contain a solubilizer. Such solutions can be advantageously used as biocides.

[0020] Furthermore, the ability to easily adjust the state of matter can be used for technical penetration and fixation, i.e. for attachment to materials.

[0021] Therefore, the present invention provides:

[0022] (1) An aqueous solution having a diamine component, wherein the diamine component comprises at least 75 to 100 wt % of 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) based on the total weight of the diamines in the aqueous solution or at least 35 wt % of 5-N-formylamino-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine (Py-C14) based on the total weight of the diamines in the aqueous solution, the aqueous solution preferably being used for attaching Py-C12 and / or Py-C14 to a material, preferably by curing Py-C12 and / or Py-C14, and wherein the solution has a pH of 8 or less and does not contain a solubilizing agent.

[0023] (2) A method for attaching a diamine (preferably Py-C12) selected from 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) and / or 5-N-formylamino-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine (Py-C14) to a material, the method comprising: contacting the material with an aqueous solution having a diamine component containing Py-C12 and / or Py-C14, wherein the pH of the solution is 8 or less and does not contain a solubilizing agent, and after contacting: curing the diamine.

[0024] Alternative and preferred embodiments are described in the dependent claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 : Textiles treated with Py-C12 exhibit high wash resistance in aqueous systems and maintain their biocidal activity.

[0026] Figure 2 : Adjustment of the state of C12 species due to pH changes using HCl and NaOH.

[0027] Figure 3 : Adjustment of the state of C12 substances due to pH changes caused by the use of CO2.

[0028] Figure 4 : Regulation of the material state of Py-C12 caused by salt concentration.

[0029] Figure 5 :Regulation of the material state of Py-C12 caused by temperature changes.

[0030] Figure 6 : Penetration and subsequent immobilization of Py-C12 in synthetic sponges.

[0031] Figure 7 : Penetration and subsequent fixation of Py-C12 in porous textiles.

[0032] Figure 8 : Penetration and subsequent fixation of Py-C12 in wood.

[0033] Fig. 9 : Penetration and subsequent fixation of Py-C12 in leather.

[0034] Fig.10 : Penetration of Py-C12 into bone tissue and subsequent fixation.

[0035] Fig.11 : Polyester fabrics treated with Py-C12 exhibit high washing resistance in aqueous systems and maintain their biocidal activity.

[0036] Fig.12 : Silk fabrics treated with Py-C12 exhibited high wash resistance in aqueous systems and maintained their biocidal activity.

[0037] Fig.13 : Cotton fabrics treated with Py-C12 showed high washing fastness in aqueous systems and maintained their biocidal activity.

[0038] Fig.14 : Wood samples treated with Py-C12 showed high wash resistance in aqueous systems and maintained their biocidal activity. DETAILED DESCRIPTION OF THE INVENTION

[0040] The present invention provides an aqueous solution as described in (1) above, the use of the solution as a biocide and related methods as described in (2) above.

[0041] The present invention is based on the discovery that changes in pH, temperature and / or salt concentration allow reversible regulation of the material state of a diamine component, wherein the diamine component comprises at least 75 to 100 wt. % Py-C12 based on the total weight of the diamines in the aqueous solution or at least 35 to 100 wt. % Py-C14 based on the total weight of the diamines in the aqueous solution in an aqueous environment.

[0042] The aqueous solution contains Py-C12 having the following formula (I):

[0043]

[0044] and / or Py-C14 having the following formula (II):

[0045]

[0046] Formulae (I) and (II) encompass all stereoisomers and mixtures thereof.

[0047] Preferably, Py-C12 is (S)-5-N-formylamino-2-pyrrolidone-N′-n-dodecylpropane-1,3-diamine according to formula (Ia).

[0048]

[0049] Preferably, Py-C14 is (S)-5-N-formylamino-2-pyrrolidone-N′-n-tetradecylpropane-1,3-diamine (IIa).

[0050]

[0051] The pH value of the aqueous solution according to the present invention is 8 or lower.

[0052] For solutions of the present invention having a pH of 8 or less, the diamine component (wherein the diamine component comprises at least 75 to 100 weight percent Py-C12 based on the total weight of diamines in the aqueous solution or at least 35 to 100 weight percent Py-C14 based on the total weight of diamines in the aqueous solution) remains in solution / liquid material regardless of the temperature of the solution.

[0053] Notably, at a pH of 8 or less, the diamine components (wherein the diamine components comprise at least 75 to 100 wt % Py-C12 based on the total weight of the diamines in the aqueous solution or at least 35 to 100 wt % Py-C14 based on the total weight of the diamines in the aqueous solution) are already in liquid form at temperatures as low as about 16°C, enabling them to be used, for example, as biocides.

[0054] In a related embodiment, the aqueous solution according to the present invention has a temperature of 44°C or higher.

[0055] In the case where the solution of the present invention has a temperature of 44° C. or higher, the diamine components (wherein the diamine components contain at least 75 to 100 wt % Py-C12 based on the total weight of the diamines in the aqueous solution or at least 35 to 100 wt % Py-C14 based on the total weight of the diamines in the aqueous solution) remain in solution / liquid substances even at high concentrations such as 40% (w / v) in water, enabling their use as biocides.

[0056] At lower concentrations, i.e., in the range of about 1% to about 10%, the diamine components (wherein the diamine components contain at least 75 to 100 wt % Py-C12 based on the total weight of the diamines in the aqueous solution or at least 35 to 100 wt % Py-C14 based on the total weight of the diamines in the aqueous solution) have remained in solution / liquid material at a temperature of 40°C, which further expands their practical applications, for example as biocides.

[0057] The terms "biocide" and "biocidal agent" are interchangeable and, as used herein, refer to a chemical substance intended to destroy, prevent, render harmless, or exert a control over any harmful organism. Biocides are commonly used in medicine, agriculture, forestry, and industry. Biocides may include preservatives, pesticides (insecticides), disinfectants, and pesticides. The aqueous solution according to the present invention does not contain a solubilizing agent.

[0058] In line with this, the solution is different from alkaline protamine. According to Karlheinz Disch (Disch K. "Glucoprotamine-a new antimicrobial substance". Zentralbl Hyg Umweltmed. 1994Jun; 195 (5-6): 357-65. PMID: 7916863), protamine is defined as the conversion product of L-glutamic acid and cocoyl propylene-1,3-diamine. The latter is a mixture of various acyclic N-alkyl propylene-1,3-diamines and N-alkylamines whose main difference is the chain length of the N-alkyl residue. The conversion using L-glutamic acid is achieved by a thermal condensation method, which produces protamine, which is a complex mixture of unreacted components of different condensation products and cocoyl propylene-1,3-diamine starting materials. In short, these mixtures are described as being soluble in water. Good water solubility is caused by a variety of reasons. Firstly, the major part of the glucoprotamine mixture consists of unreacted starting materials (i.e. acyclic N-alkylpropylene-1,3-diamine and N-alkylamine), which are generally soluble in water. This is also valid for the glutamic acid condensation product, which still has carboxyl groups and therefore exhibits good water solubility due to its zwitterionic properties. Secondly, a smaller part of the condensation product, which as a single component substance exhibits poor solubility in water, is simply dissolved by the additional water-soluble substances used as "soap-like" solubilizers. Overall, this leads to good water solubility of the glucoprotamine, which, however, is not conducive to the purpose of the aggregation state management described in the present invention and is therefore fundamentally different from the solution of the present invention.

[0059] The term "solubilizer" as used herein generally refers to additives and adjuvants that merely facilitate the solubility of the active agent, ie, Py-C12 and / or Py-C14.

[0060] According to the invention, the aqueous solution may contain additives and auxiliaries which are detrimental to the solubility of Py-C12 and / or Py-C14, such as, for example, dyes, viscosity regulators, perfumes, flavorings, oils or emulsifiers.

[0061] The solubilizing agent includes any organic solvent: open chain esters such as ethyl acetate; open chain amides such as dimethylformamide; lactones such as gamma-butyrolactone; lactams such as N-methyl-2-pyrrolidone (NMP); nitriles such as acetonitrile, open chain ketones such as acetone, methyl ethyl ketone; cyclic ketones such as cyclohexanone; aldehydes such as propionaldehyde, benzaldehyde; alcohols (including polyols and branched alcohols) such as methanol, ethanol, glycerol, 2-propanol; alcohol derivatives such as 2-(2-butylethoxy)ethanol, 2-phenoxyethanol; amines, especially N-alkylamines such as triethylamine; acyclic N-alkylpropylene-1,3-diamine open chain ethers and polyethers such as diethyl ether, polyethylene glycol; cyclic ethers and cyclic polyethers; Ethers such as dioxane, tetrahydrofuran; aromatic compounds such as toluene, xylene, nitrobenzene; alicycles such as cyclohexane; heterocyclic compounds such as pyridine, furan, pyrrole, pyrrolidine, piperidine; open chain alkanes and alkenes such as paraffin, petroleum ether, heptane; halogenated hydrocarbons such as dichloromethane, chloroform, tetrachloroethylene, chlorobenzene; other derived hydrocarbons such as nitromethane, carbon disulfide, dimethyl sulfoxide, urea derivatives (e.g., tetramethyl urea), cyclopentane, aniline; emulsifiers such as sodium benzoate, crown ethers, sodium dodecyl sulfate, polysorbates (TWEEN); dispersants such as surfactants and bile acids; surfactants such as ethers with polyethylene glycol monobutyl ether.

[0062] Consistent with the nature of the present invention described above and herein, the term "solubilizer" as used herein of course includes neither Py-C12 nor Py-C14.

[0063] According to the present invention, the diamine component of the solution of the present invention comprises Py-C12 and / or Py-C14, and preferably consists of them. In one embodiment, the diamine component of the solution of the present invention comprises Py-C12 and / or Py-C14, preferably consists of them, preferably wherein the diamine component of the solution of the present invention comprises 75 to 100 wt% Py-C12, more preferably the diamine component of the solution of the present invention comprises 80 to 100 wt% Py-C12, even more preferably the diamine component of the solution of the present invention comprises 85 to 100 wt% Py-C12, further preferably, the diamine component of the solution of the present invention comprises 90 to 100 wt% Py-C12, further preferably, the diamine component of the solution of the present invention comprises 95 to 100 wt% Py-C12, further preferably, the diamine component of the solution of the present invention comprises 98 to 100 wt% Py-C12, most preferably, the diamine component of the solution of the present invention comprises 99 to 100 wt% Py-C12, based on the total weight of diamines in the aqueous solution.

[0064] In an alternative embodiment, the diamine component of the solution of the present invention comprises Py-C12 and / or Py-C14, preferably consists of them, preferably wherein the diamine component of the solution of the present invention comprises 35 to 100 wt % of Py-C14, more preferably the diamine component of the solution of the present invention comprises 40 to 100 wt % of Py-C14, still more preferably the diamine component of the solution of the present invention comprises 50 to 100 wt % of Py-C14, further preferably the diamine component of the solution of the present invention comprises 60 to 100 wt % of Py-C14, further preferably the diamine component of the solution of the present invention comprises 70 to 100 wt % of Py-C14, further preferably the diamine component of the solution of the present invention comprises 75 to 10 0 wt % of Py-C14, further preferably, the diamine component of the solution of the present invention comprises 80 to 100 wt % of Py-C14, further preferably, the diamine component of the solution of the present invention comprises 85 to 100 wt % of Py-C14, further preferably, the diamine component of the solution of the present invention comprises 90 to 100 wt % of Py-C14, further preferably, the diamine component of the solution of the present invention comprises 95 to 100 wt % of Py-C14, further preferably, the diamine component of the solution of the present invention comprises 98 to 100 wt % of Py-C14, most preferably, the diamine component of the solution of the present invention comprises 99 to 100 wt % of Py-C14, based on the total weight of diamines in the aqueous solution.

[0065] Unless otherwise indicated, weight percentages refer to weight percentages based on the total weight of diamines in the solution of the present invention, which is equal to the total weight of the diamine components in the aqueous solution.

[0066] In a specific embodiment, the aqueous solution comprises Py-C12, preferably the aqueous solution comprises Py-C12 at a concentration of about 0.001% (w / v) to about 40% (w / v), more preferably the solution comprises Py-C12 at a concentration of about 0.01% (w / v) to about 10% (w / v), and most preferably the solution comprises Py-C12 at a concentration of about 0.1% (w / v) to about 5% (w / v). In a specific embodiment, the diamine component of the solution of the present invention consists of Py-C12 and / or Py-C14, preferably the diamine component of the solution of the present invention is Py-C12.

[0067] In a particular embodiment, the solutions of the invention do not contain acyclic N-alkylpropylene-1,3-diamines and / or N-alkylamines.

[0068] As used herein, the term "acyclic" refers to a compound that is an open-chain compound (ie, a linear compound, such as an aliphatic compound).

[0069] In a preferred embodiment, the solution according to the invention does not comprise N-dodecylpropane-1,3-diamine and / or N-tetradecylpropane-1,3-diamine.

[0070] In a preferred embodiment, the solution according to the invention does not contain reaction products of glutamic acid with N-(C12-C14-alkyl)propylenediamine other than Py-C12 and Py-C14, and more preferably the solution according to the invention does not contain 5-N-formylamino-2-pyrrolidone-N'-n-tridecylpropane-1,3-diamine.

[0071] In a related embodiment, the aqueous solution consists essentially of Py-C12, Py-C14, and water.

[0072] In a particular embodiment, the aqueous solution consists essentially of Py-C12 and water, preferably the aqueous solution comprises Py-C12 at a concentration of about 0.001% (w / v) to about 40% (w / v), more preferably the aqueous solution comprises Py-C12 at a concentration of about 0.01% (w / v) to about 10% (w / v), and most preferably the aqueous solution comprises Py-C12 at a concentration of about 0.1% (w / v) to about 5% (w / v).

[0073] In alternative embodiments, the aqueous solution consists essentially of Py-C14 and water, preferably the aqueous solution comprises Py-C14 at a concentration of about 0.001% (w / v) to about 40% (w / v), more preferably the aqueous solution comprises Py-C14 at a concentration of about 0.01% (w / v) to about 10% (w / v), and most preferably the aqueous solution comprises Py-C14 at a concentration of about 0.1% (w / v) to about 5% (w / v).

[0074] As used herein, the term "consists essentially of" or "consisting essentially of" means that the aqueous solution consisting of the diamine and pH adjuster of the present invention may contain certain additional additives and / or adjuvants in addition to the described ingredients. Those additives and / or adjuvants may include dyes, viscosity modifiers, perfumes, flavorings, oils or emulsifiers.

[0075] That is, the solution of the present invention may contain a pH adjuster for necessary pH adjustment in addition to one or more diamine components and water.

[0076] As used herein, "pH adjusting agent" refers to an agent capable of adjusting the pH to a desired range.

[0077] The pH adjuster may be a proton-donating agent.

[0078] As used herein, "proton donating agent" refers to any acidifying agent, such as an acidic compound or mixture thereof, which is suitable for lowering the pH value.

[0079] The proton donating agent may be an organic acid, including a polymeric acid, an inorganic acid, or a mixture thereof.

[0080] It is particularly preferred that the proton donating agent is selected from hydrochloric acid (HCl), sulfuric acid (H2SO4) and carbonic acid (H2CO3), and the most preferred proton donating agent is HCl.

[0081] Thus, in a particular embodiment, the solution of the present invention consists of Py-C12, Py-C14, water, and a proton donating agent.

[0082] In a preferred embodiment, the solution of the present invention consists of Py-C12, water and a proton donating agent.

[0083] In an alternative embodiment, the solution of the present invention consists of Py-C14, water, and a proton donating agent.

[0084] Therefore, consistent with the foregoing, the solution of the present invention is preferably obtainable by mixing a diamine component with water and a pH adjuster (preferably a proton donating agent), wherein the diamine component consists of at least 75 to 100 wt % Py-C12 or at least 35 to 100 wt % Py-C14 based on the total weight of the diamine component, and the pH adjuster is used to adjust the pH value to 8 or lower.

[0085] Therefore, in a preferred embodiment, the solution of the present invention is obtained by combining or mixing a diamine component with water and a pH adjuster (preferably a proton donating agent, most preferably HCl), wherein the diamine component consists of at least 75 to 100 wt% of a Py-C12 or at least 35 to 100 wt% of a Py-C14 diamine component based on the total weight of the diamine component.

[0086] Thus, in a preferred embodiment, the solution of the present invention is obtained by combining or mixing a diamine component with water and a pH adjuster, preferably a proton donating agent, most preferably HCl, wherein the diamine component consists of Py-C12 or Py-C14.

[0087] In a further related aspect, the present invention provides a method of attaching a diamine selected from Py-C12 and / or Py-C14 (preferably Py-C12) to a material, the method comprising:

[0088] The material is contacted with an aqueous solution having a diamine component comprising Py-C12 and / or Py-C14, wherein the solution has a pH of 8 or less and does not contain a solubilizing agent, and after the contacting: curing the diamine.

[0089] In a related aspect, the present invention provides a method of attaching a diamine to a material, wherein the diamine component of the solution of the present invention consists of at least 75 to 100 weight percent Py-C12 or at least 35 to 100 weight percent Py-C14 based on the total weight of the diamine in the aqueous solution, the method comprising:

[0090] The material is contacted with an aqueous solution having a diamine component, and after contacting: curing the diamine.

[0091] Notably, the attached diamine retains its biocidal activity; and / or its activity in denaturing proteins; and / or its activity in interacting with membrane lipids, ie, acting as a detergent.

[0092] As used herein, the term "attachment" or "attachment" refers to non-covalent interactions. That is, the attachment to the material is based on non-covalent interactions, however, this does not exclude the additional presence of covalent interactions. Most preferably, the attachment is non-covalent attachment (also known as adhesive fixation). The attachment to the material preferably involves one or more of hydrogen bonding, van der Waals forces and / or ionic interactions.

[0093] Materials to which Py-C12 and / or Py-C14 can be attached (i.e., adhesively fixed) include both internal and external surfaces of materials. Such materials include absorbents, adsorbents, hygroscopic and porous materials such as fabrics (textiles), for example cotton, wool, linen, silk, polyester, polyamide; building materials, for example straw, glass wool, rock wool, silicone, gypsum, lime, cement, concrete, brick, porous and absorbent stone, clay; glues and gels, biological and synthetic sponges for cleaning and medical applications, porous and sintered metals, porous and absorbent ceramics, biological tissues, natural and processed biomaterials, for example extracellular matrix molecules, scaffolds, bones, wood, leather, paper, cardboard, resins, plastics and composites.

[0094] The material according to the invention includes in particular materials which contain or consist of different polymers, such as polyamides, polyurethanes, polypeptides, polyols or polyesters.

[0095] Polyols include polysaccharides, particularly cellulose and chitosan.

[0096] In a particular embodiment, the material is selected from synthetic sponges, fabrics, leather, bone tissue or wood. In a particularly preferred embodiment, the material is a fabric, and the fabric comprises cellulose, silk or polyester, more preferably the fabric is cotton, i.e. the fabric comprises cellulose and may additionally comprise wax, fat, pectin and / or water.

[0097] For attachment to occur, the material will be contacted with an aqueous solution of Py-C12 and / or Py-C14, preferably a solution according to aspect (1) above.

[0098] Specific and preferred embodiments of the aqueous solution of the diamine component according to the invention are described above in relation to aspect (1), and these apply equally to the method according to aspect (2).

[0099] The contacting of the method of the present invention may also be referred to as "incubation". Typically, the contacting lasts for at least about 10 seconds, preferably for about 20 hours.

[0100] A suitable period of time can be readily determined by the skilled person and need only be that which allows the diamine to penetrate into the material.

[0101] This penetration depends on the diamine component being in the liquid phase (state of matter), ie the diamine component being dissolved.

[0102] In an aqueous environment, solubility can be achieved by adjusting pH, temperature and / or salt concentration.

[0103] Once the liquid diamine component has penetrated into the material, it may be advantageous to convert the diamine component into the solid phase (state of matter) and thereby improve the adhesion, ie the adhesive fixation of the diamine to the material.

[0104] This solidification can be achieved by adjusting the pH, temperature and / or salt concentration. For a diamine component consisting of at least 75 to 100 wt % Py-C12 or at least 35 to 100 wt % Py-C14 based on the total weight of the diamine in the aqueous solution, for example, cooling (i.e., lowering the temperature), increasing the pH and / or increasing the salt concentration can convert the liquid phase (state of matter) into a solid phase (state of matter).

[0105] The method may include the steps of first heating the diamine component of the present invention to dissolve the diamine, preferably heating to 50°C, contacting the material with the solution of the present invention after heating; and after contacting, subsequently cooling the material, preferably cooling to at least room temperature, for curing the diamine.

[0106] The method of the present invention may further comprise, after curing, liquefying the diamine, wherein liquefying preferably comprises one or more of: heating the material; reducing the pH value of the material; reducing the salt concentration of the material, and adding a solvent.

[0107] Solvents suitable for liquefying the diamine may include any type of organic solvents such as toluene, 1-propanol, 2-propanol, ethanol, 1-butanol, methanol, chloroform, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, and cyclohexane.

[0108] In a preferred embodiment, the method of the present invention for attaching a diamine (wherein the diamine is Py-C12) to a material comprises contacting the material with an aqueous solution of Py-C12 having a concentration of at least about 0.05% (w / v), preferably an aqueous solution of Py-C12 having a concentration of about 0.1% (w / v) to about 5% (w / v), the method optionally further comprising curing the diamine after contacting.

[0109] In a related preferred embodiment, the method of the present invention for attaching a diamine (wherein the diamine is Py-C14) to a material comprises contacting the material with an aqueous solution of Py-C14 having a concentration of at least about 0.05% (w / v), preferably an aqueous solution of Py-C14 having a concentration of about 0.1% (w / v) to about 5% (w / v), the method optionally further comprising curing the Py-C14 after contacting.

[0110] According to the foregoing, the present invention particularly includes the following specific embodiments:

[0111] An aqueous solution consisting of 5% (w / v) or less Py-C12, preferably 1% (w / v) or less Py-C12, more preferably 0.01% (w / v) or less Py-C12, water and a proton donating agent (preferably HCl), wherein the pH of the solution is 8 or less, preferably 7.8 or less.

[0112] A method of attaching Py-C12 to a synthetic sponge, the method comprising contacting the sponge with an aqueous solution of Py-C12 and optionally solidifying the Py-C12 by subsequent cooling of the sponge.

[0113] A method of attaching Py-C12 to a porous textile, the method comprising contacting the textile with an aqueous solution of Py-C12 and optionally solidifying the Py-C12 by subsequent cooling of the textile.

[0114] A method of attaching Py-C12 to a dry pine wood sample, the method comprising contacting the wood sample with an aqueous solution of Py-C12 and optionally curing the Py-C12 by subsequent cooling of the wood sample.

[0115] A method of attaching Py-C12 to leather, the method comprising contacting the leather with an aqueous solution of Py-C12 and optionally curing the Py-C12 by subsequent cooling of the leather.

[0116] A method of attaching Py-C12 to bone tissue, the method comprising contacting the bone tissue with an aqueous solution of Py-C12, and optionally solidifying the Py-C12 by subsequent cooling of the bone tissue.

[0117] Method for attaching Py-C12 to a polyester fabric, the method comprising contacting the fabric with an aqueous solution of Py-C12 and optionally curing the Py-C12 by subsequently cooling the fabric.

[0118] Method for attaching Py-C12 to a silk fabric, the method comprising contacting the fabric with an aqueous solution of Py-C12 and optionally curing the Py-C12 by subsequently cooling the fabric.

[0119] Method for attaching Py-C12 to a cotton fabric, the method comprising contacting the fabric with an aqueous solution of Py-C12 and optionally curing the Py-C12 by subsequently cooling the fabric.

[0120] The present invention will be further described in the following examples, which should not be construed as limiting the present invention. Examples

[0121] Example 1 Effect of pH on the physical state of Py-C12 at 20 °C

[0122] The 1% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base was adjusted to a pH value between 3.0 and 10.0 with HCl or NaOH. At pH ≤ 7.8, Py-C12 was completely soluble in water at room temperature. In contrast, at pH ≥ 8, Py-C12 existed as a solid substance (see Table 1).

[0123] Table 1: Effect of pH on the physical state of Py-C12 (1% w / v) at 20 °C

[0124]

[0125] X: Liquid o: Solid

[0126] Example 2 Effect of temperature on the physical state of Py-C12 (1% w / v) at pH 7.0 and pH 9.0

[0127] The 1% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base was adjusted to pH values of 7.0 and 9.0 with HCl or NaOH and then incubated at temperatures between 2 °C and 60 °C. At pH 7, Py-C12 was completely soluble in water within the temperature range used. In contrast, at pH 9.0, Py-C12 was only liquid at the test temperatures of 50 °C and 60 °C (see Table 2).

[0128] Table 2: Effect of temperature on the physical state of Py-C12 (1% w / v) at pH 7.0 and pH 9.0

[0129]

[0130] X: Liquid o: Solid

[0131] Example 3 Interactions between salt concentration, temperature and pH on the material state of Py-C12

[0132] 5% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base was adjusted to pH values ​​of 4.0, 5.0 and 10.0 with HCl or NaOH. The samples were mixed with aqueous NaCl solutions, using concentrations between 0M and 3M, and then incubated at temperatures between 24°C and 45°C. The data show the complex interaction of different parameters on the material state of Py-C12 (see Table 3).

[0133] Table 3: Interactions between salt concentration, temperature and pH for the material state of Py-C12 (5% w / v)

[0134]

[0135] X: Liquid o: Solid

[0136] Example 4 Effect of Temperature on the Physical State of Py-C12 (Free Base) at Different Concentrations in Water

[0137] 5-N-Formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base at concentrations of 1% (w / v), 2.5% (w / v), 5% (w / v), 10% (w / v), 20% (w / v), 30% (w / v), and 40% (w / v) were incubated at temperatures between 36°C and 50°C (see Table 4).

[0138] Table 4: Effect of temperature on the material state of Py-C12 free base at different concentrations in water

[0139]

[0140] x: liquid o: solid

[0141] Example 5 Biocidal effect of Py-C12 against bacteria and fungi at pH 7.0.

[0142] To evaluate the bactericidal and fungicidal efficacy of Py-C12, quantitative suspension tests were performed according to a modified DIN EN ISO 11930:2019 under dirty conditions with an organic load and an incubation time of one and three days. For this purpose, a solution of 5-N-formamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) was adjusted to pH 7.0 with HCl and subsequently diluted to the corresponding test concentrations. Table 5 shows the respective reduction factor (log 10 ).

[0143] Table 5: Biocidal effect of Py-C12 at pH 7.0. Quantitative suspension tests for the assessment of bactericidal and fungicidal activity were performed according to a modified DIN EN ISO 11930:2019 using an organic load and an incubation time of one and three days, respectively.

[0144]

[0145] Example 6 Textiles treated with 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine

[0146] (Py-C12) exhibits high wash resistance in aqueous systems and maintains its biocidal activity.

[0147] Round sterile cotton textile samples were treated with a liquid Py-C12 solution (1% (w / v) in water; pH 7.0) followed by an intensive washing step. For the control, the samples were treated with water instead of Py-C12.

[0148] To test wash fastness in aqueous systems, the samples were incubated in water at 50°C for 20 hours and then washed 16 times in water at 37°C for 5 to 10 minutes each.

[0149] To test the wash durability in the alcohol / acid system, the samples were washed 8 times with 2-propanol / 1 mN HCl solution and a total of 8 times with water.

[0150] After all washing steps, all samples were inoculated with an Escherichia coli (E. coli) strain expressing β-galactosidase and then incubated at 37°C for 3 days.

[0151] The results are as follows Figure 1 shown.

[0152] In aqueous systems, the samples treated with Py-C12 showed high wash fastness and maintained their biocidal effect. This is evident from the fact that blue bacterial colonies appeared only at the edges of the samples treated with Py-C12 ( Figure 1, upper right), while the control (water) sample was completely colonized by bacteria ( Figure 1 , left picture).

[0153] In contrast, in the alcohol / acid system, i.e. when acidic 2-propanol was used instead of water in the washing step, Py-C12 was clearly removed from the cotton samples. This is evident from the fact that the samples treated with Py-C12 were completely colonized ( Figure 1 , lower right), similar to the control (water).

[0154] Example 7 Regulation of the physical state of Py-C12 by pH changes using HCl and NaOH

[0155] 1% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base adjusted to pH 7 with HCl is completely soluble in water at room temperature (see Figure 2 , left). After the addition of NaOH to raise the pH above 9.0, Py-C12 began to precipitate in a time-dependent manner (see Figure 2 , right: white indicates precipitation).

[0156] Example 8 Regulation of the state of Py-C12 material due to pH changes caused by the use of CO2

[0157] 5-N-Formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base in water at 1% (w / v) and 5% (w / v) was aerated with carbon dioxide to reduce the pH from 9.5 to 7. Under these pH conditions, Py-C12 was completely soluble at room temperature (see Figure 3 , left). After degassing the solution filled with CO2, Py-C12 precipitated in a time-dependent manner due to the increase in pH (see Figure 3 , right).

[0158] Example 9 Regulation of the state of Py-C12 material due to salt concentration

[0159] 2% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) was adjusted to pH 7 with HCl and mixed with different concentrations of NaCl ranging from 0.5 M to 3 M in water at room temperature. A clearly visible precipitate (white) was observed at concentrations of 1.5 M or higher (see Figure 4 ).

[0160] Example 10 Regulation of the state of Py-C12 material due to temperature change

[0161] 1% (w / v) and 5% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base are completely soluble in water at 50°C (see Figure 5 , left), but easily precipitates at room temperature (see Figure 5 , white in the right image).

[0162] Example 11 Penetration of Py-C12 into synthetic sponge and subsequent fixation

[0163] The synthetic sponge was treated with 5% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base in water. In the first step, Py-C12 was heated to 50°C to obtain a liquid solution. After incubating the sponge with the Py-C12 solution, the sponge was cooled to room temperature, at which time the liquid Py-C12 was converted to a solid phase, thereby being fixed within the sponge. The results are depicted in Figure 6 , where both images represent the same area and show the pores of a sponge filled with solid Py-C12 (right).

[0164] Example 12 Penetration of Py-C12 into porous fabrics and subsequent fixation

[0165] The porous textile sheet was treated with 5% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base in water. In the first step, Py-C12 was heated to 50°C to obtain a liquid solution. After incubation of the textile sheet with the Py-C12 solution, the textile sheet was cooled to room temperature, at which point the liquid Py-C12 was converted to a solid phase, thereby being fixed within the textile sheet. The results are depicted in Figure 7 , where both images represent the same area and show the waxy surface of the material due to solid Py-C12 (right).

[0166] Example 13 Penetration of Py-C12 into wood and subsequent fixation

[0167] Dried pine wood samples were treated with 5% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base in water. In the first step, Py-C12 was heated to 50°C to obtain a liquid solution. After incubation of the wood sample with the Py-C12 solution, the wood sample was cooled to room temperature, at which point the liquid Py-C12 converted to a solid phase, thereby being fixed in the wood sample. The results are depicted in Figure 8 , where both images represent the same area and show the waxy surface of the wood sample due to solid Py-C12 (right).

[0168] Example 14 Penetration of Py-C12 into leather and subsequent fixation.

[0169] The dried leather samples were treated with 5% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base in water. In the first step, Py-C12 was heated to 50°C to obtain a liquid solution. After incubation of the leather samples with the Py-C12 solution, the samples were cooled to room temperature, at which point the liquid Py-C12 was converted to a solid phase, thereby being fixed in the leather samples. The results are depicted in Fig. 9 , where both images represent the same sample and show the waxy surface of the leather sample due to solid Py-C12 (right).

[0170] Example 15 Penetration of Py-C12 into bone tissue and subsequent fixation.

[0171] Bone tissue was treated with 5% (w / v) 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base in water. In the first step, Py-C12 was heated to 50°C to obtain a liquid solution. After incubation of the bone tissue with the Py-C12 solution, the sample was cooled to room temperature, at which point the liquid Py-C12 converted to a solid phase, thereby being fixed within the bone tissue. The results are depicted in Fig.10 , where all images represent the same sample. Left: untreated bone matrix; middle: sample with pre-warmed liquid Py-C12; right: solid Py-C12 fixed within bone tissue. The lower images represent enlarged views of the upper images.

[0172] Example 16 The polyester fabric treated with Py-C12 exhibits high wash durability in aqueous systems and maintains its biocidal activity.

[0173] Polyester fabrics treated with 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base showed high washing resistance in aqueous systems and maintained their biocidal activity even after 20 washing steps. In the first step, 5% (w / v) of Py-C12 free base in water was heated to 50°C to obtain a liquid solution. After incubation with the Py-C12 solution, the samples were cooled to room temperature, at which time the liquid Py-C12 was converted into a solid phase and thus fixed to the material. After drying, the samples were washed with water at room temperature for 10, 20 and 30 times for 15 minutes each. Thereafter, all samples were inoculated with an Escherichia coli strain expressing β-galactosidase and then incubated at 37°C for 3 days. Blue bacteria appeared only in the control and Py-C12-treated samples washed 30 times with water (see Fig.11). The undyed groups (10 and 20 washing steps) showed that the polyester fabric treated biocidally with 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) showed high wash fastness even after 20 washing steps.

[0174] Example 17 The silk fabric treated with Py-C12 exhibits high washing resistance in aqueous systems and maintains its biocidal activity.

[0175] Silk fabrics treated with 5-N-formamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base showed high washing resistance in aqueous systems and maintained their biocidal activity even after 30 washing steps. In the first step, 1% (w / v) of Py-C12 free base in water was heated to 50°C to obtain a liquid solution. After incubation with the Py-C12 solution, the samples were cooled to room temperature, at which time the liquid Py-C12 was converted into a solid phase and thus fixed to the material. After drying, the samples were washed with water at room temperature for 10, 20 and 30 times for 15 minutes each. Thereafter, all samples were inoculated with an Escherichia coli strain expressing β-galactosidase and then incubated at 37°C for 3 days. Blue bacteria appeared only in the control samples (see Fig.12 ). The data show that the silk fabric treated biocidally with 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) showed high wash fastness even after 30 washing steps.

[0176] Example 18 Washing durability of Py-C12 immobilized in cotton fabric

[0177] Cotton fabrics treated with 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base showed high wash fastness in aqueous systems, maintaining its biocidal activity even after 30 washing steps. In the first step, 1% (w / v) of Py-C12 free base in water was heated to 50°C to obtain a liquid solution. After incubation with the Py-C12 solution, the samples were cooled to room temperature, at which time the liquid Py-C12 was converted into a solid phase and thus fixed to the material. After drying, the samples were washed with water at room temperature 10 times and 30 times for 15 minutes each. Thereafter, all samples were inoculated with an Escherichia coli strain expressing β-galactosidase and then incubated at 37°C for 3 days. Blue bacteria were distributed throughout the control samples and in several spots on the Py-C12-treated samples washed 30 times. The cotton samples washed 10 times did not show any bacterial growth (see Fig.13). The data showed that the cotton fabric treated with biocide 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) showed high wash fastness even after 30 washing steps.

[0178] Example 19 The wood sample treated with Py-C12 exhibited high wash resistance in aqueous systems and maintained its biocidal activity.

[0179] Wood samples treated with 5-N-formamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base showed high washing resistance in aqueous systems and maintained their biocidal activity even after 30 washing steps. In the first step, 1% (w / v) of Py-C12 free base in water was heated to 50°C to obtain a liquid solution. After incubation of beech wood slices with the Py-C12 solution, the samples were cooled to room temperature, at which time the liquid Py-C12 was converted into a solid phase and thus fixed to the material. After drying, the samples were washed with water at room temperature 10 and 30 times for 15 minutes each. Thereafter, all samples were inoculated with an Escherichia coli strain expressing β-galactosidase and then incubated at 37°C for 4 days. Blue bacteria appeared only on the control samples (see Fig.14 ). The data show that wood samples treated biocidally with 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) showed high wash fastness even after 30 washing steps.

Claims

1. An aqueous solution having a diamine component, wherein the diamine component comprises at least 75 to 100 wt % of 5-N-formylamino-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) based on the total weight of the diamines in the aqueous solution or at least 35 to 100 wt % of 5-N-formylamino-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine (Py-C14) based on the total weight of the diamines in the aqueous solution, the solution preferably being used to attach Py-C12 and / or Py-C14 to a material, more preferably by curing, and wherein the solution has a pH of 8 or less and does not contain a solubilizing agent.

2. The solution of claim 1, wherein the diamine component consists of Py-C12 and / or Py-C14, preferably consists of Py-C12.

3. The solution of claim 1 or 2, wherein the aqueous solution does not contain acyclic N-alkylpropylene-1,3-diamine.

4. The solution of any one of the preceding claims, wherein the aqueous solution consists of Py-C12 and / or Py-C14, preferably Py-C12, water and a pH adjuster.

5. Use of the aqueous solution according to any one of claims 1 to 4 as a biocide and / or for denaturing proteins and / or as a detergent.

6. The use according to claim 5, wherein the use is carried out at a temperature of 37°C or lower.

7. A method for attaching a diamine selected from Py-C12 and / or Py-C14, preferably Py-C12, to a material, the method comprising: The material is contacted with an aqueous solution having a diamine component comprising Py-C12 and / or Py-C14, wherein the solution has a pH of 8 or less and does not contain a solubilizing agent, and after the contacting: curing the diamine.

8. The method according to claim 7, wherein the diamine component comprises at least 75 to 100 wt. % Py-C12 or at least 35 to 100 wt. % Py-C14 relative to the material, the method comprising: The material is contacted with an aqueous solution having a diamine component according to any one of claims 1 to 4, and after contacting: curing the diamine.

9. The method of claim 7 or 8, wherein the material is porous and / or an absorbent and / or an adsorbent.

10. The method of claim 9, wherein the material is selected from the group consisting of synthetic sponge, fabric, leather, bone tissue, or wood.

11. The method of claim 9, wherein the material is a fabric, and the fabric comprises cellulose, silk and / or polyester.

12. The method of claim 11, wherein the fabric is cotton.

13. The method of claim 7 or 8, wherein the curing comprises one or more of: (i) cooling the aqueous solution; (ii) increasing the pH of the aqueous solution; (iii) increasing the salt concentration of the aqueous solution.

14. The method of claim 7 or 8, comprising the steps of: (i) heating the diamine component, preferably heating the diamine component to 50° C.; And after heating (ii) contacting the material with the aqueous solution having the diamine component; And after contact (iii) cooling the material, preferably allowing the material to cool to at least room temperature, to solidify the diamine.

15. The method of claim 14, further comprising, after curing: liquefying the diamine.

16. The method of claim 15, wherein the liquefaction comprises one or more of: (i) heating the material; (ii) Adding solvent.

Images