Biocides and their adhesive bonds

Abstract

The present invention provides an aqueous solution having a diamine component, the diamine component consisting of at least 75-100% by weight of 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine, also referred to as Py-C12, or at least 35% by weight of 5-N-carboxamido-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine, also referred to as Py-C14, based on the total weight of diamines in the aqueous solution, for attaching the diamine to a material, the solution having a pH of 8 or less and free of a solubilizing agent. These solutions are particularly useful as biocides. In a related aspect, the present invention provides a method for attaching the diamine component according to the present invention to a material.

Description

[Technical field]

[0001] The present invention provides an aqueous solution having a diamine component, in particular 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine, also referred to as Py-C12, and / or 5-N-carboxamido-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine, also referred to as Py-C14, preferably Py-C12 and / or Py-c14, for attaching to a material, the aqueous solution having a pH of 8 or less and not containing a solubilizing agent. Preferably, Py-C12 and / or Py-C14 are attached to the material by solidifying the diamine. These solutions are particularly useful as biocides. In a related aspect, the present invention provides a method for attaching Py-C12 and / or Py-C14 to a material. [Background technology]

[0002] 2. Background of the Invention Derivatives of propylenediamine have long been used for disinfection purposes. The commercially available diamine with biocidal activity is "C12", i.e., N-dodecyl-1,3-diaminopropane (C 15 H 34 N 2 ; 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 N 3 ; 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 formulations and dressings for microbial control.

[0004] A well-known biocide is the alkaline glucoprotamine. Glucoprotamine (CAS 164907-72-6) is by definition "the reaction product of glutamic acid with N-(C12-14-alkyl)propylenediamines". The latter is usually used in the form of cocopropylene-1,3-diamine for the synthesis of glucoprotamine, which is a mixture of various acyclic N-alkylpropylene-1,3-diamines and N-alkylamines. It differs mainly in the chain length of the N-alkyl residues. The conversion with L-glutamic acid is achieved by a thermal condensation process, which gives glucoprotamine as a complex mixture of diverse condensation products, as well as the 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. The waxy alkaline glucoprotamine is readily soluble in water with a solubility of 440 g / L (i.e., 44% (w / v) at pH 9.2 for a 33% aqueous solution), whereas Py-C12 (free base) is only sparingly soluble in water with a solubility of 33 mg / L (i.e., 0.0033% (w / v) at pH 9.5).

[0005] The good aqueous solubility of glucoprotamine containing Py-C12 and Py-C14 is due to other components in glucoprotamine that act as solubilizers.

[0006] Generally, the presence of additional materials, such as solubilizers, in biocidal products limits their practical application because the additional materials are often potentially hazardous and cost intensive.

[0007] It is therefore an object of the present invention to provide a solution comprising Py-C12 and / or Py-C14, particularly one that is free of solubilizing agents.

[0008] Furthermore, biocides are often associated with negative ecotoxicological potential, making their immobilization of interest but also technically challenging.

[0009] The available techniques can be differentiated by the way in which immobilization is achieved, i.e., by covalent bonds (coupling), on the one hand, and by adhesive interactions, depending on the effects of, for example, ionic bonds or van der Waals forces, on the other hand.

[0010] For 5-oxo-pyrrolidine-2-carboxylic acid derivatives such as Py-C12 and Py-C14, the possibility of coupling via the heterocyclic oxo-pyrrolidine, i.e., covalent immobilization, has been proposed (see WO2016 / 016168A1 and WO2016 / 016167A1).

[0011] Adhesive immobilization techniques, ie, techniques based on non-covalent interactions, may offer an alternative, but they frequently suffer from inadvertent and uncontrolled leaching.

[0012] In particular, N,N'-alkyl-1-ω-diamines exhibit different physical characteristics with regard to their solubility in aqueous and non-aqueous media and their adhesion behavior to surfaces, depending on their pattern of substitution.

[0013] In addition, depending on the concrete intended use of the diamines, their physical and chemical properties can be very important. In particular, solubility is often an issue observed for many applications, and the liquid phase (state of matter) is of great importance. On the one hand, the liquid phase and the flow parameters are important for technological process control. On the other hand, good solubility can cause problems with leaching or undesired rinsing.

[0014] This can lead to serious problems, for example, since many of the N,N'-alkyl-1-ω-diamines are toxic or environmentally toxic chemicals, and therefore their release into soil or water should be avoided or at least minimized. Thus, rinsing such species upon contact with water is, for example, a problem in outdoor applications, causing costs and hassles, for example, in terms of facility infrastructure and wastewater management.

[0015] There is therefore a need for the possibility to combine desirable functionalities, such as biocidal activity, with physical parameters, such as adhesive bonding to various materials, that ultimately enable their use in specific applications. It is therefore another object of the present invention to provide a method by which Py-C12 and / or Py-C14 may be readily and persistently attached to materials, the resulting materials being employable in a number of applications and offering beneficial properties. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] International Publication No. 2016 / 016168 [Patent Document 2] International Publication No. 2016 / 016167 Summary of the Invention [Means for solving the problem]

[0017] Short description of the invention Surprisingly, it has now been found that changes in pH, temperature and / or salt concentration make it possible to reversibly tune the state of matter of Py-C12 and Py-C14 in an aqueous environment.

[0018] Based on this finding, it is now possible to provide an aqueous solution having a diamine component, free of solubilizers, the diamine component consisting of at least 75-100% by weight Py-C12, based on the total weight of diamines in the aqueous solution, or at least 35% by weight Py-C14, based on the total weight of diamines in the aqueous solution, such a solution can advantageously be used as a biocide.

[0019] Furthermore, the ability to easily adjust the state of matter can be used for technological infiltration and immobilization, i.e. attachment to materials.

[0020] Thus, the present invention provides (1) An aqueous solution having a diamine component, the diamine component comprising at least 75-100% by weight of 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) based on the total weight of diamines in the aqueous solution, or at least 35% by weight of 5-N-carboxamido-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine (Py-C14) based on the total weight of diamines in the aqueous solution, the aqueous solution being preferably for attaching Py-C12 and / or Py-C14 to a material, more preferably for attaching Py-C12 and / or Py-C14 by solidifying it, the solution having a pH of 8 or less, and not containing a solubilizing agent. (2) A method for attaching a diamine selected from 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) and / or 5-N-carboxamido-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine (Py-C14), preferably Py-C12, to a material, said method comprising contacting the material with an aqueous solution having a diamine component including Py-C12 and / or Py-C14, the solution having a pH of 8 or less and free of a solubilizing agent, and solidifying the diamine after said contacting. to provide.

[0021] Alternative and preferred embodiments are set out in the dependent claims. [Brief description of the drawings]

[0022] [Figure 1] Fabrics treated with Py-C12 exhibit high wash resistance in aqueous systems and maintain their biocidal activity.

[0023] [Diagram 2] Adjustment of the state of matter of Py-C12 due to pH shift using HCl and NaOH.

[0024] [Diagram 3] Tuning the material state of Py-C12 due to pH shift using CO2.

[0025] [Figure 4] Adjustment of the material state of Py-C12 due to salt concentration.

[0026] [Diagram 5] Tuning the state of matter of Py-C12 due to temperature shift.

[0027] [Figure 6] Infiltration and subsequent immobilization of Py-C12 in synthetic sponges.

[0028] [Figure 7] Penetration and subsequent immobilization of Py-C12 in perforated fabrics.

[0029] [Figure 8] Penetration of Py-C12 in wood and subsequent immobilization.

[0030] [Figure 9] Penetration of Py-C12 in leather and subsequent immobilization.

[0031] [Figure 10] Penetration of Py-C12 in bone tissue and subsequent immobilization.

[0032] [Figure 11] Polyester fabrics treated with Py-C12 exhibit high wash resistance in aqueous systems and maintain their biocidal activity.

[0033] [Figure 12] Silk fabrics treated with Py-C12 exhibit high wash resistance in aqueous systems and maintain their biocidal activity.

[0034] [Figure 13] Cotton fabrics treated with Py-C12 exhibit high wash resistance in aqueous systems and maintain their biocidal activity.

[0035] [Figure 14] Wood samples treated with Py-C12 exhibit high washability in aqueous systems and maintain their biocidal activity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] Detailed Description of the Invention The present invention provides an aqueous solution as described in (1) above, the use of said solution as a biocide, and an associated method as described in (2) above.

[0037] The present invention is based on the discovery that changes in pH, temperature and / or salt concentration allow reversibly adjusting the state of matter of a diamine component, wherein in an aqueous environment, said diamine component comprises at least 75-100 wt. % Py-C12, based on the total weight of diamines in the aqueous solution, or at least 35-100 wt. % Py-C14, based on the total weight of diamines in the aqueous solution.

[0038] The aqueous solution is a solution of the following formula (I): [ka] and / or Py-C12 having the following formula (II): [ka] Py-C14 with Includes.

[0039] Formulas (I) and (II) encompass all stereoisomers and mixtures thereof.

[0040] Preferably, Py-C12 is (S)-5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine according to formula (Ia). [ka]

[0041] Preferably, Py-C14 is (S)-5-N-carboxamido-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine (IIa). [ka]

[0042] The aqueous solutions according to the present invention have a pH of 8 or less.

[0043] When the solutions of the present invention have a pH of 8 or less, the diamine components, including at least 75-100 wt. % Py-C12 based on the total weight of diamines in the aqueous solution, or at least 35-100 wt. % Py-C14 based on the total weight of diamines in the aqueous solution, remain in a dissolved / liquid state of matter regardless of the temperature of the solution.

[0044] In particular, diamine components comprising at least 75-100% by weight of Py-C12, based on the total weight of diamines in the aqueous solution, or at least 35-100% by weight of Py-C14, based on the total weight of diamines in the aqueous solution, are already in liquid form at a pH of 8 or less and at temperatures as low as about 16° C., enabling their use, for example, as biocides.

[0045] In a related embodiment, the aqueous solution according to the invention has a temperature of 44° C. or higher.

[0046] When the solutions of the present invention have a temperature of 44° C. or higher, the diamine components, including at least 75-100 wt. % Py-C12 based on the total weight of diamines in the aqueous solution, or at least 35-100 wt. % Py-C14 based on the total weight of diamines in the aqueous solution, remain in a dissolved / liquid state of matter even at high concentrations, such as 40% (w / v) in water, enabling their use as biocides.

[0047] At lower concentrations, i.e. in the range of about 1% to about 10%, the diamine components comprising at least 75-100% by weight of Py-C12 relative to the total weight of diamines in the aqueous solution, or at least 35-100% by weight of Py-C14 relative to the total weight of diamines in the aqueous solution, remain in a dissolved state / liquid state of matter already at a temperature of 40° C., which further broadens their practical application, for example as biocides.

[0048] The terms "biocide" and "biocide" are interchangeable and as used herein refer to chemicals intended to kill, deter, render harmless, or exert a pesticidal effect on any harmful microorganism. Biocides are commonly used in medicine, agriculture, forestry, and industry. Biocides may include preservatives, insecticides, disinfectants, and pesticides. The aqueous solutions according to the present invention do not include solubilizing agents.

[0049] Consistent with this, the solution is different from alkaline glucoprotamine. According to Karlheinz Disch (Disch K. "Glucoprotamine - a new antimicrobial substance". ZentralblHyg Umweltmed. 1994 Jun;195(5-6):357-65. PMID: 7916863), glucoprotamine is by definition a conversion product of L-glutamic acid and cocopropylene-1,3-diamine. The latter is a mixture of various acyclic N-alkylpropylene-1,3-diamines and N-alkylamines, differing mainly in the chain length of the N-alkyl residues. The conversion with L-glutamic acid is achieved by a thermal condensation process, which gives glucoprotamine as a complex mixture of various condensation products, and the unreacted components of the cocopropylene-1,3-diamine starting material. In summary, these mixtures are described as readily soluble in water. The good solubility in water is due to various reasons. First, the main part of the glucoprotamine mixture consists of unreacted starting materials, i.e., non-cyclic N-alkylpropylene-1,3-diamines and N-alkylamines, which can generally be dissolved in water. The same applies to the glutamic acid condensation products, which still have carboxyl groups and therefore exhibit good water solubility due to their zwitterionic nature. Second, the smaller part of the condensation products, which would show low water solubility as single-component substances, is easily dissolved by other water-soluble species acting as "soap-like" solubilizers. In general, this leads to good water solubility of glucoprotamine, but is disadvantageous for the purpose of aggregation state management, as explained in the present invention, and therefore fundamentally different from the solution of the present invention.

[0050] The term "solubilizer" as used herein generally refers to additives and auxiliaries that are merely favorable for the solubility of the active agents, i.e., Py-C12 and / or Py-C14.

[0051] According to the invention, the aqueous solution may contain additives and auxiliaries that are not favorable for the solubility of Py-C12 and / or Py-C14, such as, for example, dyes, viscosity modifiers, fragrances, flavorings, oils, or emulsifiers.

[0052] Solubilizers include 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); open-chain ketones such as nitriles such as acetonitrile, acetone, methyl ethyl ketone; cyclic ketones such as cyclohexanone; aldehydes such as propanal, benzaldehyde; alcohols (including polyalcohols and branched chain alcohols) such as methanol, ethanol, glycerin, 2-propanol; derivatives of alcohols such as 2-(2-butylethoxy)ethanol, 2-phenoxyethanol; amines, especially N-alkylamines such as triethylamine; open-chain ethers and polyethers such as acyclic N-alkylpropylene-1,3-diamines, diethyl ether, polyethylene glycol; dioxane, tetrahydrofuran, etc. aromatic compounds such as toluene, xylene, nitrobenzene; alicyclic compounds such as cyclohexane; heterocyclic compounds such as pyridine, furan, pyrrole, pyrrolidine, piperidine; open chain alkanes and alkenes such as paraffins, petroleum ether, heptane; halogenated hydrocarbons such as dichloromethane, chloroform, tetrachloroethylene, chlorobenzene; other derivatized hydrocarbons such as nitromethane, carbon disulfide, dimethyl sulfoxide, urea derivatives (e.g., tetramethylurea), sulfolane, aniline; emulsifiers such as sodium benzoate, crown ethers, sodium dodecyl sulfate, polysorbates (TWEEN®); dispersing agents such as surfactants and bile acids; and surfectants such as ethers with polyethylene glycol mono-Bu ether.

[0053] In accordance with the principles of the invention as described above and herein, the term "solubilizer" as used herein does not, of course, exclude Py-C12 or Py-C14.

[0054] In accordance with the present invention, the diamine component of the solutions of the present invention comprises, and preferably consists of, Py-C12 and / or Py-C14. In one embodiment, the diamine component of the solution of the present invention comprises Py-C12 and / or Py-C14, preferably consisting of Py-C12 and / or Py-C14, preferably wherein, based on the total weight of the diamine in the aqueous solution, the diamine component of the solution of the present invention comprises 75-100% by weight of Py-C12, more preferably, the diamine component of the solution of the present invention comprises 80-100% by weight of Py-C12, even more preferably, the diamine component of the solution of the present invention comprises 85-100% by weight of Py-C12, even more preferably, the diamine component of the solution of the present invention comprises 90-100% by weight of Py-C12, even more preferably, the diamine component of the solution of the present invention comprises 95-100% by weight of Py-C12, even more preferably, the diamine component of the solution of the present invention comprises 98-100% by weight of Py-C12, and most preferably, the diamine component of the solution of the present invention comprises 99-100% by weight of Py-C12.

[0055] In an alternative embodiment, the diamine component of the solution of the present invention comprises Py-C12 and / or Py-C14, preferably consisting of Py-C12 and / or Py-C14, preferably wherein, based on the total weight of diamines in the aqueous solution, the diamine component of the solution of the present invention comprises 35-100 wt.% Py-C14, more preferably the diamine component of the solution of the present invention comprises 40-100 wt.% Py-C14, even more preferably the diamine component of the solution of the present invention comprises 50-100 wt.% Py-C14, even more preferably the diamine component of the solution of the present invention comprises 60-100 wt.% Py-C14, even more preferably the diamine component of the solution of the present invention comprises 70-100 wt.% Py-C14, Even more preferably, the diamine component of the solution of the present invention contains 75 to 100% by weight of Py-C14, even more preferably, the diamine component of the solution of the present invention contains 80 to 100% by weight of Py-C14, even more preferably, the diamine component of the solution of the present invention contains 85 to 100% by weight of Py-C14, even more preferably, the diamine component of the solution of the present invention contains 90 to 100% by weight of Py-C14, even more preferably, the diamine component of the solution of the present invention contains 95 to 100% by weight of Py-C14, even more preferably, the diamine component of the solution of the present invention contains 98 to 100% by weight of Py-C14, and most preferably, the diamine component of the solution of the present invention contains 99 to 100% by weight of Py-C14.

[0056] Unless otherwise stated, weight percentages refer to weight percentages relative to the total weight of the diamine in the solution of the present invention, which is equal to the total weight of the diamine component in the aqueous solution.

[0057] In certain embodiments, 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 certain embodiments, the diamine component of the solution of the invention consists of Py-C12 and / or Py-C14, preferably the diamine component of the solution of the invention is Py-C12.

[0058] In certain embodiments, the solutions of the present invention are free of acyclic N-alkylpropylene-1,3-diamines and / or N-alkylamines.

[0059] The term "non-cyclic" as used herein refers to open-chain compounds, i.e. compounds that are linear, such as, for example, aliphatic compounds.

[0060] In a preferred embodiment, the solution of the present invention does not contain N-dodecylpropane-1,3-diamine and / or N-tetradecylpropane-1,3-diamine.

[0061] In a preferred embodiment, the solution according to the invention does not contain reaction products of glutamic acid with N-(C12-C14-alkyl)propylenediamines that are not Py-C12 and Py-C14, more preferably the solution according to the invention does not contain 5-N-carboxamido-2-pyrrolidone-N'-n-tridecylpropane-1,3-diamine.

[0062] In a related embodiment, the aqueous solution consists essentially of Py-C12, Py-C14, and water.

[0063] In certain embodiments, the aqueous solution consists essentially of Py-C12 and water, preferably the aqueous solution comprises Py-C12 at a concentration of from about 0.001% (w / v) to about 40% (w / v), more preferably the aqueous solution comprises Py-C12 at a concentration of from about 0.01% (w / v) to about 10% (w / v), and most preferably the aqueous solution comprises Py-C12 at a concentration of from about 0.1% (w / v) to about 5% (w / v).

[0064] In an alternative embodiment, the aqueous solution consists essentially of Py-C14 and water, preferably the aqueous solution comprises Py-C14 at a concentration of from about 0.001% (w / v) to about 40% (w / v), more preferably the aqueous solution comprises Py-C14 at a concentration of from about 0.01% (w / v) to about 10% (w / v), and most preferably the aqueous solution comprises Py-C14 at a concentration of from about 0.1% (w / v) to about 5% (w / v).

[0065] The terms "consists essentially of" or "consisting essentially of" as used herein means that the aqueous solution of the diamine and pH adjuster of the present invention may have certain additional additives and / or auxiliaries other than those described. The additives and / or auxiliaries may include dyes, viscosity modifiers, fragrances, flavorings, oils, or emulsifiers.

[0066] That is, the solutions of the present invention, in addition to the diamine component and water, may also contain a pH adjuster for the necessary adjustment of pH.

[0067] As used herein, "pH adjusting agent" refers to an agent capable of adjusting the pH to a desired range.

[0068] The pH adjuster may be a proton donating agent.

[0069] As used herein, "proton donating agent" means any acidifying agent, such as, for example, an acid compound or a mixture thereof, which is suitable for lowering the pH.

[0070] The proton donating agent may be a polymeric acid, a mineral acid, or an organic acid, including mixtures thereof.

[0071] The proton donor is hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ), and carbonic acid (H 2 CO 3 ), and most preferably the proton donating agent is HCl.

[0072] Thus, in certain embodiments, the solution of the present invention consists of Py-C12, Py-C14, water, and a proton donating agent.

[0073] In a preferred embodiment, the solution of the present invention consists of Py-C12, water, and a proton donating agent.

[0074] In an alternative embodiment, the solution of the present invention consists of Py-C14, water, and a proton donating agent.

[0075] Thus, in accordance with the above, the solution of the present invention can be obtained by mixing a diamine component with water and a pH adjusting agent, preferably a proton donating agent, for adjusting the pH to a value of 8 or less, wherein said diamine component consists of at least 75-100 wt. % Py-C12 or at least 35-100 wt. % Py-C14, based on the total weight of the diamine component.

[0076] Therefore, in a preferred embodiment, the solution of the present invention is obtained by combining or mixing water and a pH adjusting agent, preferably a proton donating agent, most preferably HCl, with a diamine component, wherein said diamine component consists of at least 75-100 wt. % Py-C12 or at least 35-100 wt. % Py-C14, based on the total weight of the diamine component.

[0077] Therefore, in a preferred embodiment, the solution of the present invention is obtained by combining or mixing water and a pH adjusting agent, preferably a proton donating agent, most preferably HCl, with a diamine component, wherein said diamine component consists of Py-C12 or Py-C14.

[0078] In a further related aspect, the invention provides a method for attaching a diamine selected from Py-C12 and / or Py-C14, preferably Py-C12, to a material, said method comprising: contacting the material with an aqueous solution having a diamine component including Py-C12 and / or Py-C14, the solution having a pH of 8 or less and free of a solubilizing agent; and solidifying the diamine after the contacting. The present invention provides a method comprising:

[0079] In a related aspect, the invention provides a method for attaching a diamine to a material, the diamine component of the solution of the invention consisting of at least 75-100 wt. % Py-C12 or at least 35-100 wt. % Py-C14, based on the total weight of the diamine in the aqueous solution, the method comprising:

[0080] contacting the material with an aqueous solution having a diamine component; and solidifying the diamine after said contacting. The present invention provides a method comprising:

[0081] It is noted that the attached diamine maintains its biocidal activity; and / or its activity to denature proteins; and / or its activity to interact with membrane lipids, ie, it acts as a detergent.

[0082] The term "attach" or "attachment" as used herein refers to non-covalent interactions. That is, the attachment to the material is based on non-covalent interactions, but this does not exclude the presence of additional covalent interactions. Most preferably, the attachment is a non-covalent attachment, also referred to as adhesive immobilization. The attachment to the material preferably includes one or more of hydrogen bonds, van der Waals forces, and / or ionic interactions.

[0083] Materials to which Py-C12 and / or Py-C14 may be attached, i.e., adhesively immobilized, include the inner and outer surfaces of materials. Such materials include absorbent, adsorbent, hygroscopic, and porous materials such as fabrics (textiles), e.g., cotton, wool, hemp, silk, polyester, polyamide, etc.; building materials, e.g., 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, e.g., extracellular matrix molecules, scaffolds, bones, wood, leather, paper, cardboard, resins, synthetic resins, and composite materials.

[0084] Materials according to the invention especially include materials which comprise or consist of various polymers such as, for example, polyamides, polyurethanes, polypeptides, polyols or polyesters.

[0085] Polyols include polysaccharides, especially cellulose and chitosan.

[0086] In certain embodiments, the material is selected from synthetic sponge, cloth, leather, bone tissue, or wood. In particularly preferred embodiments, the material is cloth, the cloth comprises cellulose, silk, or polyester, more preferably the cloth is cotton, i.e. the cloth comprises cellulose and may additionally comprise wax, fat, pectin, and / or water.

[0087] For the attachment to take place, the material should be contacted with an aqueous solution of Py-C12 and / or Py-C14, preferably a solution according to embodiment (1) above.

[0088] Particular and preferred embodiments of the aqueous solution of the diamine component according to the invention are described above in connection with aspect (1), which are equally applicable to the process according to aspect (2).

[0089] The contacting of the methods of the present invention may also be referred to as “incubating.” Typically, the contacting continues for at least about 10 seconds, and preferably for about 20 hours.

[0090] A suitable period of time can be readily determined by one skilled in the art and need only be to allow the diamine to penetrate the material.

[0091] Such penetration depends on whether the diamine component is in the liquid phase (state of matter), ie, whether the diamine component is dissolved.

[0092] In an aqueous environment, solubility can be achieved by adjusting the pH, temperature, and / or salt concentration.

[0093] Once the liquid diamine component has infiltrated the material, it may be advantageous to convert the diamine component to a solid phase (state of matter), thereby improving the attachment, i.e., adhesive immobilization, of the diamine to the material.

[0094] This solidification can be achieved by adjusting the pH, temperature, and / or salt concentration. For a diamine component consisting of at least 75-100 wt. % Py-C12 or at least 35-100 wt. % Py-C14, based on the total weight of diamine in the aqueous solution, for example cooling, i.e. decreasing the temperature, increasing the pH, and / or increasing the salt concentration, can convert the liquid phase (state of matter) to a solid phase (state of matter).

[0095] The method may include first heating the diamine component of the present invention to dissolve the diamine, preferably to 50° C., and after heating, contacting the material with the solution of the present invention; and after contacting, subsequently cooling the material to solidify the diamine, preferably to at least room temperature.

[0096] The method of the present invention may further comprise liquifying the diamine after solidifying, wherein said liquifying preferably comprises one or more of: heating the material; reducing the pH of the material; reducing the salt concentration of the material, and adding a solvent.

[0097] Suitable solvents for rendering the diamine liquid can include any type of class of organic solvents such as toluene, 1-propanol, 2-propanol, ethanol, 1-butanol, methanol, chloroform, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, and cyclohexane.

[0098] In a preferred embodiment, the method of the invention for attaching a diamine to a material, wherein the diamine is Py-C12, comprises contacting the material with an aqueous solution of Py-C12 at a concentration of at least about 0.05% (w / v), preferably from about 0.1% (w / v) to about 5% (w / v), said method optionally further comprising solidifying said diamine after said contacting.

[0099] In a related preferred embodiment, the method of the invention for attaching a diamine to a material, wherein the diamine is Py-C14, comprises contacting the material with an aqueous solution of Py-C14 at a concentration of at least about 0.05% (w / v), preferably from about 0.1% (w / v) to about 5% (w / v), said method optionally further comprising solidifying the Py-C14 after said contacting. In line with the foregoing, the present invention specifically includes the following specific embodiments.

[0100] 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, water, and a proton donating agent, preferably HCl, having a pH of 8 or less, preferably 7.8 or less.

[0101] 1. A method for attaching Py-C12 to a synthetic sponge, the method comprising contacting the sponge with an aqueous solution of Py-C12 and, optionally, subsequently solidifying the Py-C12 by cooling the sponge.

[0102] 1. A method for applying Py-C12 to a fabric having holes therein, the method comprising contacting the fabric with an aqueous solution of Py-C12 and, optionally, subsequently solidifying the Py-C12 by cooling the fabric.

[0103] 1. A method for attaching Py-C12 to a dried pine wood sample, the method comprising contacting the wood sample with an aqueous solution of Py-C12 and, optionally, subsequently solidifying the Py-C12 by cooling the wood sample.

[0104] 1. A method for applying Py-C12 to leather, the method comprising contacting the leather with an aqueous solution of Py-C12 and, optionally, subsequently solidifying the Py-C12 by cooling the leather.

[0105] A method for attaching Py-C12 to bone tissue, the method comprising contacting the bone tissue with an aqueous solution of Py-C12 and, optionally, subsequently solidifying the Py-C12 by cooling the bone tissue.

[0106] 1. A method for applying Py-C12 to a polyester fabric, the method comprising contacting the fabric with an aqueous solution of Py-C12 and, optionally, subsequently solidifying the Py-C12 by cooling the fabric.

[0107] 1. A method for attaching Py-C12 to silk fabric, the method comprising contacting the fabric with an aqueous solution of Py-C12 and, optionally, subsequently solidifying the Py-C12 by cooling the fabric.

[0108] 1. A method for applying Py-C12 to a cotton fabric, the method comprising contacting the fabric with an aqueous solution of Py-C12 and, optionally, subsequently solidifying the Py-C12 by cooling the fabric.

[0109] The present invention is further illustrated in the following examples, which should not be construed as limiting the invention. EXAMPLES

[0110] Example 1 Effect of pH on the state of matter of Py-C12 at 20 °C 1% (w / v) 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base was adjusted to pH values ​​between 3.0 and 10.0 with HCl or NaOH. At pH values ​​≦7.8, Py-C12 was completely soluble in water at room temperature. In contrast, at pH values ​​≧8, Py-C12 exists as a solid substance (see Table 1). [Table 1]

[0111] Example 2 Effect of temperature on the state of matter of Py-C12 (1% w / v) at pH 7.0 and pH 9.0 1% (w / v) of 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base was adjusted to pH values ​​of 7.0 and 9.0 using HCl or NaOH, followed by incubation 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 exists in a liquid state only at the temperatures tested, 50°C and 60°C (see Table 2). [Table 2]

[0112] Example 3 Interaction of salt concentration, temperature, and pH on the state of matter of Py-C12 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base, 5% (w / v), was adjusted to pH values ​​of 4.0, 5.0, and 10.0 with HCl or NaOH. NaCl solutions were combined with the samples using concentrations between 0 and 3M in water, followed by incubation at temperatures between 24°C and 45°C. The data demonstrate the complex interplay of various parameters on the state of matter of Py-C12 (see Table 3). [Table 3]

[0113] Example 4 Effect of temperature on the state of matter of Py-C12 (free base) at different aqueous concentrations 5-N-carboxamido-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). [Table 4]

[0114] Example 5 Biocidal effect of Py-C12 on bacteria and fungi at pH 7.0. To evaluate the bactericidal and fungicidal efficacy of Py-C12, quantitative suspension tests were carried out under contaminated conditions according to modified DIN EN ISO11930:2019 with organic loads using incubation periods of 1 and 3 days, respectively. For this purpose, 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) solutions were adjusted to pH 7.0 with HCl and subsequently diluted to the corresponding test concentrations. Table 5 shows the respective germ reduction factors (log 1000) for each microorganism with the corresponding Py-C12 concentrations and incubation periods. 10 ) is shown. [Table 5]

[0115] Example 6 Fabric treated with 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) exhibit high washability in aqueous systems and maintain their biocidal activity.

[0116] Circular sterile cotton fabric samples were treated with a liquid solution of Py-C12 (1% (w / v) in water; pH 7.0), followed by an extensive washing step. For control, samples were treated with water instead of Py-C12.

[0117] To test the wash resistance in aqueous systems, the samples were incubated in water at 50°C for 20 h, then washed with water at 37°C 16 times, for 5-10 min each time.

[0118] To test the wash resistance in an alcohol / acid system, the samples were washed 8 times with a 2-propanol / 1 mN HCl solution and a total of 8 times with water.

[0119] After all washing steps, all samples were inoculated with a β-galactosidase expressing E. coli strain and then incubated at 37° C. for 3 days.

[0120] The results are shown in Figure 1.

[0121] In aqueous systems, the samples treated with Py-C12 demonstrated high washability and retained their biocidal efficacy, as evidenced by the fact that blue-stained bacterial colonies were only found at the edges of the Py-C12-treated samples (Figure 1, top right frame), whereas the control (water) samples were entirely colonized with bacteria (Figure 1, left frame).

[0122] In contrast, in the alcohol / acid system, i.e., when acidic 2-propanol was used instead of water during the washing step, Py-C12 was clearly removed from the cotton samples, as evidenced by the fact that the samples treated with Py-C12 were completely colonized (Figure 1, bottom right panel) as well as the control (water).

[0123] Example 7 Adjustment of the state of matter of Py-C12 due to pH shift using HCl and NaOH 1% (w / v) 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base adjusted to pH 7 with HCl was completely soluble in water at room temperature (see FIG. 2, left panel). After increasing the pH above 9.0 by adding NaOH, Py-C12 began to precipitate in a time-dependent manner (see FIG. 2, right panel: white represents precipitation).

[0124] Example 8 CO 2 Tuning the state of matter of Py-C12 due to pH shift using 1% (w / v) and 5% (w / v) aqueous solutions of 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base were gassed 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 FIG. 3, left panel). 2 After degassing the gassed solution, Py-C12 precipitates due to a time-dependent increase in pH (see FIG. 3, right panel).

[0125] Example 9 Adjustment of the material state of Py-C12 due to salt concentration 2% (w / v) 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) was adjusted to pH 7 with HCl and combined at room temperature in water with various concentrations of NaCl ranging from 0.5 M to 3 M. At concentrations of 1.5 M or higher, a clearly visible precipitate (white color) is observed (see FIG. 4).

[0126] Example 10 Adjustment of the state of matter of Py-C12 due to temperature shift 1% (w / v) and 5% (w / v) aqueous solutions of 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base were completely soluble at 50°C (see Figure 5, left panel) but readily precipitated at room temperature (see white in Figure 5, right panel).

[0127] Example 11 Infiltration and subsequent immobilization of Py-C12 in synthetic sponges The synthetic sponge was treated with 5% (w / v) aqueous solution of 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base. In a first step, Py-C12 was warmed to 50°C to obtain a liquid solution. After incubating the sponge with the Py-C12 solution, the sponge was cooled to room temperature, whereupon the liquid Py-C12 was converted to a solid phase and thus immobilized within the sponge. The results are depicted in Figure 6, where both images represent the same area and show the small pores of the sponge filled with solid Py-C12 (right).

[0128] Example 12 Penetration and subsequent immobilization of Py-C12 in perforated fabrics The perforated fabric sheet was treated with 5% (w / v) 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base in water. In a first step, Py-C12 was warmed to 50°C to obtain a liquid solution. After incubating the fabric sheet with the Py-C12 solution, the fabric sheet was cooled to room temperature, whereupon the liquid Py-C12 was converted to a solid phase and thus immobilized within the fabric sheet. The results are depicted in Figure 7, where both images represent the same area and the figure shows the waxy surface of the material due to the solid Py-C12 (right).

[0129] Example 13 Penetration of Py-C12 in wood and subsequent immobilization Dry pine wood samples were treated with 5% (w / v) aqueous solution of 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base. In a first step, Py-C12 was warmed to 50°C to obtain a liquid solution. After incubating the wood sample with the Py-C12 solution, the wood sample was cooled to room temperature, whereupon the liquid Py-C12 was converted to a solid phase and thus immobilized within the wood sample. The results are depicted in Figure 8, where both images represent the same area and the figure shows the waxy surface of the wood sample due to the solid Py-C12 (right).

[0130] Example 14 Penetration of Py-C12 in leather and subsequent immobilization. Dried leather samples were treated with 5% (w / v) 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base in aqueous solution. In a first step, Py-C12 was warmed to 50°C to obtain a liquid solution. After incubating the leather samples with the Py-C12 solution, the samples were cooled to room temperature, whereupon the liquid Py-C12 was converted to a solid phase and thus immobilized within the leather sample. The results are depicted in Figure 9, where both images represent the same sample and the figure shows the waxy surface of the leather sample due to the solid Py-C12 (right).

[0131] Example 15 Penetration of Py-C12 in bone tissue and subsequent immobilization. Bone tissue was treated with 5% (w / v) aqueous solution of 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base. In a first step, Py-C12 was warmed 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, whereupon the liquid Py-C12 was converted to a solid phase and thus immobilized within the osteogenic tissue. The results are depicted in Figure 10, where all images represent the same sample. Left: untreated bone matrix; center: sample with pre-warmed liquid Py-C12; right: solid Py-C12 immobilized within the bone tissue. The lower box represents a magnified view of the upper box.

[0132] Example 16 Polyester fabrics treated with Py-C12 exhibit high wash resistance in aqueous systems and maintain their biocidal activity. Polyester fabrics treated with 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base exhibit high wash resistance in aqueous systems and maintain their biocidal activity even after 20 washing steps. In the first step, 5% (w / v) Py-C12 free base in water was warmed to 50°C to obtain a liquid solution. After incubation with the Py-C12 solution, the samples were cooled to room temperature, whereupon the liquid Py-C12 was transformed into a solid phase and thus immobilized on the material. After drying, the samples were washed with water at room temperature for 10, 20, and 30 times, 15 min each time. All samples were then inoculated with a β-galactosidase expressing E. coli strain and then incubated at 37°C for 3 days. Blue stained bacteria are only seen in the control and Py-C12 treated samples washed 30 times with water (see FIG. 11). The unstained groups (10 and 20 washing steps) demonstrated that polyester fabric biocidal treated with 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) exhibited high wash resistance even after 20 washing steps.

[0133] Example 17 Silk fabrics treated with Py-C12 exhibit high wash resistance in aqueous systems and maintain their biocidal activity. Silk fabrics treated with 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base exhibit high wash resistance in aqueous systems and maintain their biocidal activity even after 30 washing steps. In the first step, 1% (w / v) of Py-C12 free base in water was warmed to 50°C to obtain a liquid solution. After incubation with the Py-C12 solution, the samples were cooled to room temperature, whereupon the liquid Py-C12 was transformed into a solid phase and thus immobilized on the material. After drying, the samples were washed with water at room temperature for 10, 20, and 30 times, 15 minutes each time. All samples were then inoculated with a β-galactosidase expressing E. coli strain and then incubated at 37°C for 3 days. Blue-stained bacteria are only found in the control sample (see Figure 12). The data demonstrated that silk fabric biocidal treated with 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) exhibited high wash resistance even after 30 washing steps.

[0134] Example 18 Washability of immobilized Py-C12 on cotton fabric Cotton fabrics treated with 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base exhibit high wash resistance in aqueous systems and maintain their biocidal activity even after 30 washing steps. In the first step, 1% (w / v) Py-C12 free base in water was warmed to 50°C to obtain a liquid solution. After incubation with the Py-C12 solution, the samples were cooled to room temperature, whereupon the liquid Py-C12 was transformed into a solid phase and thus immobilized on the material. After drying, the samples were washed with water at room temperature for 10 and 30 times, 15 min each time. All samples were then inoculated with a β-galactosidase expressing E. coli strain and then incubated at 37°C for 3 days. The blue stained bacteria were distributed throughout the control sample and in a few locations on the Py-C12 treated sample that had been washed 30 times. The cotton sample that had been washed 10 times did not show any bacterial growth (see FIG. 13). The data demonstrated that the 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) biocidal treated cotton fabric exhibited high wash resistance even after 30 washing steps.

[0135] Example 19 Wood samples treated with Py-C12 exhibit high washability in aqueous systems and maintain their biocidal activity. Wood samples treated with 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) free base show high washing resistance in aqueous systems and maintain their biocidal activity even after 30 washing steps. In the first step, 1% (w / v) of Py-C12 free base in water was warmed to 50°C to obtain a liquid solution. After incubation of the beech wood sheets with the Py-C12 solution, the samples were cooled to room temperature, whereupon the liquid Py-C12 was converted to a solid phase and thus immobilized on the material. After drying, the samples were washed with water at room temperature for 10 and 30 times, 15 minutes each time. All samples were then inoculated with a β-galactosidase expressing E. coli strain and then incubated at 37°C for 4 days. Blue-stained bacteria are only found in the control sample (see Figure 14). The data demonstrated that wood samples biocidal treated with 5-N-carboxamido-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) exhibited high wash resistance even after 30 washing steps.

Claims

1. An aqueous solution having a diamine component, wherein the diamine component comprises at least 75 to 100% by weight of 5-N-carboxamide-2-pyrrolidone-N'-n-dodecylpropane-1,3-diamine (Py-C12) or at least 35 to 100% by weight of 5-N-carboxamide-2-pyrrolidone-N'-n-tetradecylpropane-1,3-diamine (Py-C14) relative to the total weight of diamine in the aqueous solution, wherein the aqueous solution is preferably used to adhere Py-C12 and / or Py-C14 to a material, more preferably to adhere Py-C12 and / or Py-C14 by solidifying it, and the solution has a pH of 8 or less and does not contain a solubilizer.

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

3. The solution according to claim 1, wherein the aqueous solution does not contain acyclic N-alkylpropylene-1,3-diamine.

4. The solution according to claim 1, wherein the aqueous solution comprises 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 performed at a temperature of 37°C or below.

7. A method for attaching a diamine selected from Py-C12 and / or Py-C14, preferably Py-C12, to a material, the method comprising contacting the material 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 solubilizer, and solidifying the diamine after contact.

8. The diamine component comprises at least 75 to 100% by weight of Py-C12 or at least 35 to 100% by weight of Py-C14 in the material, and the method comprises contacting the material with an aqueous solution having the diamine component according to any one of claims 1 to 4, and after the contact, The method according to claim 7, comprising solidifying the diamine.

9. The method according to claim 7, wherein the material is porous and / or absorbent and / or adsorbent.

10. The method according to claim 9, wherein the material is selected from synthetic sponge, cloth, leather, bone tissue, or wood.

11. The method according to claim 9, wherein the material is a cloth, and the cloth comprises cellulose, silk, and / or polyester.

12. The method according to claim 11, wherein the cloth is made of cotton.

13. The aforementioned solidification process (i) Cooling the aqueous solution, (ii) Increasing the pH of the aqueous solution, (iii) Increasing the salt concentration of the aqueous solution The method according to claim 7, comprising one or more of the above.

14. (i) a step of heating the diamine component, preferably a step of heating the diamine component to 50°C, and after heating (ii) The step of bringing the aqueous solution having the diamine component into contact with the material, and after contact, (iii) A step of cooling the material in order to solidify the diamine, preferably a step of cooling the material to at least room temperature. The method according to claim 7, including the method described in claim 7.

15. The method according to claim 14, further comprising liquefying the diamine after solidification.

16. To make it into the aforementioned liquid, (i) Heating the material, (ii) Adding a solvent The method according to claim 15, comprising one or more of the above.

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