JP2021516731A - Antibacterial organic fabric - Google Patents

Abstract

The present invention relates to a method for imparting antibacterial properties to a fabric by treating the fabric with at least one amino acid and / or at least one amino acid derivative in a liquid preparation process, and an antibacterial fabric having washing durability obtained by the method. Is.

Description

The present invention relates to a method for imparting antibacterial properties to a fabric by treating the fabric with at least one amino acid and / or at least one amino acid derivative in the liquid preparation process. The resulting fabric has high antibacterial performance that is durable against multiple wash cycles.

Background of the invention

Disinfectants are widely used in daily life in the medical field, food industry, agriculture, daily necessities, etc. to prevent the spread of pathogens and microbial infections.

However, one important problem posed by the heavy use of disinfectants is the continuous pollution of the environment by these disinfectants. Disinfectants are usually provided in solution and applied directly to contaminated surfaces such as hospital, laboratory equipment, or skin wounds. In such cases, the disinfectants are not neutralized, such as by autoclaves, or are not easily neutralized, and they eventually accumulate in the waste water. Similarly, bactericidal materials such as antibacterial plastics and coatings or fabrics, wound dressings, or functional clothing throughout the food packaging industry accumulate in the environment and even in these materials. The antibacterial agent used can constantly exude. Such contamination can ultimately result in the emergence of microbial strains that are resistant to commonly used antibacterial agents.

In the prior art, several methods for preparing antibacterial fabric materials are known. However, these methods rely solely on the use of synthetic antibacterial agents that are not easily biodegradable in the environment. Moreover, many of the antibacterial agents known in the prior art are not approved for use as food additives or preservatives and, as a result, cannot be used in combination with food packaging.

Therefore, there is a need for a method that gives the fabric antibacterial properties and that uses environmentally friendly chemicals. The agent that imparts antibacterial activity to the fabric is preferably a natural, organic compound. Such compounds are usually biodegradable, thus reducing the risk of accumulation and pollution of the environment. The raw tissue must be resistant to the resulting antibacterial fabric and must also be usable in delicate applications such as food preservation packages and wound dressings. Moreover, such antibacterial fabric products must be cost effective, especially in terms of the cost of the chemicals used.

The present invention eliminates the drawbacks of the prior art by providing the following methods in the first embodiment of the present invention. This method is a method of imparting antibacterial properties to the fabric and includes a main process cycle, which is the main process cycle.
A step of treating the fabric in a main liquid application process such as padding or preferably exhaustion, wherein the liquid agent of the main liquid application process contains at least one amino acid and / or at least one amino acid derivative.
The process of heat-treating the treated fabric and
The process of washing the heat-treated fabric as needed, and
Including the step of drying the washed fabric as needed.
The method preferably comprises a sub-process cycle performed after the step of the main process cycle, wherein the sub-process cycle is:
A step of treating the fabric using an auxiliary liquid addition process such as exhaustion or preferably a padding process, wherein the liquid agent of the secondary liquid addition process is at least one amino acid, at least one amino acid derivative, and / or. A process involving at least one antibacterial agent and
The process of heat-treating the treated fabric and
The process of washing the heat-treated fabric as needed, and
It includes a step of drying the washed fabric as needed.

The main solution application process combined with heat treatment allows the production of fabrics with durable antibacterial properties. The main solution application process may be a padding process or any other solution application process, but preferably exhaustion is used. This is because such a process allows amino acids and / or amino acid derivatives to diffuse substantially uniformly across the cross section of the fabric material. The sub-process may be, among other things, a padding process. A side process can enhance the overall antibacterial activity of the fabric. At least one amino acid and / or at least one amino acid derivative in the subprocess cycle may differ from at least one amino acid and / or at least one amino acid derivative in the main process cycle.

According to the second embodiment, in the first embodiment, the amino acids and / or the amino acid derivatives contained in the liquid preparation of the main liquid agent applying process and / or the auxiliary liquid agent applying process are 7 or more, preferably 8. As described above, more preferably, it has an isoelectric point of 8.5 or more, and / or has a positive charge independent of pH.

The use of amino acids and / or amino acid derivatives with an isoelectric point higher than 7 allows amino acids and / or amino acid derivatives to have a positive effective charge at any pH value below the isoelectric point. Thus, the higher the isoelectric point, the wider the range of pH values suitable for providing positive charges. Alternatively or additionally, amino acids such as quaternary ammonium and / or amino acid derivatives, including amino acid derivatives, may have a constant positive charge independent of pH. It has been found that the positive charge of amino acids and / or amino acid derivatives applied to the fabric generally enhances antibacterial activity, especially against Gram-positive and Gram-negative bacteria. Positive charges are thought to exert a bactericidal action by adhering to the cell membranes of negatively charged micro-organisms and destroying the integrity of the cell membranes.

According to the third embodiment, in any one of the preceding embodiments, the at least one amino acid contained in the liquid preparation of the main liquid preparation process and / or the secondary liquid preparation process is a natural amino acid or an artificial amino acid. It is selected from the group consisting of amino acids and amino acids that do not constitute proteins, and / or at least one amino acid derivative is selected from the group consisting of quaternary ammonium containing peptides and amino acid derivatives.

The present inventors have found that quaternary ammoniums containing common amino acids, peptides, and amino acid derivatives can bring unexpectedly high antibacterial activity to fabrics by adhering to the fabrics. In contrast, these compounds do not act as effective antibacterial agents when they are diluted with a solution or suspension. Therefore, the antibacterial activity of these compounds will be neutralized when the compounds are washed off the fabric.

According to the fourth embodiment, in any one of the preceding embodiments, the natural amino acid, the artificial amino acid, or the amino acid that does not constitute the protein is L-form, and / or the peptide is L. -Peptide.

L-enantiomers of amino acids and peptides can be easily obtained, for example, from cultures of E. coli, lactobacilli or yeast, eliminating the need for complex and cost-effective chemical synthesis.

According to a fifth embodiment, in any one of the preceding embodiments, the peptide is a dipeptide or polypeptide, which preferably comprises 3 to 50 amino acids.

According to the sixth embodiment, in any one of the preceding embodiments, the at least one amino acid contained in the solution of the main solution application process and / or the accessory solution application process is lysine, arginine, and the like. Alternatively, histidine, preferably arginine.

Naturally-derived amino acids, lysine, arginine or histidine are environmentally friendly as they are obtained from common biological cultures. Moreover, because these amino acids are non-toxic to living tissues, they can also be used as food additives and preservatives in the context of processing fabrics used in the food industry. Arginine is one of the preferred amino acids because it is available at a relatively low cost.

According to the seventh embodiment, in any one of the preceding embodiments, the at least one amino acid derivative contained in the liquid preparation of the main liquid agent applying process and / or the auxiliary liquid agent applying process is a lunch biotic. Nisin is preferred.

Nisin is commonly used as a food preservative and is therefore also used in the treatment of fabrics used in the food industry.

According to the eighth embodiment, in any one of the preceding embodiments, the at least one amino acid derivative contained in the solution of the main solution application process and / or the accessory solution application process is carnitine or betaine. , Preferably carnitine.

Carnitine and betaine are naturally occurring amino acid derivatives, which have a pH-independent, positively charged quaternary ammonium group. In particular, carnitine is known to have sufficient antibacterial activity when attached to fabrics.

According to the ninth embodiment, in any one of the preceding embodiments, the liquid preparation of the main liquid agent application process and / or the auxiliary liquid agent application process contains at least arginine and carnitine.

The combination of arginine and carnitine provides the fabric with particularly high antibacterial activity against both Gram-negative and Gram-positive bacteria, for example.

According to a tenth embodiment, in any one of the preceding embodiments, the at least one amino acid or amino acid derivative in the solution for all process cycles is in total, based on the weight of the fabric. An amount of 0.1% or more, preferably 0.2% or more, more preferably 0.5% or more, or 1% or more, 2% or more, 3% or more, or 4% or more by weight is applied to the fabric.

According to the eleventh embodiment, in any one of the preceding embodiments, the at least one amino acid or amino acid derivative in the solution for all process cycles is in total, based on the weight of the fabric. 20% or less, preferably 18% or less, or 16% or less, or 14% or less, or 12% or less, or 10% or less, or 8% or less, or 6% or less or 4% or less, most preferably 12 by weight. An amount of% or less is applied to the fabric.

According to the twelfth embodiment, in any one of the preceding embodiments, the preparation of the liquid preparation in the main liquid agent application process and / or the auxiliary liquid agent application process is carried out at least one amino acid and / or an amino acid derivative. In a step of preparing an aqueous reaction mixture containing the above reaction mixture and a step of keeping the reaction mixture warm for 10 minutes or longer, preferably 20 minutes or longer, more preferably 30 minutes or longer, even more preferably 40 minutes or longer, most preferably 50 minutes or longer. The temperature of the reaction mixture during heat retention includes a step of preferably 30 ° C. or higher, more preferably 40 ° C. or higher, even more preferably 50 ° C. or higher, and most preferably 60 ° C. or higher.

The pH is preferably lower than 6.5, preferably lower than 6.0, more preferably lower than 5.5, even more preferably lower than 5.0, most preferably the pH is about 4.5, and / or the pH is preferably higher than 3.0, more. Further increasing the antibacterial activity of the finished fabric by performing a heat retention step on the amino acids and / or amino acid derivatives in the reaction mixture, preferably above 4.0, even more preferably above 5.0, most preferably at about 5.5. I found that I could do it.

According to the thirteenth embodiment, in any one of the preceding embodiments, the liquid agent of the main solution application process and / or the accessory solution application process contains glucosamine and / or polyglucosamine.

The combination of polyglucosamine (chitosan) with one or more amino acids and / or amino acid derivatives can synergistically increase the antibacterial performance of the treated fabric.

Preferably, the polyglucosamine is of non-animal origin. For example, non-animal-derived polyglucosamine can be isolated from fungi such as Mucorales.

Of the amine groups of polyglucosamine, preferably 0.8% or less, more preferably 0.1% or less, are functionalized with at least one amino acid and / or amino acid derivative.

It has been found that complex binding of an amino acid or amino acid derivative to polyglucosamine in the sense of a peptide bond between the carboxy group of an amino acid or amino acid derivative and the amine group of polyglucosamine is not required to obtain high antibacterial activity. It was. Rather, the compounds may simply bind in the solution or in the reaction mixture without cross-linking or condensation reactions. In addition, an ester bond between the hydroxyl group of chitosan and the carboxy group of the amino acid and / or amino acid derivative can be created in the acidic solution, thereby adding the amine group of polyglucosamine, the amine group of the amino acid, and / or the amino acid. It has been found that the potential functional groups can be defunctionalized, for example to have a positive charge in a solution at neutral pH.

According to the fourteenth embodiment, in any one of the preceding embodiments, the polyglucosamine and / or glucosamine is in a water-soluble form.

A water-soluble form of polyglucosamine can be provided by dissolving a powder or flakes containing polyglucosamine in an acidic medium. By using the water-soluble form in the liquid, polyglucosamine can be well diffused over the cross section of the fabric.

According to the fifteenth embodiment, in the fourteenth embodiment, polyglucosamine and / or glucosamine is 50% or less, preferably 40% or less, more preferably 30% or less, most preferably 20% or less, and further /. Alternatively, it is provided as a concentrated solution or suspension of polyglucosamine and / or glucosamine of 1% or more, preferably 5% or more, more preferably 10% or more, and most preferably 15% or more.

According to the sixteenth embodiment, in the fifteenth embodiment, the pH of the concentrated solution or suspension is lower than 6.5, preferably lower than 6.0, more preferably lower than 5.5, and even more preferably 5.0. The pH is adjusted to be lower, most preferably about 4.5, further / or preferably higher than 3.0, more preferably higher than 4.0, even more preferably higher than 5.0, and most preferably about 5.5.

According to the seventeenth embodiment, in the sixteenth embodiment, the pH of the concentrated solution or concentrated suspension is an organic acid, more preferably a monocarboxylic acid, even more preferably acetic acid, lactic acid, formic acid, propionic acid. , P-Toluenesulfonic acid, or a combination thereof.

According to the eighteenth embodiment, in any one of the preceding thirteenth to seventeenth embodiments, the glucosamine and / or polyglucosamine in the solution for all process cycles is based on the weight of the fabric. For example, a total amount of 0.1% or more, preferably 0.2% or more, more preferably 0.3% or more, 0.7% or more, or 1% or more is applied to the fabric.

According to the nineteenth embodiment, in any one of the preceding thirteenth to eighteenth embodiments, glucosamine and / or polyglucosamine in the solution for all process cycles is added to the weight of the fabric material. Based on, the total amount is 5% or less by weight, preferably 4% or less by weight, more preferably 3% or less by weight, even more preferably 2% or less, most preferably 1.6% or less, or 1% or less. Granted to the fabric.

According to the twentieth embodiment, in any one of the preceding embodiments, the preparation of the liquid agent in the main liquid agent applying process and / or the auxiliary liquid agent applying process is performed.
The step of preparing at least one amino acid and / or amino acid derivative in the form of powder or liquid, and
The step of preparing the above-mentioned glucosamine and / or polyglucosamine in the form of powder or liquid, and
A step of preparing a preferably aqueous reaction mixture containing at least one amino acid and / or an amino acid derivative and glucosamine and / or polyglucosamine.
A step of keeping the reaction mixture warm for 10 minutes or longer, preferably 20 minutes or longer, more preferably 30 minutes or longer, even more preferably 40 minutes or longer, most preferably 50 minutes or longer, and the temperature of the reaction mixture during heat retention. Includes a step of preferably 30 ° C. or higher, more preferably 40 ° C. or higher, even more preferably 50 ° C. or higher, and most preferably 60 ° C. or higher.

The steps of preparing and warming the reaction mixture of polyglucosamine with amino acids and / or amino acid derivatives result in a further increase in antibacterial activity. We believe that the polyglucosamine molecule reacts with an amino acid and / or an amino acid derivative in the reaction mixture so that an ester bond is created. This new product can further react with the fabric during the liquid application process, for example via the free hydroxyl group of the polyglucosamine molecule. It was found that the temperature of the reaction mixture that promotes the reaction during the heat retention step was 30 ° C. or higher, more preferably 40 ° C. or higher, even more preferably 50 ° C. or higher, and most preferably 60 ° C. or higher.

According to the 21st embodiment, in the preceding 12th or 20th embodiment, the temperature of the reaction mixture during heat retention is 95 ° C. or lower, preferably 90 ° C. or lower, more preferably 85 ° C. or lower, and further. It is more preferably 80 ° C. or lower, and most preferably 75 ° C. or lower.

According to the 22nd embodiment, in the 12th, 20th, or 21st embodiment, the reaction mixture is stirred at a rotation speed of preferably 10 rpm or more during the heat retention step.

According to the 23rd embodiment, in any one of the preceding 12th or 20th to 22nd embodiments, the pH of the reaction mixture is lower than 6.5, preferably lower than 6.0, more preferably. Lower than 5.5, even more preferably lower than 5.0, most preferably about 4.5, and / or preferably higher than 3.0, more preferably higher than 4.0, even more preferably higher than 5.0, most preferred. Is about 5.5.

In concentrated solutions and / or aqueous reaction mixtures, acidic pH improves the solubility of polyglucosamine.

According to the twenty-fourth embodiment, in the preceding embodiment, the pH of the reaction mixture is an organic acid, more preferably a monocarboxylic acid, even more preferably acetic acid, lactic acid, formic acid, propionic acid, p-toluenesulfone. It is adjusted by using an acid or a combination thereof.

These acids have been found to be compatible with general fabric treatments, as described in more detail below.

According to the 25th embodiment, in any one of the preceding embodiments, at least one amino acid, an amino acid derivative and /, which is bound to the fabric in the main solution application process and / or the accessory solution application process. Alternatively, 50% or more, preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and most preferably 95% or more of polyglucosamine are dispersed or dissolved in the above-mentioned liquid preparation. Not combined.

According to the 26th embodiment, in any one of the preceding embodiments, the liquid agent in the main process cycle and / or the sub-process cycle is an azole compound, a silver ion, a polyhexamethylene biguanide, a fourth. Includes one, two, three, or all four antibacterial agents selected from the group consisting of quaternary ammonium organosilanes.

These antibacterial agents are not biodegradable. However, they enhance the antibacterial activity of the fabric in general, so it may be desirable to add them in some applications. The present inventors have found that these antibacterial agents can be well compatible with amino acids and / or amino acid derivatives.

According to the 27th embodiment, in the preceding 26th embodiment, the azole compound is propiconazole.

According to the 28th embodiment, in any one of the 26th or 27th embodiments, the quaternary ammonium organosilane is a hydrophilic quaternary ammonium organosilane, preferably an organomethoxysilane compound. More preferably, it is N-trimethoxysilylpropyl-n, n, n-trimethylammonium chloride.

According to the 29th embodiment, in any one of the 26th to 28th embodiments, the quaternary ammonium organosilane compound in the solution for all process cycles is based on the weight of the fabric material. A total amount of 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.25% by weight or more, and most preferably 0.3% by weight or more is applied to the fabric.

According to the thirtieth embodiment, in any one of the 26th to 29th embodiments, the quaternary ammonium organosilane compound in the solution for all process cycles is based on the weight of the fabric material. A total amount of 5% by weight or less, preferably 1.5% by weight or less, more preferably 1.2% by weight or less, particularly 1.0% by weight or less, and most preferably 0.8% by weight or less is applied to the fabric.

According to the 31st embodiment, in any one of the 26th to 30th embodiments, the silver cations in the above solution or the silver cations trapped in the inorganic matrix or the organic matrix in all the process cycles are described above. Based on the weight of the fabric material, a total amount of 0.1% by weight or less, preferably 0.05% by weight or less, more preferably 0.02% by weight or less, and most preferably about 0.01% by weight or less is imparted to the fabric.

According to the 32nd embodiment, in any one of the 26th to 31st embodiments, the silver cations in the above solution or the silver cations trapped in the inorganic matrix or the organic matrix in all the process cycles are described above. Based on the weight of the fabric material, a total amount of 0.001% by weight or more, preferably 0.002% by weight or more, more preferably 0.003% by weight or more, and most preferably about 0.005% by weight or more is imparted to the fabric.

According to the 33rd embodiment, in any one of the 26th to 32nd embodiments, the polyhexamethylene biguanide in the above solution for all process cycles is in total based on the weight of the fabric material. An amount of 0.5% by weight or less, preferably 0.4% by weight or less, more preferably 0.3% by weight or less, and most preferably 0.2% by weight or less is applied to the fabric.

According to a thirty-fourth embodiment, in any one of the twenty-sixth to thirty-third embodiments, the polyhexamethylene biguanide in the solution for all process cycles is in total, based on the weight of the fabric material. An amount of 0.03% by weight or more, preferably 0.05% by weight or more, or 0.10% by weight or more, preferably 0.15% by weight or more is applied to the fabric.

According to the 35th embodiment, in any one of the 26th to 34th embodiments, the azole compounds in the liquid preparation for all process cycles are in total based on the weight of the fabric material. An amount of 0.6% by weight or less, preferably 0.5% by weight or less, more preferably 0.4% by weight or less, and most preferably 0.3% by weight or less is applied to the fabric.

According to a thirty-sixth embodiment, in any one of the twenty-sixth to thirty-five embodiments, the azole compounds in the solution for all process cycles total, based on the weight of the fabric material. An amount of 0.05% by weight or more, preferably 0.10% by weight or more, more preferably 0.15% by weight or more, and most preferably 0.20% by weight or more is applied to the fabric.

According to the 37th embodiment, in any one of the preceding embodiments, the liquid agent in the main solution application process and / or the accessory solution application process contains water, preferably water and isopropanol, more preferably. Isopropanol is contained in the above solution at a concentration of between 0.05% by weight and 2% by weight, preferably between 0.1% by weight and 1% by weight, and more preferably between 0.2% by weight and 0.6% by weight.

Isopropanol reduces the surface tension of water, thereby promoting the penetration of amino acids and / or amino acid derivatives into fabric fibers. Isopropanol evaporates during the liquid application process and / or heat treatment.

According to the 38th embodiment, in any one of the preceding embodiments, the pH of the liquid agent in the main liquid agent applying process and / or the auxiliary liquid agent applying process is 6.5 or less, preferably 6.0 or less, more preferably. Is 5.5 or less, even more preferably 5.0 or less, most preferably about 4.5, and / or preferably higher than 3.0, more preferably higher than 4.0, even more preferably higher than 5.0, most preferably about 5.5. is there.

Acidic pH catalyzes the reaction between the fabric and the amino acids and / or amino acid derivatives, especially if it is an esterification reaction.

According to the 39th embodiment, in the preceding 38th embodiment, the pH of the liquid agent in the main solution application process and / or the accessory solution application process is an organic acid, more preferably a monocarboxylic acid, particularly acetic acid. , Lactic acid, formic acid, propionic acid, p-toluenesulfonic acid, or a combination thereof.

Organic acids can be used for many fabric materials such as viscose or cotton, whereas hydrochloric acid can damage the fabric, for example. In particular, monocarboxylic acids can be used during the liquid preparation process because the acid does not affect the total charge of the fabric after the addition of the amino acid and / or the amino acid derivative. In contrast, dicarboxylic acids such as citric acid or polyfunctional acids such as tricarboxylic acids increase the total negative total charge of the fabric when attached to the fabric via one of the functional groups. Can be made to.

According to the 40th embodiment, in any one of the preceding embodiments, the solution comprises a cross-linking reagent, preferably an isocyanate cross-linking agent or an acrylic cross-linking agent, more preferably a blocked isocyanate cross-linking agent.

Crosslinkers are typically not biodegradable. However, they can be covalently attached to amino acids and / or amino acid derivatives to the functional groups of the fabric, thereby increasing the washing durability of the resulting antibacterial properties of the fabric, so they can be added in some applications. It may be desirable.

According to the 41st embodiment, in any one of the preceding embodiments, during the exhaustion process, the liquid is 40 ° C. or higher, particularly 45 ° C. or higher, preferably 50 ° C. or higher, more preferably 55. It has a temperature of ° C. or higher, even more preferably 60 ° C. or higher, most preferably about 65 ° C. or higher.

According to the 42nd embodiment, in any one of the preceding embodiments, during the exhaustion process, the solution is subjected to a temperature below the boiling point, preferably 95 ° C. or lower, more preferably 90 ° C. or lower, in particular. It has a temperature of 85 ° C. or lower, most preferably about 80 ° C. or lower.

According to the 43rd embodiment, in any one of the preceding embodiments, the exhaustion time of the exhaustion process is 30 minutes or longer, preferably 40 minutes or longer, more preferably 50 minutes or longer, particularly 55 minutes. The above is most preferably about 60 minutes or more, and / or 120 minutes or less, particularly 90 minutes or less, preferably 80 minutes or less, more preferably 75 minutes or less, even more preferably 70 minutes or less, still more preferably. 65 minutes or less, most preferably about 60 minutes or less.

According to the 44th embodiment, in any one of the preceding embodiments, the heat treatment of the main process cycle and / or the sub-process cycle includes drying and / or curing.

According to the 45th embodiment, in the preceding 44th embodiment, the drying is performed at an ambient temperature of 190 ° C. or lower, preferably 180 ° C. or lower, more preferably 170 ° C. or lower, and / or 60 ° C. or higher. It is preferably carried out at an ambient temperature of 80 ° C. or higher, more preferably 100 ° C. or higher, and most preferably about 120 ° C. or higher.

According to the 46th embodiment, in any one of the preceding 44th or 45th embodiments, the curing is at 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, especially 175. At an ambient temperature of ° C. or higher, most preferably about 180 ° C. or higher, and / or around 205 ° C. or lower, preferably 195 ° C. or lower, more preferably 190 ° C. or lower, particularly 185 ° C. or lower, most preferably about 180 ° C. or lower. It is done at temperature.

The curing temperature is adapted to promote (covalent) binding of amino acids and / or amino acid derivatives to the fabric.

According to the 47th embodiment, in any one of the preceding embodiments, the starting fabric comprises a hydroxyl group, a peptide group and / or a carbonyl group, particularly a hydroxyl group and / or a peptide group.

These groups allow the fixation, binding, attachment or adhesion of one or more amino acids and / or amino acid derivatives to the fabric. In an exemplary embodiment, the starting fabric material comprises a peptide group and / or a hydroxyl group, particularly a hydroxyl group.

According to the 48th embodiment, in any one of the preceding embodiments, the starting fabric is a cellulose-based fabric material, an animal-derived fabric material, a synthetic fabric material, or a cellulose-based fabric material, an animal-derived fabric material. And / or a mixture of synthetic fabric materials.

According to the 49th embodiment, in the 48th embodiment, the cellulosic fabric was selected from the group consisting of cotton, viscose, rayon, linen, hemp, ramie, jute, and a combination thereof (blend). Includes one or more. In particular, the cellulose fabric contains 50% or more, preferably 60% or more, more preferably 70% or more viscose.

According to the 50th embodiment, in the 48th embodiment, the animal-derived fabric comprises one or more selected from the group consisting of wool and silk.

According to the 51st embodiment, in the 48th embodiment, the synthetic fabric is polyester, polyamide (nylon), acrylic polyester, spandex (elastan, lycra), aramid, modal, sulfur, polylactide (PLA), Includes one or more selected from the group consisting of lyocell, polybutyltetrachloride (PBT), and combinations thereof (blends).

According to the 52nd embodiment, in any one of the preceding 47th to 51st embodiments, 90% or more, preferably 95% or more, more preferably 98% or more, and even more of the starting fabric. Preferably 99% or more, most preferably about 100%, is formed from renewable raw materials and is further / or biodegradable and / or naturally organic.

According to the 53rd embodiment, in any one of the preceding embodiments, the fabric is selected from the group consisting of woven fabrics, knit fabrics, crochet fabrics, bonded fabrics, warp knitted fabrics, and non-woven fabrics. Preferably, the antibacterial fabric is a woven fabric.

A preferred fabric is a multifilament fabric, i.e. a woven fabric made from multifilament yarn. Woven fabrics are preferred because the treatment of fabrics is significantly cheaper than the treatment of yarns and fibers. Fabrics made from multifilament yarns are preferred over yarns made from monofilament yarns because they are stronger, have a larger surface area and are capable of blending.

According to a 54th embodiment, the present invention is further an antibacterial fabric obtained by any one of the preceding embodiments, preferably at least one amino acid and / or an amino acid derivative is the fabric. And / or, if present, preferably, the glucosamine, polyglucosamine and / or additional antibacterial agents are also attached, bound or covalently attached to the fabric. , About antibacterial fabrics.

According to the 55th embodiment, in the 54th embodiment, the amino acid, amino acid derivative, glucosamine, polyglucosamine and / or additional antibacterial agent attached to, bound to, or covalently bound to the fabric is the embodiment 10. , 11, 18, 19, 29 to 36, each having an individual weight specified for each antibacterial agent.

According to the 56th embodiment, in the 54th or 55th embodiment, the antibacterial fabric has a reduction value of Pseudomonas aeruginosa ATCC 9027 and / or Staphylococcus aureus ATCC 6538 measured according to AATCC test method 100-2012. Within a 24-hour contact time, preferably within a 6-hour contact time, more preferably within a 1-hour contact time, even more preferably within a 15-minute contact time, especially within a 10-minute contact time. , 99% or more, preferably 99.9% or more, more preferably 99.99% or more, and most preferably 99.999% or more.

According to the 57th embodiment, in the 56th embodiment, the reduction value is 20 in a washing machine at 40 ° C., preferably using a non-antibacterial, non-ionic, non-chlorine-containing laundry detergent product. It is obtained even after washing 5 times or more over a minute to 40 minutes, preferably after a standard rinse cycle, and more preferably after washing 10 times or more.

According to the 58th embodiment, in any one of the 54th to 57th embodiments, the antibacterial fabric was tested according to AATCC Test Method 30-2013 Part III (agar plate, Aspergillus niger or Candida albicans). In some cases, it exhibits zero growth of microorganisms.

According to the 59th embodiment, in the 58th embodiment, the zero growth value is set in a washing machine at 40 ° C., preferably using a non-antibacterial, non-ionic, non-chlorine-containing laundry detergent product. It is obtained even after washing 5 times or more over 20 to 40 minutes, preferably after a standard rinse cycle, and more preferably after washing 10 times or more.

According to the 60th embodiment, in any one of the 54th to 59th embodiments, 90% of all antibacterial agents attached to the fabric or all antibacterial agents contained in the fabric, based on weight. Above, preferably 95% or more, more preferably 98% or more, even more preferably 99% or more, particularly 99.5%, most preferably about 100% are biodegradable and / or naturally organic. It is a thing.

All percentages below are for weight unless otherwise stated. "% Owf" or "% o.w.f." means "of weight fabric" and is the weight percentage of the uptake of the antibacterial agent into the woven fabric. "Gpl" or "GPL" means "gram per liter". "R.t." means "room temperature", the temperature of which is in the range of 15 ° C to 35 ° C.

The term "antibacterial" as used in the context of the present invention relates to the ability to kill at least some types of microbes or to prevent the growth or reproduction of at least some types of microbes. The terms relate to compounds, agents, products, or processes that are harmful to one or more "microorganisms" used in the context of the present invention. Preferably, one or more "microorganisms" are killed by a product or process that has "antibacterial properties".

As used herein, the term "antibacterial agent" means all chemical compounds that have antibacterial activity against at least some types of microbes. Exemplary antibacterial agents are chitosan, quaternary ammonium organosilanes, silver cations, polyhexamethylene biguanide (PHMB), propiconazole. Amino acids and / or amino acid derivatives are not antibacterial agents by themselves, but become antibacterial by adhesion and / or binding to fabrics. Thus, in the context of the attachment of amino acids and / or amino acid derivatives to fabrics, these compounds can also be understood as antibacterial agents.

The terms "microorganisms" and "microorganisms" are used interchangeably in the context of the present invention and are defined to include organisms that are invisible to the naked eye, such as unicellular organisms. In particular, the terms "microorganisms" and "microorganisms" refer to viruses, as well as prokaryotes including bacteria and archaea, eukaryotes including protists, animals such as dust mites and spider mites, fungi, and plants such as green algae. Is included.

As used herein, the term "fabric" means any form of fabric or fabric material, including fibers, threads, sewing threads, twisted threads, woven fabrics made from fibers and / or threads, and fibers, threads. And / or final products made from woven fabrics. The fabric may be a woven fabric, a knit fabric, a crochet fabric, a bonded fabric, and / or a non-woven fabric. The fabric material may be spun, electrospun, stretched or extruded.

As used herein, the term "biodegradable" means any form of fabric, amino acids, amino acid derivatives, chitosan, antibacterial agents or other chemicals that can be degraded by living cells such as bacteria. ..

As used herein, the term "natural organic" means an organic compound that can be produced from living organisms. For example, all amino acids or chitosans synthesized by living cells are naturally organic compounds.

Detailed description of the invention

Preferred embodiments and examples of the invention are described in the following detailed description. However, it should be emphasized that the present invention is not limited to these embodiments.

The present invention relates to a method of imparting antibacterial properties to a fabric. Advantageously, this method allows the use of naturally occurring functional agents such as amino acids and peptides for the finishing of fabrics, or the use of combinations of their compounds and chitosan.

The present inventors have found that the accumulation of positive charges on the surface of the fabric by (covalent) bonding of the amino acid arginine and / or the amino acid derivative carnitine to the fabric imparts a high antibacterial effect to the fabric. Without wishing to be bound by any theory, it is believed that the high density of positive charges of amino acids and / or amino acid derivatives causes the cell membranes of micro-organisms, such as Gram-negative or Gram-positive bacteria, to divide. ing.

Since antibacterial agents such as natural amino acids are biodegradable, the resulting antibacterial fabric is environmentally friendly. Moreover, the use of amino acids and / or amino acid derivatives as antibacterial agents reduces the production cost of antibacterial fabrics as compared to, for example, antibacterial fabrics composed solely of chitosan.

Liquid application process:

The method according to the invention includes a liquid preparation process for the addition of amino acids and / or amino acid derivatives, particularly an exhaustion process. As is known in the art, during the exhaustion process, the fabric material is brought into contact with a liquid containing components that are transferred to the object during the exhaustion process. This can be done by guiding the fabric material into a container filled with the liquid agent. The yarn and woven fabric are typically processed in an exhaustion process. In a typical exhaustion process, the chemicals applied to the fabric material are dissolved or diffused in a solvent, such as water, in the required material-liquid ratio. The material-liquid agent ratio is the ratio between the weight of the fabric to be treated and the weight of the liquid agent. For example, if the desired material-liquid agent ratio is 1: 2, the liquid agent will be 600 kg for 300 kg of the fabric material to be absorbed. For example, the fabric material is brought into contact with the liquid by immersing the fabric material in the liquid, whereby the chemical preferably comes into contact with the fibers and more preferably enters the fibers. Each liquid temperature and each exhaustion time so that kinematic and thermodynamic reactions occur as required for proper diffusion of the drug and proper penetration of the drug into the fibers. Is set. As the fabric material and its fibers absorb the chemicals, the concentration of the chemicals in the liquid is reduced. As is known in the art, the degree of liquid agent exhaustion as a function of elapsed time is called the degree of exhaustion process. The percentage of chemicals that are exhausted on the fabric at the end of the process but were initially present in the liquid is called the exhaust rate or exhaust rate.

In the exhaustion process, the fabric opens and the fibers are individually exposed to permeation by amino acids and / or amino acid derivatives. This is especially true for woven fabrics made from multifilament yarns or multifilament yarns. Woven fabrics made from multifilament yarns or multifilament yarns are preferred for many applications because they are stronger, have a larger surface area and can be blended. Thus, by utilizing the exhaustion process, the drug can diffuse into the fibers, as in the case of more superficial liquid application processes such as padding and spraying, the surface space of the fibers. Does not occupy. Therefore, by utilizing the release process in the main process cycle, it is possible for the sub-antibacterial process cycle, especially the sub-process cycle using the padding process, to improve antibacterial performance, or in further process cycles other functional The drug can be applied to the fabric. On the other hand, the performance is not improved, and the performance is not improved at least to the same extent, even if the liquid agent is repeatedly applied to the surface so as to repeatedly apply the padding. Furthermore, we have found that leaching is at its lowest value only when release is used in the main process cycle. On the other hand, in the case of a non-woven fabric, the non-woven fabric often cannot withstand the force exerted by a discharge device such as a jigger, so that the discharge may not be preferable.

Suction can be done by any suitable technique on any suitable device such as thread dyeing device, beam device, winch device, jet dyeing machine, continuous dyeing machine (CDR), continuous bleaching machine (CBR), or jigger device. You may go with.

Due to exhaustion, the liquid agent spreads evenly over the entire cross section of the fabric material so that there is preferably no portion of the fabric material that does not come into contact with the liquid agent. As a result, at this time, interactions and / or bonds can occur between the fabric material and one or more amino acids and / or amino acid derivatives. Preferably, most of the liquid antibacterial agents are evenly absorbed over the entire cross section of the fabric material. Preferably, the release rate of the exhaustion process is 75% or more, more preferably 85% or more, more preferably 90% or more, most preferably 95% or more, and most preferably the amino acid contained in the exhaust liquid agent. , Amino acid derivatives, or uptake about 95% of antibacterial agents. Due to this release rate, most of the components of the liquid agent are absorbed by the fabric material, so that the cost can be reduced. It is also more ecological than processes with low uptake rates.

In general, applying a lot of heat to the woven ground is good for bonding. Therefore, preferably, the temperature of the liquid agent during the exhaustion process is sufficiently high so that one or more antibacterial agents in the liquid agent are diffused substantially uniformly over the cross section of the fabric material as a result of the exhaustion process. Make the exhaustion time long enough. Thus, the temperature of the liquid agent should be sufficiently high and the exhaustion time should be sufficiently long so that it preferably penetrates sufficiently into the fabric material and the antibacterial agent diffuses throughout the fabric material. Preferably, the exhaustion time is sufficiently long and the temperature of the liquid during the exhaustion process is sufficiently high so that the fabric material can exert the desired antibacterial performance after each curing process, as outlined below. To do.

However, excessive heat causes yellowing and weakens the woven fabric. Therefore, preferably, as a result of the exhaustion process, the fabric material does not discolor and / or turn yellow and / or its breaking (tensile) strength exceeds 15%, preferably more than 10%. The temperature of the liquid during the exhaustion process is sufficiently lowered and / or the exhaustion time is sufficiently shortened so as not to decrease more preferably by more than 7% and most preferably by more than 5%. As is known in the art, excessive heat causes yellowing of the fabric material. This yellowing is not desirable. Therefore, the temperature of the liquid should not be too high. If the temperature is too high, too much steam will be formed and the process will be less efficient. Furthermore, if the temperature of the liquid agent is too high, turbulence may occur in the liquid agent bathtub, which may damage the fabric material. Also, as the exhaustion time increases, the fabric material can become weaker, that is, its breaking strength can decrease.

When used in the context of the present invention, the term exhaustion time preferably means that at least a portion of the entire batch of fabric material comes into contact with the liquid for the first time and the last portion of the batch is from the liquid. It is defined as the period until it is taken out. The ideal exhaustion time can vary significantly for a given application. If the fabric is a woven fabric, the ideal exhaustion time will depend on the type of equipment, the size of the liquid bath, and the length and weight of the woven fabric. For example, if the ideal exhaustion time for a 1,500 meter long woven fabric is 60 minutes, the ideal exhaustion time for a 3,000 meter woven fabric can be 100 minutes otherwise under the same conditions. .. Where exhaustion times are specified herein, exhaustion times are operated at standard weaving speeds (eg, 50 meters / minute) for fabrics of length 1,500 meters and weight 200 g / m2. The time equivalent to the exhaustion time with a standard jigger device (for example, model number Y1100 manufactured by Yamada). For any given fabric material and release device, one of ordinary skill in the art will be able to determine an exhaustion time equivalent to the exhaustion time specified for the parameters described above, using common general knowledge. Let's do it.

Therefore, the exhaustion process disperses one or more amino acids and / or amino acid derivatives, preferably antibacterial agents, substantially uniformly across the cross section of the fabric material.

Heat treatment is performed after the exhaustion process. If there is only one process cycle, the heat treatment can include drying and curing. Curing occurs at high temperatures, preferably 180 ° C, but this curing is necessary to fully bind the amino acids and / or amino acid derivatives to the fabric material in a non-leaching or substantially non-leaching manner. is there. The temperature of the fabric must not exceed 100 ° C until the moisture in the fabric evaporates, so the fabric must be dried prior to curing. If the main process cycle is followed by a further process cycle, i.e. a sub-process cycle as described herein, or a process cycle that imparts other properties such as hydrophilicity or hydrophobicity to the fabric, this step, i.e. The main process cycle preferably does not cure. This is for economic reasons, but also because curing seals or seals the fabric, reducing the effectiveness of the process in further process cycles. If there are additional process cycles, the fabric must be dry. Otherwise, the fabric will not absorb the liquid for additional process cycles. Drying can be done at a lower temperature, such as room temperature. However, in order to speed up the manufacturing process, drying is preferably carried out by heat treatment. In addition, this heat treatment results in the basic binding of the chemical to the fabric and prevents the chemical from being washed away in subsequent cleaning steps.

Drying can be done by a normal heat setting process depending on the fabric material actually used. Preferably, the fabric material is dried at least partially at a temperature of 60 ° C. or higher, more preferably 100 ° C. or higher, even more preferably 110 ° C. or higher, most preferably about 120 ° C. or higher. The lower the temperature, the longer the dwell time required. Longer dwell times are not desirable as they adversely affect the fabric from the standpoint of yellowing and also the strength of the woven fabric.

Preferably, the fabric material is dried at a temperature of 190 ° C. or lower, more preferably 180 ° C. or lower, particularly 170 ° C. or lower. Even more preferably, the fabric material is dried at a temperature of 150 ° C. or lower, more preferably 140 ° C. or lower, particularly 130 ° C. or lower, and most preferably about 120 ° C. or lower.

Preferably, the drying time at the above temperatures is 30 seconds or longer, preferably 40 seconds or longer, more preferably 50 seconds or longer, most preferably about for every 100 g of woven fabric weight per ^{m 2 (when the fabric material is woven fabric).} 60 seconds or more. More preferably, the drying period is 120 seconds or less, preferably 90 seconds or less, more preferably 75 seconds or less, and most preferably about 60 seconds or less for every 100 g of woven fabric weight per ^{m 2} (when the fabric material is woven fabric). Do over. It is understandable that as the weight of the fabric ( ^{per m 2) increases, so does the drying time.} Those skilled in the art will understand that similar drying times apply when the fabric material is yarn, and that they choose a drying time that depends on the diameter of the yarn.

The drying process may typically be carried out by passing the fabric material through a similar drying device, typically a tenta or tenta frame (sometimes also referred to as a "tenter"). Drying the fabric material preferably removes excess moisture.

If there are no more process cycles, a curing process may be performed after the drying process. In this case, the curing process may be as described below. However, in the sub-process cycle, the curing process is preferably carried out with the drying process in one single pass via the tenta, but if there is only one process cycle, it is preferably drying and curing. There are two separate paths via the tenta for. This is because if there is only one process cycle, the fabric is typically wet and therefore the drying process can be better controlled by performing the drying process in a separate path through the tenta. ..

On the other hand, if there is an additional antibacterial or liquid application process cycle, a cleaning step may be performed after the drying process. During washing, the fabric material is preferably washed in water, more preferably without the use of detergents. Preferably, the fabric material is washed in a bathtub having a temperature of 30 ° C to 50 ° C, more preferably 35 ° C to 45 ° C, for example a water bath. The washing time is preferably 35 minutes or longer, more preferably 40 minutes or longer.

After the main process cycle, the resulting fabric material already has antibacterial properties. However, antibacterial properties can be further improved by performing an optional subprocess cycle such as padding. Alternatively, other liquid agent application processes such as exhaustion process, coating process, or spraying process can be used. However, the padding process requires less time and is therefore cheaper than effusion, providing a more uniform distribution of liquid than spraying (and unlike spraying, it can be applied to both sides of the woven fabric at the same time). The padding process has proven to be particularly beneficial, as coating pastes typically contain leaky components that give better results in terms of non-leaching properties than coatings.

Any suitable method can be used to carry out the padding process. Preferably, each liquid preparation (which may or may not be the same liquid preparation as the liquid preparation of the exhaustion process 11 but will be described in detail later) is prepared and each padding is performed via a pump. Supply to the mangle. Therefore, the padding process 15 preferably involves applying one or more rolls to optimize the wet pickup of the liquid on the fabric material. Typically, the appropriate padding mangle pressure is pre-determined depending on the quality of the fabric material and is generally set to optimize the wet pickup of the antibacterial agent. The liquid may be at room temperature or may be heated during the padding process.

Preferably, the padding process is carried out within the padding mangle at a pressure of 0.5 bar to 4 bar, more preferably 1.0 bar to 3.0 bar, even more preferably 1.5 bar to 2.5 bar, most preferably about 2 bar. The pick-up rate (or "wet pick-up") indicates the amount of liquid applied and is defined as a percentage of the weight of the dry untreated fabric as follows. % Pickup rate = weight of applied liquid x 100 / weight of dry fabric. For example, a 65% pickup rate means that 1 kg of fabric is given 650 grams of liquid. The pick-up rate of the padding process according to the present invention is preferably 40% or more, more preferably 50% or more, even more preferably 55% or more, particularly 60% or more, and most preferably about 65% or more. The pick-up rate of the padding process according to the present invention is preferably 90% or less, more preferably 80% or less, even more preferably 75% or less, particularly 70% or less, and most preferably about 65% or less.

After padding, heat treatment including drying and curing may be performed. Curing can be defined as a heat treatment of a dry fabric material at the temperatures referred to in this application. Drying means that the fabric is 99% dry. Typically, a tenter may be used for curing.

Preferably, the curing is at least partially performed at a curing temperature of 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, even more preferably 175 ° C. or higher, most preferably about 180 ° C. or higher. Preferably, the curing is carried out at a temperature of 205 ° C. or lower, preferably 195 ° C. or lower, more preferably 190 ° C. or lower, even more preferably 185 ° C. or lower, and most preferably about 180 ° C. or lower. Thus, the preferred curing temperature is about 180 ° C.

Preferably, the curing is 20 seconds or longer, preferably 24 seconds or longer, more preferably 28 seconds or longer, most preferably about 30 seconds or longer per 100 g of woven fabric weight per ^{m 2} (when the fabric material is woven fabric). It is carried out at the temperatures mentioned above over a period of time. Preferably, the period during which this temperature is applied is 50 seconds or less, preferably 45 seconds or less, more preferably 40 seconds or less, even more preferably, for 100 g of woven weight per ^{m 2 (when the fabric material is woven).} Is 35 seconds or less, most preferably about 30 seconds or less. Thus, in the most preferred embodiment, a curing temperature of about 180 ° C. is applied for about 30 seconds to 100 g of fabric weight per ^{m 2.} However, for heavy woven fabrics, the preferred curing time is longer than this ^{, for woven fabrics from 350 g / m 2} to 500 g / m ² for 45 seconds at the above temperatures and for woven fabrics above 500 g / m ^2. It will be 60 seconds. This is because as the thickness of the woven fabric increases, it takes more time for the heat rays to reach the center of the woven fabric. It can be understood that if the fabric material is yarn, the modified temperature is applied and the dwell time and curing temperature depend on the diameter of the yarn. Since the curing temperature is substantially independent of the fabric material, only the curing time (and drying time) needs to be adjusted when using different fabric materials. The present inventors have found that the curing time or dwell time increases substantially linearly as the weight of the fabric material increases.

Preferably, curing is performed immediately after drying. As such, preferably the fabric material is substantially uncooled between drying and curing. Therefore, when drying and curing are performed in direct succession, both steps are preferably 45 seconds or more, preferably 50 seconds or more for 100 g of woven weight per ^{m 2 (if the fabric material is woven).} It is carried out for a total period of seconds or longer, more preferably 55 seconds or longer, and most preferably about 60 seconds or longer. More preferably, drying and curing is 75 seconds or less, preferably 70 seconds or less, more preferably 65 seconds or less, and most preferably about about 100 g of woven weight per ^{m 2 (when the fabric material is woven).} It is performed for a total period of 60 seconds or less.

Functional drug:

The liquid preparation of the main liquid preparation cycle and, if necessary, the liquid preparation of the sub-process cycle contains at least one amino acid and / or at least one amino acid derivative.

Both amino acids and amino acid derivatives contain at least two functional groups, one of which is a carboxy group and the other of which is an amine group or a quaternary amine group. Unless otherwise indicated, carboxy and amino groups are not derivatized, for example, by cross-linking agents. As shown by the structural formula below, the amino acid may be an α-amino acid.

In other embodiments, the amino acid may be a β-amino acid, a γ-amino acid, or a δ-amino acid.

An example of the amino acid L-arginine that constitutes a protein is shown by the following structural formula.

An example of the amino acid derivative L-carnitine that does not constitute a protein is shown by the following structural formula.

Nisin is a lunch biotic having the following structure.

Under the reaction conditions according to the method of the present invention, the R'-COOH group of an amino acid and / or an amino acid derivative reacts with the R'-OH group of cellulose by forming an ester bond R'-COO-R'. Can be done.

In certain embodiments of the invention, polyglucosamine (chitosan) is applied to the fabric. Chitosan has the structure shown below, and n represents the number of monomer units known in the art.

Under the reaction conditions disclosed herein, chitosan can react with the functional groups of cellulosic materials, resulting in the covalent bonds shown below.

When amino acids and / or amino acid derivatives are used in combination with chitosan, under the reaction conditions disclosed herein, the R'-COOH groups of amino acids and / or amino acid derivatives are ester-bonded R'-COO-R'. By forming a', it can react with the R''-OH group of chitosan.

Example

The present invention will be further described by the following examples exemplifying the preparation of fabric materials, but these are not limited to the present invention.

AATCC100-2012 test method for antibacterial performance:

The antibacterial performance of the antibacterial fabric according to the present invention was carried out according to the AATCC 100-2012 test method. The AATCC 100-2012 test procedure for antibacterial performance is described in detail on pages 166-168 of the AATCC Technical Manual 2013.

Simply put, from the autoclaved fabric material (at 121 ° C. for 15 minutes), three circular fabric swatches with a diameter of 48 mm were prepared and the specified number of fabric swatches were added to a 250 ml Erlenmeyer flask. The cloth sample was stained with the prepared 1 ml of inoculation material (in phosphate buffered water). The test inoculum was Pseudomonas aeruginosa ATCC 9027 or Staphylococcus aureus ATCC 6538 (10 ⁷ CFU / ml), and the inoculum load was 1% BSA. Contact times were varied from 0 minutes, 10 minutes, 30 minutes, and 1 hour. Cloth samples with a contact time of 0 minutes were analyzed immediately after inoculation. For the cloth samples with other contact times, the Erlenmeyer flask was sealed immediately after inoculation and kept warm at 37 ° C. at each contact time.

After the specified contact time, 100 ml of Dey-Engley neutralized broth was added to each flask and the flask was shaken by hand for 1 minute. Dilution series were prepared and each diluted sample was placed on a nutrient agar medium. The agar medium plate was kept warm at 37 ° C. for 24 hours and 48 hours.

Bacterial logarithm reduction (R) is B [logarithm (immediately after inoculation, that is, the number of bacteria recovered from the inoculation test cloth sample in the bottle at 0 minutes of contact time)]-A [logarithm (heat retention over the desired contact time) Inoculation treatment test in the bottle The number of bacteria collected from the sample cloth sample)] was calculated.

AATCCTM-30 (Part III) test method for antibacterial performance:

The antifungal activity of the fabric according to the present invention was tested using Aspergillus Niger or Candida albicans as test organisms according to the standard test method "AATCC test method 30-2013" ("Part III" of the standard test method. ").

A 48-hour culture of Candida albicans or Aspergillus niger was used in the test. The cultured culture was scraped from a sublodextrose agar containing 3% glucose and inoculated with glass beads in 50 ml sterile distilled water. The flask was shaken to make a suspension and the final density ^{was kept at 2 × 10 6} CFU / ml. Test medium (15 mL) was poured into sterile Petri dishes and coagulated. 1 ml of inoculum material was spread on the surface.

A fabric sample (3.8 ± 0.5 cm disc, autoclaved at 121 ° C for 15 minutes before the test) was placed on the surface of the agar and 0.2 mL of inoculum was added on top of each sample. The agar plates were cultured at 28 ° C. for 4-5 days. At the final stage of culturing, agar plates were tested for yeast / fungal growth according to the following assessments.

Chemicals

The following chemicals were used in the experiments described below.

L-arginine is known in the art and is commercially available, for example, by Sciencelab. In the following examples, 100% by weight of L-arginine was provided as a powder.

L-carnitine was provided by Lonza Specialty Chemicals of Switzerland, with more than 98% by weight provided as a powder.

Chitosan was provided as a storage solution by Go Yen Chemical (Goyenchem-102) in Taiwan. The measurement results made by the present inventors showed that this storage solution contained about 8% of the active ingredient, that is, 8% of chitosan.

Propiconazole is known in the art and is commercially available, for example, as Utconazol (manufactured by Utpan Chempro). Propiconazole can be bonded to the fabric material by using a cross-linking agent, particularly preferably a blocked isocyanate compound that provides a urethane bond, or an acrylate-based product. When propiconazole is used, it is preferable to use a cross-linking agent in the liquid agent, particularly the exhaust liquid agent. It is even more preferred that the propiconazole agent comprises a cross-linking agent or that the cross-linking agent is part of a propiconazole agent. In the following examples, propiconazole (Utpan Chempro) was provided as a 25% storage solution.

The quaternary ammonium organosilane may contain organomethoxysilane, preferably N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride provided by Gelest as a 50% storage solution.

Polyhexamethylene biguanides are known in the art and are commercially available. In the following examples, polyhexamethylene biguanide (Thor PHMB) was provided as a 20% storage solution.

Antibacterial agents may include silver cations. In certain embodiments, the silver cations are trapped in an inorganic or organic matrix. Preferably, the inorganic matrix is an aluminosilicate. Preferably, the organic matrix is a polymeric matrix. Such silver-containing antibacterial agents are known in the art and are commercially available. In the following examples, Silvadur 930 Flex (0.17% silver cation trapped in a polymeric matrix) was provided by Dow Chemical Company.

As the cross-linking agent, blocked polyisocyanate, for example, oxime blocked polyisocyanate can be used. Oxime-blocked polyisocyanates are provided, for example, by Schoeller Technologies.

Fabric

The following fabrics were used in the experiments described below.
・ 100% viscose: 117 grams per square meter (GSM), count / composition 30 * 30/68 * 64
・ 100% cotton: 40th, 140GSM
・ 50% cotton / 50% viscose (CVC mixed): 140GSM
-65% polyester / 35% cotton (PC mixed): 165GSM

Liquid application process

In the following examples, unless otherwise specified, the liquid preparation process was carried out as follows.

In the first step (“Liquid Preparation”), a liquid was prepared in a reaction mixture containing an amino acid / amino acid derivative and / or an antibacterial agent and water. The pH of the reaction mixture was adjusted to be specified in the examples by applying an acid. The reaction mixture was stirred at a specific temperature for a specific period of time.

After liquid preparation, the liquid was used undiluted with specific parameters in the main liquid application process, which is either an exhaustion process or a padding process. In one example, the main solution addition process was followed by a sub-addition process, which is a padding process.

Some fibers were made using an exhaust jigger device (Yamuna model number Y1100) and others were made under experimental conditions simulated to approach this process. The inventors speculate that the amount of chemicals added to the fabric during the exhaustion process corresponded to the amount of chemicals contained in about 100% wet pickup. Therefore, when the liquid preparation contained the medicine at a concentration of, for example, 30 gpl (gram per liter), the amount of the medicine on the cloth after the exhaustion process was about 3% by weight of the fiber. The padding process was performed with about 65% wet pickup. Therefore, when the liquid preparation contained the drug at a concentration of, for example, 30 gpl, the amount of the drug added to the fabric in the padding process was about 1.95% by fiber weight.

Drying and curing

The fabric was dried and occasionally dried and cured between the main solution application process and the secondary agent application process. After the final liquid application process, the fabric was dried and cured. Unless otherwise indicated below, drying was performed at 120 ° C. for 2 minutes and curing was performed at 180 ° C. for 2 minutes.

Washing

In one example, the cured fabric was washed several times under the following conditions as shown in the examples. The temperature in the wash cycle was 40 ° C. Clax 200s (Johnson Wax Professional) was used as soap in normal amounts. After each wash cycle, the fabric was rinsed with 0.05% citric acid for 10 minutes.

Example 1: Viscose fabric treated with L-arginine

100% viscose fabric was treated with L-arginine in a two-cycle process including an exhaustion process in the main solution application cycle and a padding process in the subprocess cycle.

Liquids for the exhaustion process and padding process containing 30 grams or 40 grams (gpl) of L-arginine per liter were prepared. The pH was adjusted to pH 4.5 with citric acid. The solution was stirred at 70 ° C. for 1 hour.

As a result of the exhaustion process with about 100% wet pickup, 3.0 / 4.0% L-arginine add-on by fiber weight was obtained. After exhausting at 60 ° C. for 1 hour using a non-diluted solution, drying was performed at 120 ° C.

Padding was performed with the concentration of L-arginine in the solution being 10 gpl. The padding pickup rate was about 65%. Therefore, it can be estimated that the total amount of L-arginine added to the fabric by the exhaustion process and the padding process is 3.0 / 4.0% + 0.65% = 3.65 / 4.65% o.w.f.

After padding, the fabric was dried at 120 ° C and cured at 180 ° C. The cured sample was washed 10 times in a laboratory washer with the nonionic detergent Clax 200 S.

The finishing method and test results are summarized in Table 1 below.

As can be seen from Table 1, L-arginine already provides a high antibacterial performance against Gram-negative Pseudomonas aeruginosa after 10 minutes with a logarithmic value of 2.76 (that is, a reduction of more than 99%). The antibacterial performance against Gram-positive Staphylococcus aureus is logarithmic about 1 (ie, about 90% reduction) after 1 hour. The overall antibacterial performance is unaffected by washing the fabric in detergent, allowing the fabric to be washed and reused. Such washing durability could not be realized in an experiment conducted by the present inventors using only the padding process without using the exhaustion process. This wash durability indicates that the amino acids are covalently attached to the fabric. Although not bound by theory, process conditions such as elevated temperature exhaustion at low pH and high temperature curing while water is evaporating are the carboxyl groups and viscoses of L-arginine. It is considered that the esterification reaction between the hydroxyl groups of the cellulose molecules contained in the viscose fabric is promoted. Finally, the data show that there is a positive correlation between the concentration of L-arginine used in the solution and the antibacterial efficiency.

Colorimetric test for detection of L-arginine:

An improved Sakaguchi test method was performed to detect and quantify L-arginine on the fabric samples in Table 1. A compatible Sakaguchi reagent consisting of 1-naphthol and sodium hypochlorite aqueous solution drops (2.5%) was used. The procedure of the improved Sakaguchi test method was as follows.

Preparation of 4 reagents:
(1) 500 mg 1-naphthol (Sigma-Aldrich N100-10G) in 100 ml ethanol corresponds to 0.5% 1-naphthol aqueous solution in EtOH (newly prepared each time).
(2) 5 g of NaOH in 100 ml of deionized water corresponds to a 5% NaOH aqueous solution.
(3) Javel water corresponds to 2.5% NaOCl aqueous solution
(4) 5 g of urea in 100 ml of deionized water corresponds to a 5% aqueous urea solution in water.

protocol:
・ Place the fabric sample on the Petri dish ・ Apply 1 ml of reagent (1) to the fabric sample ・ Apply 1 ml of reagent (2) to the fabric sample ・ Apply 1 ml of reagent (3) to the fabric sample ・ Apply 1 ml of reagent (3) to the fabric sample Add 1 ml of reagent (4) to the sample.

The red tint indicates the presence of L-arginine.

In the first step, a dilution series of L-arginine was tested to estimate the limits of detection. In this series, 1 ml of each of 1% L-arginine aqueous solution, 0.1% L-arginine aqueous solution, 0.01% L-arginine aqueous solution, and 0.001% L-arginine aqueous solution was applied to 6 cm × 6 cm fibers (mass = 408 mg). Then, the Sakaguchi reaction was tested for each fiber. Coloring could be observed for the 0.01% L-arginine aqueous solution and the aqueous solution having a higher concentration. Since 1 ml of 0.01% L-arginine aqueous solution applied to 408 mg of fiber corresponds to 0.1 mg of L-arginine, the detection limit was estimated to be about 0.025% o.w.f arginine.

The washed fabrics in Table 1 were tested by the Sakaguchi test method. The resulting coloration was compared to the dilution series. The o.w.f. concentration of L-arginine in sample "Arg 30 gpl" could be estimated to be between 0.25 and 2.5% arginine on viscose. The o.w.f. concentration of L-arginine in sample "Arg 40 gpl" could be estimated to be higher than 2.5% arginine on viscose.

The Sakaguchi test method confirmed that L-arginine was stably bound to the fabric sample in a wash-durable form.

Example 2: Viscose fabric treated with L-carnitine

100% viscose fabric was treated with L-carnitine in a two-cycle process including a main process cycle involving the exhaustion process and a sub-process cycle including the padding process.

A liquid preparation was prepared by dissolving 40 gpl of L-carnitine as a powder in water and adjusting the pH to pH 4.5 with citric acid. The liquid was stirred at 60 ° C. for 30 minutes, applied to the fabric sample by exhaustion, then dried at 120 ° C. and padded.

As a result of the exhaustion process with about 100% wet pickup, an L-carnitine add-on with a fiber weight of 4.0% was obtained. The padding pickup rate was about 65%. Therefore, it can be estimated that the total amount of L-carnitine added to the fabric by the exhaustion process and the padding process is 4.0% + 2.6% = 6.6% o.w.f.

After padding, the fabric was dried at 120 ° C and cured at 180 ° C for 2 minutes. After curing, the antibacterial activity of one treated sample was directly tested. Another treated sample was washed 10 times as described above before testing for antibacterial activity.

The prepared fabric samples were tested according to AATCC 100-2012 described above. In addition, the prepared fabric samples were tested against Candida albicans according to the AATCC TM-30 (Part III) described above.

As can be seen from Table 2, L-carnitine provides a high antibacterial performance against Pseudomonas aeruginosa 30 minutes after culturing, which is a logarithmic 2.82 (that is, a reduction of more than 99%). On the other hand, the antibacterial performance against Staphylococcus aureus is extremely low. The overall antibacterial performance is unaffected by washing the fabric in detergent at 40 ° C. This indicates that it is wash durable and reusable. Such washing durability could not be realized in an experiment conducted by the present inventors using only the padding process without using the exhaustion process. This wash durability indicates that L-carnitine can also be covalently bonded to the fabric, probably in the sense of an ester group between the carboxyl group of L-carnitine and the hydroxyl group of the cellulose molecule contained in the viscose fabric. In addition, test results for Candida albicans show that fabrics treated with L-carnitine have antifungal activity.

Example 3: Viscose fabric treated with a combination of L-arginine and chitosan

The 100% viscose fabric was treated with chitosan or L-arginine and chitosan in a two-cycle process including an exhaustion step in the main solution application cycle and a padding step in the subprocess cycle.

A solution for the exhaustion process was prepared containing 40 grams of chitosan storage solution (8%) per liter or 40 grams of chitosan storage solution per liter and 60 grams of L-arginine. The pH was adjusted to pH 4.5 with citric acid or acetic acid. The solution was stirred at 70 ° C. for 1 hour. The exhaustion process with approximately 100% wet pickup resulted in a 0.32% o.w.f. chitosan add-on and (if applicable) a 6% o.w.f. L-arginine add-on. After exhaustion was performed at 60 ° C. for 1 hour, drying was performed at 120 ° C.

The solution used in the padding process contained 10 grams of chitosan storage solution (8%) per liter or 10 grams of chitosan storage solution per liter and 30 grams of L-arginine. The padding pickup rate of the secondary process cycle was about 65%. Therefore, it can be estimated that the total amount of chitosan added to the fabric by the exhaustion process and the padding process is 0.32% + 0.052% = 0.372% o.w.f. It can be estimated that the total amount of L-arginine added to the fabric by the exhaustion process and the padding process (if applicable) is 6% + 1.95% = 7.95% o.w.f.

After padding, the fabric was dried and cured at 180 ° C. The cured sample was washed 10 times in a laboratory washer with the nonionic detergent Clax 200 S.

The finishing method and test results are summarized in Table 3 below.

As can be seen from Table 3, the combination of L-arginine and chitosan has a logarithmic antibacterial performance of 2.47 or more (that is, a reduction of more than 99%) against Pseudomonas aeruginosa 10 minutes after culturing, and an antibacterial performance against Staphylococcus aureus. It gives a very high antibacterial performance of 2.92 or more in logarithm. Thirty minutes after culturing, the reduction rate increased logarithmically to 5.17 and 4.82. Such high performance was not obtained when chitosan alone was used as an antibacterial agent.

Example 4: Viscose fabric treated with a combination of L-arginine, L-carnitine, and chitosan

In a one-cycle exhaustion process, 100% viscose fabric was treated with a combination of L-arginine, L-carnitine, and chitosan. Chitosan was provided as an aqueous storage solution containing 8% water soluble chitosan.

Depending on the concentration of the activator in the wicking agent, the concentration was 0 / 0.56% o.w.f. chitosan, 7% o.w.f. L-arginine, and 7% o.w.f. L-carnitine. After exhaustion, the fabric was dried at 120 ° C and cured at 180 ° C for 2 minutes.

The fabric sample thus prepared was washed and tested according to AATCC 100-2012 described in Example 1 above.

The combination of L-carnitine and L-arginine in the exhaustion process significantly increases the antibacterial activity against S. aureus compared to the use of only one of L-carnitine and L-arginine. Also, with the addition of chitosan, the antibacterial activity is significantly increased to at least a logarithm of 4 (ie, a reduction of more than 99.99%) after a contact time of 30 minutes.

Example 5: Different fabrics treated with a combination of L-arginine, carnitine, chitosan, and optionally silver cations.

From different fabrics according to the invention, namely 100% viscose fabrics, 100% cotton fabrics, 50% cotton and 50% polyester mixed fabrics (CVC), and 65% polyester and 35% cotton mixed fabrics. Cloth (PC) was processed.

120 gpl of chitosan storage solution (8%), 70 gpl of L-arginine, 70 gpl of L-carnitine, and optionally After applying a solution containing 10 gpl of Silvadur 930 Flex to each fabric material, it includes padding, drying at 120 ° C and curing at 180 ° C using the same solution used for the exhaustion process. A sub-process cycle was performed.

The concentration of activator in the solution resulted in 1.584% owf chitosan, 11.55% owf L-arginine, 11.55% owf L-carnitine, and (if applicable) 0.002805% owf silver add-on estimates. ..

The prepared fabric samples were tested according to AATCC 100-2012 described above.

As can be seen from Tables 5 and 6 above, all four fabric materials tested were washed 10 times in the nonionic detergent Clax 200 S and then at least logarithmic 3 (ie, 30 minutes after contact time). It showed high antibacterial performance (a decrease of more than 99.9%). The addition of silver ions further increased the antibacterial activity against Staphylococcus aureus. In general, the treated viscose fabrics showed higher antibacterial activity than other fabric materials. The antibacterial performance decreased in the following order. Viscose> Cotton> CVC mixed> PC mixed. From the viewpoint of lowering the concentration of cellulose molecules and reactive hydroxyl groups, the functional groups of the fabric can be the decisive factor for the stable binding of L-arginine, L-carnitine, and chitosan for CVC mixing and PC mixing.

Finally, sample "PC, + Ag" was partially resistant to Aspergillus niger when tested according to AATCC-30 (contact time 7 days) (not shown in the table above). ..

Example 6: 100% viscose fabric treated with a combination of L-arginine and chitosan in different types of acids

100% viscose fabric samples were treated with L-arginine and chitosan in a two-cycle process including an exhaustion process in the main solution application cycle and a padding process in the subprocess cycle. The pH of the solution was adjusted with either acetic acid, citric acid or hydrochloric acid.

About 0.32% owf of chitosan and 6% owf by applying a solution containing 40 grams per liter (gpl) of chitosan storage solution (concentration: 8%) and 60 gpl of L-arginine by exhaustion in the main process. It became the concentration of L-arginine. After exhaustion, it was dried at 120 ° C. The accessory application cycle included padding, drying at 120 ° C, and curing at 180 ° C. The padding solution contained 10 grams per liter (gpl) of chitosan storage solution and 30 gpl of L-arginine. Additional add-ons were obtained for 0.052% o.w.f. chitosan and 1.95% o.w.f. L-arginine. Therefore, the active add-ons in both process cycles totaled 0.372% o.w.f. chitosan and 7.95% o.w.f. L-arginine.

After exhaustion, it was dried at 120 ° C. After drying, the samples were washed 30 times at 40 ° C. with Clax 200 S before testing for antibacterial activity.

The results in Table 7 show that the highest antibacterial performance can be obtained when acetic acid is used to adjust the pH of the liquid preparation. The result of citric acid is a little worse than this, which can be due to an increase in free carboxylic acid groups, i.e. an increase in negative charge on the fabric. Hydrochloric acid, on the other hand, can affect fabrics, especially cellulosic fabrics.

Example 7: 100% polyethylene fabric treated with a combination of L-arginine, L-carnitine, chitosan, and additional antibacterial agents.

Fine fibers were prepared by the method according to the present invention.

100% polyester fabric (22GSM) was treated with L-arginine in a one-cycle process involving only the padding process.

A liquid preparation for the padding process containing 5 gpl each of L-arginine and L-carnitine was prepared. In addition, the solution contains 1 gpl of 25% propiconazole storage solution, 1.5 gpl of 25% PHMB storage solution, 25 gpl of 8% chitosan storage solution, and 8% of Silvadur 930 Flex (containing 0.17% silver). There was. The pH was adjusted to pH 6.5 using acetic acid. In addition, the solution contained 4 gpl of isopropanol. The solution was stirred at 50 ° C. for 1 hour.

The padding process was performed with about 50% wet pickup. The resulting add-on drugs can be collected from the table below. After padding, drying at 100 ° C. for 3 minutes and curing at the same temperature for 2 minutes were performed.

The antibacterial performance of the cured sample was tested. The test results are summarized in Table 8.

The fabric was treated with padding only and was cured at only 100 ° C due to its low weight, but it was found to have high antibacterial performance.

Example 7: 100% viscose fabric treated with a combination of L-arginine and chitosan in padding

A 100% viscose fabric sample was treated with L-arginine and chitosan in a one-cycle process including a padding step in the main solution application cycle and a padding step in the subprocess cycle. The pH of the solution was adjusted to pH 7 using hydrochloric acid.

The padding solution contained 40 grams per liter (gpl) of chitosan storage solution (concentration: 8%) and 5 gpl of L-arginine. Additional add-ons were obtained for 0.052% o.w.f. chitosan and 0.325% o.w.f. L-arginine.

The temperature of the padding bath was maintained at room temperature. After padding, the fabric sample was dried at 150 ° C. for 2 minutes and cured at 180 ° C. for 2 minutes. In the following, the fabric was washed 5 times with water. Each wash cycle was performed at 27 ° C. for 10 minutes and tested according to AATCC 100-2012 described above. The process parameters and test results are summarized in Table 9.

The results in Table 9 show that the padding process can produce antibacterial fabrics with some degree of wash resistance. However, there is a slight decrease in performance when washing the fabric. On the other hand, as described above, the exhaustion process gives the fabric high wash durability and makes it reusable as an antibacterial fabric. Therefore, it is now preferred to apply the exhaustion process in the main process cycle.

Example 8: Cotton fabric treated with L-arginine

100% cotton fabric was treated with L-arginine in a two-cycle process including an exhaustion process in the main solution application cycle and a padding process in the subprocess cycle.

Liquids containing 120 grams per liter (gpl) of L-arginine were prepared as liquids for both the exhaustion process and the padding process. To assess the effect of pH on wash resistance, a series of tests were performed using samples with pH 4.0, 4.5, 5.0, 5.5, and 6.0.

An exhaustion process was carried out at 60 ° C. for 1 hour using a non-diluted solution, and then drying was carried out at 120 ° C.

Padding (2 nip and 2 dip) was performed at room temperature with the concentration of L-arginine in the solution being 120 gpl.

After padding, the fabric was dried at 120 ° C and cured at 180 ° C. The cured sample was washed 5 times in a laboratory washer with the nonionic detergent Clax 200 S. After each wash with Clax, the fibers were washed with water and then with 0.05% citric acid. Then, the fiber was dried at 150 ° C. for 2 minutes. The antibacterial efficiency of the samples was tested before and after each wash cycle.

The test results are summarized in Table 10 below.

As can be seen from Table 10, the 12% amount of L-arginine without the addition of antibacterial agent has a logarithmic antibacterial performance of more than 4.41 (that is, a reduction of more than 99.99%) against E. coli after 24 hours. Is to give.

It can also be seen from Table 10 that the washing durability is affected by the pH of the liquid agent. The sample with the highest washing durability was Arg 120-4, which had a pH of 5.5, and even after the third washing cycle, the antibacterial performance against Escherichia coli exceeded 4.41 logarithmically. did.

Claims (60)

It ’s a way to make the fabric antibacterial.
The main process cycle includes the main process cycle.
A step of treating the fabric in a main liquid application process such as padding or preferably exhaustion, wherein the liquid agent of the main liquid application process contains at least one amino acid and / or at least one amino acid derivative.
The step of heat-treating the treated fabric and
The step of washing the heat-treated fabric as needed, and
Including the step of drying the washed fabric as needed.
The method preferably comprises a sub-process cycle performed after the step of the main process cycle, wherein the sub-process cycle is:
A step of treating the fabric using a secondary liquid application process such as exhaustion or preferably a padding process, wherein the liquid agent of the secondary liquid application process is at least one amino acid, at least one amino acid derivative, and / or. A process involving at least one antibacterial agent and
The step of heat-treating the treated fabric and
The step of washing the heat-treated fabric as needed, and
A method comprising the step of drying the washed fabric as needed. The amino acid and / or the amino acid derivative contained in the liquid preparation of the main liquid agent applying process and / or the auxiliary liquid agent applying process has an isoelectric point of 7 or more, preferably 8 or more, more preferably 8.5 or more, and further. / Or the method of claim 1, having a positive charge independent of pH. The at least one amino acid contained in the liquid preparation in the main liquid preparation process and / or the secondary liquid preparation process is selected from the group consisting of natural amino acids, artificial amino acids, and amino acids that do not constitute a protein, and / or at least one of the above. The method according to any one of the preceding claims, wherein the amino acid derivative is selected from the group consisting of peptides and quaternary ammoniums comprising amino acid derivatives. The method according to the preceding claim, wherein the natural amino acid, the artificial amino acid, or an amino acid that does not constitute the protein is an L-form, and / or the peptide is an L-peptide. The method according to any one of claims 3 or 4, wherein the peptide is a dipeptide or a polypeptide, and the polypeptide preferably contains 3 to 50 amino acids. The preceding claim, wherein the at least one amino acid contained in the liquid preparation of the main liquid preparation process and / or the secondary liquid preparation process is lysine, arginine, or histidine, preferably arginine. the method of. The method according to any one of the preceding claims, wherein the at least one amino acid derivative contained in the liquid preparation in the main liquid preparation process and / or the secondary liquid preparation process is lanchibiotic, preferably nisin. The method according to any one of the preceding claims, wherein the at least one amino acid derivative contained in the liquid preparation in the main liquid preparation process and / or the auxiliary liquid preparation process is carnitine or betaine, preferably carnitine. .. The method according to any one of the preceding claims, wherein the liquid preparation in the main liquid preparation process and / or the secondary liquid preparation process contains at least arginine and carnitine. The at least one amino acid or amino acid derivative in the solution for all process cycles is 0.1% or more, preferably 0.2% or more, more preferably 0.5% or more, or 1 by weight in total, based on the weight of the fabric. The method according to any one of the preceding claims, wherein an amount of% or more, 2% or more, 3% or more, or 4% or more is applied to the fabric. The at least one amino acid or amino acid derivative in the solution for all process cycles is 20% or less, preferably 18% or less, or 16% or less, or 14% or less in total by weight, based on the weight of the fabric. , Or 12% or less, or 10% or less, or 8% or less, or 6% or less or 4% or less, most preferably 12% or less, any one of the preceding claims. The method described in the section. The preparation of the liquid agent in the main liquid agent application process and / or the auxiliary liquid agent application process
The step of preparing an aqueous reaction mixture containing at least one amino acid and / or an amino acid derivative, and
A step of keeping the reaction mixture warm for 10 minutes or longer, preferably 20 minutes or longer, more preferably 30 minutes or longer, even more preferably 40 minutes or longer, most preferably 50 minutes or longer, and the temperature of the reaction mixture during heat retention. The method according to any one of the preceding claims, comprising a step of preferably 30 ° C. or higher, more preferably 40 ° C. or higher, even more preferably 50 ° C. or higher, and most preferably 60 ° C. or higher. .. The method according to any one of the preceding claims, wherein the liquid agent in the main solution application process and / or the accessory solution application process contains glucosamine and / or polyglucosamine. The method according to the preceding claim, wherein the polyglucosamine and / or glucosamine is in a water-soluble form. The polyglucosamine and / or glucosamine is 50% or less, preferably 40% or less, more preferably 30% or less, most preferably 20% or less, and / or 1% or more, preferably 5% or more, more preferably. The method according to any one of claims 13 or 14, provided as a concentrated solution or suspension of 10% or more, most preferably 15% or more of polyglucosamine and / or glucosamine. The pH of the concentrated solution or suspension is lower than 6.5, preferably lower than 6.0, more preferably lower than 5.5, even more preferably lower than 5.0, most preferably about 4.5, and / or preferably. 15. The method of claim 15, wherein the pH is adjusted to be higher than 3.0, more preferably higher than 4.0, even more preferably higher than 5.0, and most preferably about 5.5. The pH of the concentrated solution or concentrated suspension is adjusted by using an organic acid, more preferably a monocarboxylic acid, even more preferably acetic acid, lactic acid, formic acid, propionic acid, p-toluenesulfonic acid, or a combination thereof. The method according to the preceding claim. The total amount of glucosamine and / or polyglucosamine in the solution for all process cycles is 0.1% or more, preferably 0.2% or more, more preferably 0.3% or more, or 0.7% or more, based on the weight of the fabric. The method according to any one of claims 13 to 17, wherein an amount of 1% or more is applied to the fabric. Glucosamine and / or polyglucosamine in the solution for all process cycles totals 5% or less, preferably 4% or less, more preferably 3% or less, even more preferably 2 based on the weight of the fabric material. The process according to any one of claims 13 to 18, wherein an amount of% or less, most preferably 1.6% or less, or 1% or less is applied to the fabric. The preparation of the liquid agent in the main liquid agent application process and / or the auxiliary liquid agent application process
The step of preparing at least one amino acid and / or amino acid derivative in the form of powder or liquid, and
The step of preparing the glucosamine and / or polyglucosamine in the form of powder or liquid, and
A step of preparing a preferably aqueous reaction mixture containing at least one amino acid and / or an amino acid derivative and glucosamine and / or polyglucosamine.
A step of keeping the reaction mixture warm for 10 minutes or longer, preferably 20 minutes or longer, more preferably 30 minutes or longer, even more preferably 40 minutes or longer, most preferably 50 minutes or longer, and the temperature of the reaction mixture during heat retention. The method according to any one of claims 13 to 19, further comprising a step of preferably 30 ° C. or higher, more preferably 40 ° C. or higher, even more preferably 50 ° C. or higher, and most preferably 60 ° C. or higher. .. The temperature of the reaction mixture during heat retention is 95 ° C. or lower, preferably 90 ° C. or lower, more preferably 85 ° C. or lower, even more preferably 80 ° C. or lower, and most preferably 75 ° C. or lower, claim 12 or claim. The method described in 20. The method according to any one of claims 12, 20, or 21, wherein the reaction mixture is stirred at a rotation speed of preferably 10 rpm or more during the heat retention step. The pH of the reaction mixture is lower than 6.5, preferably lower than 6.0, more preferably lower than 5.5, even more preferably lower than 5.0, most preferably about 4.5 pH, and / or preferably greater than 3.0. 12 or any one of claims 20 to 22, which is also higher, more preferably higher than 4.0, even more preferably higher than 5.0, and most preferably about 5.5. Method. The pH of the reaction mixture is adjusted by using an organic acid, more preferably a monocarboxylic acid, even more preferably acetic acid, lactic acid, formic acid, propionic acid, p-toluenesulfonic acid, or a combination thereof. The method described in the claim. 50% or more, preferably 70% or more, more preferably 80% or more, of the at least one amino acid, amino acid derivative and / or polyglucosamine bound to the fabric in the main solution application process and / or the accessory solution application process. The method according to any one of the preceding claims, wherein 90% or more, more preferably 95% or more, is not bound to the cellulose molecule dispersed or dissolved in the solution. The liquid agent in the main process cycle and / or the sub-process cycle is one, two, or two antibacterial agents selected from the group consisting of azole compounds, silver ions, polyhexamethylene biguanides, and quaternary ammonium organosilanes. The method according to any one of the preceding claims, comprising three or all four. The method according to the preceding claim, wherein the azole compound is propiconazole. The quaternary ammonium organosilane is a hydrophilic quaternary ammonium organosilane, preferably an organomethoxysilane compound, more preferably N-trimethoxysilylpropyl-n, n, n-trimethylammonium chloride. The method according to 26 or 27. The quaternary ammonium organosilane compound in the solution for all process cycles totals 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.25% by weight or more, most preferably based on the weight of the fabric material. The method according to any one of claims 26 to 28, wherein an amount of 0.3% by weight or more is preferably applied to the fabric. The quaternary ammonium organosilane compound in the solution for all process cycles totals 5% by weight or less, preferably 1.5% by weight or less, more preferably 1.2% by weight or less, in particular, based on the weight of the fabric material. The method according to any one of claims 26 to 29, wherein an amount of 1.0% by weight or less, most preferably 0.8% by weight or less is applied to the fabric. The silver cations or silver cations trapped in the inorganic or organic matrix in the solution for all process cycles total 0.1% by weight or less, preferably 0.05% by weight or less, more preferably based on the weight of the fabric material. The method according to any one of claims 26 to 30, wherein an amount of 0.02% by weight or less, most preferably about 0.01% by weight or less is applied to the fabric. The silver cations or silver cations trapped in the inorganic or organic matrix in the solution for all process cycles total 0.001% by weight or more, preferably 0.002% by weight or more, more preferably based on the weight of the fabric material. The method according to any one of claims 26 to 31, wherein an amount of 0.003% by weight or more, most preferably about 0.005% by weight or more is applied to the fabric. The polyhexamethylene biguanide in the solution for all process cycles totals 0.5% by weight or less, preferably 0.4% by weight or less, more preferably 0.3% by weight or less, most preferably 0.2% by weight, based on the weight of the fabric material. The method according to any one of claims 26 to 32, wherein an amount of weight% or less is applied to the fabric. The polyhexamethylene biguanide in the solution for all process cycles totals 0.03% by weight or more, preferably 0.05% by weight or more, or 0.10% by weight or more, preferably 0.15% by weight or more, based on the weight of the fabric material. The method of any one of claims 26-33, wherein the amount of The azole compounds in the solution for all process cycles total 0.6% by weight or less, preferably 0.5% by weight or less, more preferably 0.4% by weight or less, most preferably 0.3% or less, based on the weight of the fabric material. The method according to any one of claims 26 to 34, wherein an amount of weight% or less is applied to the fabric. The azole compounds in the solution for all process cycles total 0.05% by weight or more, preferably 0.10% by weight or more, more preferably 0.15% by weight or more, most preferably 0.20, based on the weight of the fabric material. The method according to any one of claims 26 to 35, wherein an amount of% by weight or more is applied to the fabric. The liquid agent in the main solution application process and / or the accessory application process contains water, preferably water and isopropanol, and more preferably isopropanol is between 0.05% by weight and 2% by weight, preferably from 0.1% by weight. The method according to any one of the preceding claims, which is contained in the solution in a concentration of 1% by weight, more preferably between 0.2% by weight and 0.6% by weight. The pH of the solution in the main solution application process and / or the accessory application process is 6.5 or less, preferably 6.0 or less, more preferably 5.5 or less, even more preferably 5.0 or less, most preferably about 4.55, and further /. Alternatively, the method according to any one of the preceding claims, preferably higher than 3.0, more preferably higher than 4.0, even more preferably higher than 5.0, and most preferably about 5.5. The pH of the solution in the main solution addition process and / or the accessory application process is determined by using an organic acid, more preferably a monocarboxylic acid, particularly acetic acid, lactic acid, formic acid, propionic acid, p-toluenesulfonic acid, or a combination thereof. The method according to the preceding claim, which is adjusted by use. The method according to any one of the preceding claims, wherein the liquid agent contains a cross-linking reagent, preferably an isocyanate cross-linking agent or an acrylic cross-linking agent, and more preferably a blocked isocyanate cross-linking agent. During the exhaustion process, the solution is heated to a temperature of 40 ° C. or higher, particularly 45 ° C. or higher, preferably 50 ° C. or higher, more preferably 55 ° C. or higher, even more preferably 60 ° C. or higher, most preferably about 65 ° C. or higher. The method according to any one of the preceding claims. The preceding claim, wherein during the exhaustion process, the solution has a temperature below the boiling point, preferably 95 ° C. or lower, more preferably 90 ° C. or lower, particularly 85 ° C. or lower, most preferably about 80 ° C. or lower. The method according to any one of the above. The exhaustion time of the exhaustion process is 30 minutes or longer, preferably 40 minutes or longer, more preferably 50 minutes or longer, particularly 55 minutes or longer, most preferably about 60 minutes or longer, and / or 120 minutes or shorter, in particular. Any of the preceding claims, 90 minutes or less, preferably 80 minutes or less, more preferably 75 minutes or less, even more preferably 70 minutes or less, even more preferably 65 minutes or less, most preferably about 60 minutes or less. The method described in one paragraph. The method according to any one of the preceding claims, wherein the heat treatment of the main process cycle and / or the sub-process cycle includes drying and / or curing. Drying is performed at an ambient temperature of 190 ° C. or lower, preferably 180 ° C. or lower, more preferably 170 ° C. or lower, and / or 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, most preferably about 120 ° C. The method according to the preceding claim, which is carried out at an ambient temperature of ° C. or higher. Curing is performed at an ambient temperature of 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, particularly 175 ° C. or higher, most preferably about 180 ° C. or higher, and / or 205 ° C. or lower, preferably 195 ° C. or higher. The method of claim 44 or 45, wherein the method is more preferably performed at least partially at an ambient temperature of 190 ° C. or lower, particularly 185 ° C. or lower, most preferably about 180 ° C. or lower. The method according to any one of the preceding claims, wherein the starting fabric comprises a hydroxyl group, a peptide group and / or a carbonyl group, particularly a hydroxyl group and / or a peptide group. The starting fabric is any one of the preceding claims, wherein the starting fabric is a cellulosic fabric material, an animal-derived fabric material, a synthetic fabric material, or a mixture of a cellulosic fabric material, an animal-derived fabric material, and / or a synthetic fabric material. The method described in. The cellulosic fabric according to the preceding claim, wherein the cellulosic fabric comprises one or more selected from the group consisting of cotton, viscose, rayon, linen, hemp, ramie, jute, and combinations thereof (blended). Method. The method of claim 48, wherein the animal-derived fabric comprises one or more selected from the group consisting of wool and silk. The synthetic fabrics are polyester, polyamide (nylon), acrylic polyester, spandex (elastan, lycra), aramid, modal, sulfur, polylactide (PLA), lyocell, polybutyltetrachloride (PBT), and combinations thereof (blend). 48. The method of claim 48, comprising one or more selected from the group consisting of). 90% or more, preferably 95% or more, more preferably 98% or more, even more preferably 99% or more, most preferably about 100% of the starting fabric is formed from renewable raw materials and / or raw. The method of any one of claims 47-51, which is biodegradable and / or naturally organic. The fabric is selected from the group consisting of woven fabrics, knit fabrics, crochet fabrics, bonded fabrics, warp knitted fabrics, and non-woven fabrics, preferably the antibacterial fabric is a woven fabric, any one of the preceding claims. The method described in. An antibacterial fabric obtained according to any one of the preceding claims, preferably the at least one amino acid and / or amino acid derivative is attached, bound or covalently attached to the fabric and / or , If present, preferably the antibacterial fabric, wherein the glucosamine, polyglucosamine and / or additional antibacterial agent is also attached, bound or covalently attached to the fabric. The amino acid, amino acid derivative, glucosamine, polyglucosamine and / or additional antibacterial agent attached to, bound to or covalently bound to the fabric is in any one of claims 10, 11, 18, 19, 29 to 36. The antibacterial fabric according to claim 54, which has an individual weight specified for each antibacterial agent. Decreased values of Pseudomonas aeruginosa ATCC 9027 and / or Staphylococcus aureus ATCC 6538 measured according to AATCC Test Method 100-2012 within a 24-hour contact time, preferably within a 6-hour contact time, more preferably 1 hour. Within the contact time of, even more preferably within the contact time of 15 minutes, especially within the contact time of 10 minutes, 99% or more, preferably 99.9% or more, more preferably 99.99% or more, most preferably 99.999% or more. The antibacterial fabric according to claim 54 or 55. The reduced value is washed 5 or more times in a washing machine at 40 ° C., preferably using a non-antibacterial, non-ionic, non-chlorine-containing laundry detergent product over a period of 20 to 40 minutes, preferably followed by a standard rinse. The antibacterial fabric according to claim 56, which is obtained even after a cycle, more preferably after washing 10 times or more. The antibacterial fabric according to any one of claims 54 to 57, which exhibits zero growth of microorganisms when tested according to AATCC Test Method 30-2013 Part III (Agar Plate, Aspergillus niger or Candida albicans). The zero growth value is washed 5 times or more in a washing machine at 40 ° C., preferably using a non-antibacterial, non-ionic, non-chlorine-containing laundry detergent product for 20 to 40 minutes, preferably then standard. The antibacterial fabric according to claim 58, which is obtained even after performing a rinsing cycle, and more preferably after washing 10 times or more. Based on weight, 90% or more, preferably 95% or more, more preferably 98% or more, even more preferably 99% or more, especially of all antibacterial agents attached to the fabric or all antibacterial agents contained in the fabric. The antibacterial fabric according to any one of claims 54 to 59, wherein 99.5%, most preferably about 100%, is biodegradable and / or naturally organic.