A detergent composition with long-lasting bacteriostatic effect and its use

Abstract

The application discloses a detergent composition with long-acting bacteriostatic efficiency and application thereof, and relates to the technical field of daily chemical products. The detergent composition contains a copper amine complex as a long-acting bacteriostatic agent; the copper amine complex is generated by reaction of a divalent copper ion with organic amine and / or ammonia water in an aqueous solution. The detergent composition with long-acting bacteriostatic efficiency has the copper amine complex preparation as the long-acting bacteriostatic agent, can exert long-acting antibacterial efficiency on various bacteria and fungi, and can reach a long-acting bacteriostatic rate of greater than 90.0% for 72 hours under experimental conditions. In addition, the copper amine complex preparation as the long-acting bacteriostatic agent can be well compatible with a sulfonic acid type anionic surfactant system which is difficult to be compatible with most bacteriostatic agents.

Description

Technical Field

[0001] This invention relates to the field of daily chemical product technology, specifically to a detergent composition containing a copper amine complex as a long-lasting antibacterial agent, and the application of this detergent composition in fabric washing. Background Technology

[0002] When detergents are used, the dilution ratio is large, the contact time is short, and there are multiple rinses with water, making it difficult for many antibacterial ingredients to form a sufficient and lasting effective deposit on fabrics or hard surfaces.

[0003] "Long-lasting" effects often rely on residues or films on the fiber surface, but water hardness, washing temperature / program, post-wash drying methods, and wear friction can significantly weaken the effect.

[0004] Existing long-lasting antibacterial detergents mostly rely on forming a "residual-release" antibacterial active layer on the substrate surface. The main technical routes include: cationic antibacterial systems based on quaternary ammonium salts (such as alkyl dimethyl benzyl ammonium chloride and dialkyl quaternary ammonium salts); polymeric antibacterial systems based on biguanides such as polyhexamethylene guanidine / polyhexanone (PHMG / PHMB); formulations based on inorganic antibacterial agents such as silver ions / nano silver and zinc / copper salts; and organic antibacterial substances represented by quaternized polymers, chitosan, and plant essential oils, supplemented by microcapsules, carrier adsorption, and other methods to achieve sustained release. Based on these ideas, domestic and international patent applications disclose various solutions for achieving long-lasting antibacterial effects in laundry detergents, fabric care products, and dishwashing / household cleaning agents.

[0005] Most long-lasting antibacterial agents are cationic (such as quaternary ammonium salts and PHMB), which can undergo compounding and deactivation when combined with common anionic surfactants (such as sodium linear alkylbenzene sulfonate (LAS) and sodium fatty alcohol polyoxyethylene ether sulfate (AES), affecting both cleaning power and antibacterial effect. In the prior art, CN202511867741.4 discloses a polyoxyethylene block-modified quaternary ammonium salt antibacterial agent, which can exert a bactericidal effect in systems containing sodium α-alkenyl sulfonate anionic surfactants. However, it still suffers from instability when combined with highly negatively charged anionic surfactants such as sodium alkylbenzene sulfonate, and its inability to effectively deposit on fabrics to form a long-lasting antibacterial effect.

[0006] Silver-based and microcapsule sustained-release solutions are costly; fluctuations in raw material prices and other factors that lead to substitution and re-validation increase the difficulty and time cost of development.

[0007] Copper, as a common metallic element, is widely used in the field of antibacterial and antimicrobial applications. Copper and its ions have significant advantages as antibacterial agents: broad-spectrum antibacterial activity, effective against a variety of bacteria, fungi, and some viruses, and able to inhibit biofilm formation; multi-target mechanism, killing bacteria through multiple pathways such as disrupting cell membranes, binding to proteins and nucleic acids, and promoting the generation of reactive oxygen species, resulting in a relatively low risk of drug resistance; long-lasting and passive protection, acting as a surface material or coating to continuously exert a "contact sterilization" effect without the need for continuous addition of agents; and resource and cost-effectiveness, being abundant and cheaper than precious metals such as silver.

[0008] However, under normal circumstances, copper and its ions are difficult to effectively deposit and adhere to the surface of fabrics under washing conditions, and it is also difficult to form a long-lasting antibacterial effect. CN202211516817.5 describes the use of a polysaccharide complex containing divalent copper ions and copper oxide nanoparticles as a long-lasting antibacterial agent in combination with anionic surfactants in laundry detergent, which expands the long-lasting antibacterial spectrum of the laundry detergent. However, this technical solution still has some shortcomings: ① The polysaccharide complex is sensitive to temperature and is prone to denaturation at high temperatures, which is not conducive to production and storage; ② The synthesis of copper-containing polysaccharide complexes is relatively complex and the raw material cost is high. CN121554733A discloses a detergent composition using ultrafine copper powder coated with ethanolamine as an antibacterial agent, which can effectively exert a broad-spectrum long-lasting antibacterial effect in anionic surfactant systems. However, the ultrafine copper powder, as a solid particle, limits its use to suspension detergents, which has certain limitations.

[0009] In summary, the long-lasting antibacterial technology in detergents currently still has the following shortcomings in large-scale commercial applications: 1. Poor compatibility with the main surfactant system leads to insufficient long-lasting effect. Cationic antibacterial agents such as quaternary ammonium salts and PHMB / PHMG easily form ion associations or precipitation with anionic surfactants (such as LAS, AES, and soap bases), which weakens the bactericidal / antibacterial activity and reduces the clarity and foam stability of the formulation, making it difficult for the active ingredients to maintain a persistent residue after rinsing.

[0010] 2. Commonly used antibacterial agents in laundry detergents, such as quaternary ammonium salts and phenols, have small molecular weights and are easily washed away during the actual rinsing process. This results in a small amount adsorbed onto the fabric surface, a low deposition rate, and a weakened long-lasting antibacterial effect on clothing. Previously, increasing the amount of antibacterial agent used was generally used to increase its adsorption capacity and achieve a long-lasting antibacterial effect. However, this method increases costs due to the low utilization rate of the antibacterial agent and also has a negative impact on the environment, which does not meet the requirements of green development.

[0011] Therefore, there is an urgent need to develop a detergent composition that is compatible with conventional anionic surfactant systems (especially sulfonic acid anionic surfactant systems), has a simple production process, is cost-controllable, and can be efficiently deposited on the fabric surface under washing conditions to impart long-lasting broad-spectrum antibacterial properties to the fabric. Summary of the Invention

[0012] The purpose of this invention is to provide a detergent composition with long-lasting antibacterial efficacy and its application, so as to overcome the technical defects of the prior art, such as poor compatibility between long-lasting antibacterial agents and anionic surfactants, and the difficulty of copper ions being effectively deposited on the fabric surface.

[0013] The inventors discovered that adding a copper-amine complex, formed by the reaction of divalent soluble copper salts and organic amines in an aqueous solution, as a long-lasting antibacterial agent to a detergent composition, and controlling the pH of the detergent composition within a specific range, can significantly increase the deposition of copper ions on the fabric surface, resulting in excellent long-lasting broad-spectrum antibacterial properties in the washed fabric. Based on the above findings, this invention was completed.

[0014] Specifically, the present invention provides the following technical solution.

[0015] A detergent composition with long-lasting antibacterial efficacy contains a copper amine complex as a long-lasting antibacterial agent; the copper amine complex is generated by reacting divalent copper ions with organic amines and / or ammonia in an aqueous solution.

[0016] The preparation method of the copper-amine complex is as follows: Dissolve a divalent copper salt solid in water, and slowly add a certain proportion of organic amine to the divalent copper salt solution while stirring and observing. With the addition of the organic amine, a blue precipitate first forms in the solution, then gradually dissolves, finally forming a uniform blue solution, which is the long-acting antibacterial agent of the copper-amine complex.

[0017] It is widely believed in the art that copper ions themselves can provide long-lasting antibacterial effects, but how to effectively attach copper ions to clothing during washing has been a challenge in the industry. This invention demonstrates that a rationally designed copper-amine complex formulation can significantly improve the adhesion of copper ions to clothing and its long-lasting antibacterial performance.

[0018] Preferably, in the copper amine complex, the molar ratio of divalent copper ions to organic amine is 1:(3.1-3.5). If the amount of organic amine is too low, a blue precipitate will form in the reaction system, and it cannot be completely converted into a soluble copper amine complex; if the amount of organic amine is too high, it will increase the cost and may also affect the acidity or alkalinity of the product.

[0019] Preferably, the divalent copper ions are derived from soluble copper salts such as copper sulfate, copper chloride, and copper acetate; the organic amine is selected from one or more of monoethanolamine, diethanolamine, and triethanolamine.

[0020] Preferably, the content of divalent copper ions derived from the long-acting antibacterial agent is 0.06% to 0.2% based on the total mass of the detergent composition. Within this dosage range, excellent long-acting antibacterial effect can be obtained, with high antibacterial efficiency and low usage cost.

[0021] Preferably, the long-acting antibacterial agent is a copper amine complex solution, wherein the mass percentage of copper ions in the copper amine complex solution is 3% to 7%. More preferably, the mass percentage of copper ions in the long-acting antibacterial agent is 5%.

[0022] Preferably, the detergent composition further contains a pH adjuster, and the pH value of the detergent composition is 8.5–9.0. The inventors have discovered that the degree of binding of the copper amine complex to the fabric is closely related to the pH value of the detergent composition. When the pH value is in the range of 8.5–9.0, the deposition amount of the copper amine complex on the fabric surface is significantly higher than under other pH conditions, resulting in the most superior long-lasting antibacterial effect.

[0023] More preferably, the pH adjuster is citric acid and / or monoethanolamine.

[0024] The detergent composition provided by the present invention comprises the following components in weight percentage: 0.06% to 0.2% divalent copper ions derived from the long-acting antibacterial agent, 0.5% to 60% surfactant, and the balance being detergent additives.

[0025] The surfactant is selected from one or more of anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants. Specifically, the surfactant includes sulfonic acid anionic surfactants. This invention overcomes the defect of loss of antibacterial activity when conventional cationic antibacterial agents are combined with sulfonic acid anionic surfactants. The copper amine complex has a stable structure and can effectively block direct contact and antagonism between copper ions and anionic surfactants in detergent systems, ensuring good compatibility between the antibacterial agent and the surfactant.

[0026] The sulfonic acid anionic surfactant is selected from one or more of alkyl sulfonates, alkylbenzene sulfonates, fatty acid alkyl ester sulfonates, succinate sulfonates, alkyl alcohol polyoxyethylene ether sulfonates, sulfonyl esters of fatty acids, or sulfonyl alkyl amides of fatty acids; the alkyl carbon number of the sulfonic acid anionic surfactant is 6 to 24, selected from straight-chain alkyl and / or branched-chain alkyl, and is a saturated alkyl or an alkyl containing one or more unsaturated double bonds; the cationic portion of the salt is selected from sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines.

[0027] The detergent additives include one or more of the following: solvents, fillers, excipients, softeners, binders, suspending agents, chelating agents, polymers, enzymes, viscosity modifiers, preservatives, colorants, fluorescent whitening agents, and fragrances.

[0028] This invention also provides the application of the above-described detergent composition in fabric washing. Fabrics treated with the detergent composition exhibit a 72-hour long-lasting antibacterial rate of not less than 90% against bacteria and / or fungi. The bacteria include, but are not limited to, Escherichia coli, Klebsiella pneumoniae, Staphylococcus aureus, Staphylococcus hominis, Staphylococcus epidermidis, Corynebacterium pseudodiphtheriae, and Moraxella osloi; the fungi include, but are not limited to, Candida albicans.

[0029] Preferably, the fabric comprises a fibrous material containing hydroxyl and / or amino and / or amide groups. The inventors have discovered that copper amine complexes exhibit strong interactions with free hydroxyl and other groups on the surface of fabric fibers, thus resulting in a more pronounced long-lasting antibacterial effect on fabrics containing hydroxyl, amino, and amide groups. More preferably, the fabric is a cotton fabric, linen fabric, viscose fabric, or a blended fabric primarily composed of cotton fibers.

[0030] This invention relates to a detergent composition with long-lasting antibacterial efficacy. Using a copper amine complex formulation as a long-lasting antibacterial agent, it exhibits sustained antibacterial activity against various bacteria and fungi. Under experimental conditions, it achieves a long-lasting antibacterial rate of over 90.0% for 72 hours against *Escherichia coli* and *Candida albicans*, which are currently considered difficult to inhibit effectively in the industry. As a long-lasting antibacterial agent for clothing, the copper amine complex formulation has the advantages of easy synthesis and good stability. When applied to detergents, it can impart excellent long-lasting antibacterial properties. Furthermore, the use of a copper amine complex formulation as a long-lasting antibacterial agent in this invention is highly compatible with sulfonic acid-based anionic surfactant systems, which are often incompatible with most antibacterial agents. The production process is simple, the cost is low, and the prospects for production and application are broad. Detailed Implementation

[0031] In this invention, the terms "detergent composition with long-lasting antibacterial efficacy" and "long-lasting antibacterial detergent composition" are not distinguished. Specifically, "detergent composition with long-lasting antibacterial efficacy" refers to a liquid detergent composition for fabrics. The detergent composition achieves an antibacterial finish on the fabric surface by contacting the substrate (i.e., the fabric article) in water, thus imparting long-lasting antibacterial efficacy to the washed fabric.

[0032] In this invention, the terms "washed fabric," "fabric after washing," "fabric after washing treatment," "fabric after washing treatment," "fabric after detergent treatment," and "fabric after detergent treatment" are not distinguished. Specifically, they refer to fabrics that have undergone washing, rinsing, and drying processes. Washed fabrics are in a dry state, with at least no obvious water stains or droplets on the surface, and do not feel damp to the touch. The fabric samples involved in this invention are specific test forms of fabrics. The terms "washed fabric sample," "fabric after washing," "fabric after washing treatment," "fabric after washing treatment," "fabric after detergent treatment," and "fabric after detergent treatment" are not distinguished.

[0033] Long-lasting antibacterial efficacy refers to the significant reduction in bacterial count compared to the control sample after co-culturing the fabric treated with the technical solution of this invention with bacteria or fungi for a period of time. When expressed numerically, long-lasting antibacterial efficacy means that the long-lasting antibacterial rate of the fabric treated with the technical solution of this invention is ≥90%.

[0034] In this invention, the terms "long-lasting antibacterial efficacy of fabric after sample treatment" and "long-lasting antibacterial efficacy of the sample" are not distinguished. Regardless of the expression, in the long-lasting antibacterial test, it is the fabric that exerts the inhibitory and killing effect on bacteria. The reason why the fabric has long-lasting antibacterial efficacy is that the antibacterial agent is applied to the surface of the fabric after undergoing specific sample treatment.

[0035] The bacteria are selected from one or more of Staphylococcus aureus, Staphylococcus hominis, Staphylococcus epidermidis, Escherichia coli, Klebsiella pneumoniae, Corynebacterium pseudodiphtheriae, and Moraxella osloi; the fungus is selected from Candida albicans.

[0036] Sulfonic acid surfactants are a type of anionic surfactant. The sulfonic acid surfactants involved in this invention are selected from alkyl sulfonates, alkylbenzene sulfonates, fatty acid alkyl ester sulfonates, succinate sulfonates, alkyl alcohol polyoxyethylene ether sulfonates, sulfonyl esters of fatty acids, or sulfonyl alkyl amides of fatty acids; the alkyl group of the sulfonic acid surfactant has 6 to 24 carbon atoms, is selected from straight-chain alkyl groups and / or branched alkyl groups, is a saturated alkyl group or an alkyl group containing one or more unsaturated double bonds; the cationic portion of the salt is selected from sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines.

[0037] The alkylbenzene sulfonate satisfies the following general formula (1): General formula (1); In general formula (1), R1 is an alkyl group with 6 to 24 carbon atoms, and M+ is a cationic moiety. A suitable example is sodium dodecylbenzenesulfonate.

[0038] Sodium linear dodecylbenzene sulfonate imparts excellent detergency to detergents and can enhance antibacterial effects by utilizing hard water ions. However, it has two drawbacks: 1) Sodium linear dodecylbenzene sulfonate has a very narrow antibacterial spectrum, targeting only a limited number of bacteria such as Staphylococcus aureus and Moraxella osloi. Its antibacterial efficacy against common opportunistic pathogens such as Escherichia coli is poor. 2) Sodium linear dodecylbenzene sulfonate has poor compatibility with metal ions (such as nano-silver and nano-copper) and cationic surfactants. This means that detergents using these substances as antibacterial systems cannot contain sulfonic acid surfactants.

[0039] In addition to the sulfonic acid surfactants mentioned above, anionic surfactants may also be selected from one or more of carboxylate surfactants and sulfate surfactants; specifically selected from C8 to C18 alkyl sulfates, C8 to C18 ethoxylated fatty alcohol sulfates, fatty acid alkyl ester sulfonates, C8 to C18 fatty acid salts, and ethoxylated fatty alcohol ether carboxylates.

[0040] In some implementations, the mixture of anionic surfactants contains ethoxylated fatty alcohol sulfates.

[0041] Ethoxylated fatty alcohol sulfates are derivatives of ethoxylated fatty alcohols and have the following general formula (2): In general formula (2), R1 is an alkyl group having 6 to 24 carbon atoms; x is 0.5 to 30; and M+ is a cation, such as potassium ion, sodium ion, ammonium ion, etc. R1 can be a straight-chain alkyl group or a branched alkyl group; it can be a saturated alkyl group or an alkyl group containing one or more unsaturated double bonds. Preferably, R1 is a straight-chain alkyl group having 8 to 18 carbon atoms. x represents the average degree of ethoxylation, which is 0.5 to 30, preferably 0.5 to 10, and more preferably 0.5 to 3. A suitable example is Texapon N70 from BASF.

[0042] In some embodiments, an alkyl sulfate is included, wherein the alkyl segment can be straight-chain or branched, and can be a saturated alkyl group or an alkyl group containing one or more unsaturated double bonds. Alkyl sulfates with 6 to 24 carbon atoms are preferred, and alkyl sulfates with 8 to 18 carbon atoms are more preferred. A suitable example is sodium dodecyl sulfate.

[0043] In some embodiments, an α-olefin sulfonate is contained, having the following general formula (3): In general formula (3), a is 0 to 2, and R1 is an alkyl group having 6 to 24 carbon atoms, preferably an alkyl group having 8 to 18 carbon atoms.

[0044] In some embodiments, the mixture of anionic surfactants contains a fatty acid salt, preferably a fatty acid salt having 8 to 18 carbon atoms. The alkyl segment of the fatty acid can be straight-chain or branched, and can be a saturated alkyl group or an alkyl group containing one or more unsaturated double bonds. The fatty acid salt can be a single component or a mixture of multiple fatty acids. Suitable examples are sodium oleate and sodium laurate. The fatty acid salt also contains an ethoxylated fatty alcohol ether carboxylate, wherein the fatty alcohol preferably has 8 to 18 carbon atoms and an average degree of ethoxylation preferably of 2.0 to 10.

[0045] The anionic surfactant mixture may also contain one or more mixtures of sodium alkyl disulfonate or its derivatives, preferably sodium alkyl diphenyl ether disulfonate, a suitable example being sodium dodecyl diphenyl ether disulfonate, a product of Dow Company's Dowfax series. It may also contain fatty acid alkyl ester sulfates, preferably fatty acid methyl ester sulfate (MES), with the fatty acid preferably having 8 to 18 carbon atoms. It may also contain sulfosuccinates, preferably disodium salt of fatty alcohol polyoxyethylene ether sulfosuccinate monoester, with the fatty alcohol preferably having 8 to 18 carbon atoms and an average degree of ethoxylation preferably 2.0.

[0046] The nonionic surfactants involved in this invention are selected from one or more of fatty alcohol alkoxylates, alkyl polysaccharides, fatty acid alkoxylates, fatty acid alkylolamides, fatty acid methyl ester ethoxylates, and polyether surfactants.

[0047] In some embodiments, the nonionic surfactant mixture preferably contains a fatty alcohol alkoxylate having the following general formula (4): ; In general formula (4), n is 6 to 24; x is 0.5 to 30; and y is 0 to 10.

[0048] The aforementioned fatty alcohol alkoxylates are products of ring-opening polymerization of fatty alcohols and epoxides under the action of a basic catalyst, and are essentially mixtures. Fatty alcohols include straight-chain alcohols or branched isomeric alcohols. Alkoxy groups include ethoxy groups and propoxy groups. The fatty alcohols are preferably fatty alcohols with 8 to 18 carbon atoms, and preferred alcohols include, but are not limited to, one or mixtures of hexanol, octanol, decanol, 2-ethylhexanol, 3-propylheptanol, lauryl alcohol, isotrimethylene glycol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, palmitole alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, and linolenic acid alcohol. The average degree of ethoxylation x is preferably 2 to 12. Preferred examples include SHELL's NEODOL series of straight-chain fatty alcohol ethoxylated products, DOW's ECOSURF EH series of ethoxylated and propionyl 2-ethylhexanol products, BASF's Lutensol XL series of ethoxylated and propionyl 3-propylheptanol products, and BASF's Lutensol XP series of ethoxylated 3-propylheptanol products.

[0049] In some embodiments, the nonionic surfactant mixture preferably contains an alkyl polysaccharide having the following general formula (5): ; In general formula (5), n is 6 to 24 and p is 1.1 to 3. Preferably, n is 8 to 16. Suitable alkyl polyglycosides include BASF's Glucopon series of alkyl glycosides.

[0050] Nonionic surfactant mixtures may contain fatty acid alkoxylates, preferably ethoxylated C8 to C18 fatty acid esters with an average degree of ethoxylation of 2 to 10. They may contain ethoxylated sorbitol alkyl esters with 6 to 18 alkyl carbons and an average degree of ethoxylation of 4 to 20; suitable examples are Corda's Tween series products.

[0051] Nonionic surfactant mixtures may contain fatty acid alkylolamides, wherein the fatty acids have 6 to 24 carbon atoms and can be straight-chain or branched fatty acid salts, saturated or unsaturated fatty acid salts; the number of alkylols is 0 to 2. Preferred fatty acid alkylolamides are monoethanolamides, diethanolamides, or isopropanolamides with 8 to 18 carbon atoms; a suitable example is coconut oil diethanolamide.

[0052] Nonionic surfactant mixtures may contain fatty acid methyl ester ethoxylates, as shown in the following general formula (6): In general formula (6), n is 6 to 24; x is 2 to 20. Preferably, n is 8 to 18 and x is 0.5 to 30. Preferably, x is 4 to 10. A suitable example is LION's MEE product.

[0053] Nonionic surfactant mixtures may contain polyether surfactants. Polyether surfactants are polymers containing repeating ethylene oxide and / or propylene oxide units; suitable examples include BASF's Pluronic product line.

[0054] The zwitterionic surfactants involved in this invention include betaine-type surfactants, imidazoline-type surfactants, amino acid-type surfactants, and amine oxide-type surfactants; including, but not limited to: alkyl betaine, fatty amide betaine, fatty amide propyl betaine, fatty amide propyl hydroxypropyl sulfonated betaine, sodium alkyl acetate type imidazoline, fatty acid type imidazoline, sulfonic acid type imidazoline; aminopropionic acid derivatives, glycine derivatives; alkyl dimethyl amine oxide, fatty amide propyl dimethyl amine oxide, etc.

[0055] The detergent additives involved in this invention include one or more mixtures of solvents, fillers, excipients, softeners, binders, suspending agents, chelating agents, enzyme preparations, polymers, pH adjusters, viscosity adjusters, preservatives, colorants, fluorescent whitening agents, and fragrances.

[0056] In this invention, the term "solvent" refers to water and / or an organic solvent. Organic solvents are selected from polyols and polyol ethers; suitable examples include propylene glycol and glycerol.

[0057] The detergent compositions of the present invention may contain one or more enzyme preparations to provide cleaning performance, fabric care, and / or other beneficial effects. The enzyme preparations are selected from the group consisting of: proteases, α-amylases, cellulases, hemicellulases, phospholipases, esterases, lipases, peroxidases / oxidases, pectins, lyases, mannanases, keratins, reductases, xylanases, amylopectinases, tanninases, pentosanases, maltosans, arabinases, and β-glucanases. Commonly used enzyme preparations are proteases, amylases, lipases, keratins, and / or cellulases. The enzyme preparation content is 0.001% to 5% of the detergent composition, preferably 0.01% to 2%.

[0058] The detergent composition of the present invention may contain an enzyme stabilizing system at a weight of 0.001% to 10% of the composition. The enzyme stabilizing system is compatible with the detergent composition and may contain one or a mixture of calcium ions, boric acid, borax, propylene glycol, glycerol, and polyols. The weight and amount of the enzyme stabilizing system are adjusted according to the form and composition of the detergent composition and the type of enzyme preparation.

[0059] The chelating agents are selected from ethylenediaminetetraacetic acid salt, ethylenediamine disuccinate, citrate; and methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), N,N-dicarboxylic acid amino-2-hydroxypropanesulfonic acid, 3-hydroxy-2,2'-iminodisuccinic acid, aspartic-N-acetic acid (ASMA), aspartic-N,N-diacetic acid (ASDA), aspartic-N-propionic acid (ASMP), iminodisuccinic acid (IDA), N-(2-sulfomethyl)-aspartic acid (SMAS), N-(2-sulfoethyl)-aspartic acid (SEAS), N-(2-sulfomethyl)-glutamic acid (SMGL), N-(2-sulfoethyl)-glutamic acid (SEGL), N-methyliminodiacetic acid (MIDA), α- The chelating agents are α-alanine-N,N-diacetic acid (α-ALDA), β-alanine-N,N-diacetic acid (β-ALDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid-N,N-diacetic acid (ANDA), sulfanilamide-N,N-diacetic acid (SLDA), taurine-N,N-diacetic acid (TUDA), and sulfomethyl-N,N-diacetic acid (SMDA), and their salts. The salt of the chelating agent may be selected from sodium salts, lithium salts, preferably potassium salts, and more preferably sodium salts.

[0060] The polymers described in this invention include, but are not limited to: salts of homopolymers of acrylic acid, salts of copolymers of acrylic acid; cellulose derivatives, such as carboxymethyl cellulose, ethyl hydroxyethyl cellulose, and methyl cellulose; homopolymers and copolymers of vinylpyrrolidone, such as copolymers of linear polyvinylpyrrolidone, N-vinylpyrrolidone, and vinyl acetate; and polyvinylimide derivatives, such as ethylene oxide polyvinylimide, polyethylene terephthalate and its derivatives, and polyethylene glycol and its derivatives. These polymers impart beneficial effects to detergent compositions, such as resistance to redeposition of dirt, promotion of dirt dissociation from substrate surfaces, or improvement of the appearance of the detergent composition.

[0061] Detergent additives include pH adjusters, which are divided into alkaline adjusters and acidic adjusters. Alkaline adjusters are selected from organic bases, inorganic bases, and strong base-weak base salts familiar to the daily chemical industry, preferably organic amines, alkali metal hydroxides, and alkali metal carbonates. Suitable examples include sodium hydroxide, potassium hydroxide, monoethanolamine, and triethanolamine. Acidic adjusters are selected from organic acids, inorganic acids, and strong acid-weak base salts familiar to the daily chemical industry; suitable examples include citric acid and hydrochloric acid.

[0062] The suspending agents involved in this invention include 12-hydroxy-octadecyl triglyceride (the main component of hydrogenated castor oil), alkyl aryl sulfonates, such as sodium p-toluenesulfonate, sodium xylenesulfonate, and sodium isopropylbenzenesulfonate, or one or more of these.

[0063] Suitable viscosity modifiers for this invention include inorganic salts, polysaccharides, gums, short-chain fatty alcohols, and short-chain fatty alcohol alkyl ethers. Suitable examples are sodium chloride, ethanol, propylene glycol, sodium citrate, alkyl hydroxyalkyl cellulose ethers, carrageenan, xanthan gum, and polyacrylamide derivatives.

[0064] Suitable examples of preservatives in this invention are phenoxy alcohol, sodium benzoate; isothiazolinones and their derivatives such as methylisothiazolinone, methylchloroisothiazolinone, benzisothiazolinone, or a mixture thereof. The amount of preservative used is 0.001% to 5%, preferably 0.01% to 2%.

[0065] The colorant of this invention comprises dyes and pigments. The colorant may include colorants used in detergent products, suitable examples being Acid Red G, Basic Magenta, Acid Golden Yellow G, Acid Yellow G, Basic Egg Yolk, Direct Lightfast Blue B2RL, Indigo, etc.

[0066] The fragrance comprises all fragrance ingredients suitable for washing products. The fragrances used in this invention can be of natural origin, chemically synthesized, or a mixture of both. Suitable examples include lemon, rose, jasmine, lavender, citrus, green, and woody scents.

[0067] In addition to the above-mentioned components, the detergent composition of the present invention may also contain water, cosolvents, solubilizers, structuring agents, foaming agents, defoaming agents, anti-wrinkle agents, and various other common and conventional additives. These additives and related methods of use are well known to those skilled in the art, and their specific types and dosages can be adjusted according to actual needs.

[0068] The present invention will be further described in detail below with reference to embodiments and comparative examples, but the present invention is not limited to these specific embodiments. In the following embodiments and comparative examples, unless otherwise specified, all percentages are mass percentages.

[0069] The raw materials used in the following examples and comparative examples, along with their abbreviations and categories, are explained below: Sodium dodecylbenzenesulfonate (LAS): a sulfonic acid anionic surfactant.

[0070] Sodium fatty alcohol polyoxyethylene ether sulfate (AES): an anionic surfactant.

[0071] C12 fatty alcohol polyoxyethylene ether (9) (abbreviated as AEO9): nonionic surfactant.

[0072] Fatty acid salts: Sodium or potassium salts of straight-chain alkyl fatty acids with 10 to 16 carbon atoms.

[0073] Sodium citrate: A component of detergent matrix.

[0074] Alkaline protease.

[0075] Cosolvent: Ethanol.

[0076] Suspension agent: 12-hydroxy-octadecanoic acid triglyceride.

[0077] Dodecylbenzyldimethylammonium chloride (abbreviated as 1227): cationic antibacterial agent / surfactant.

[0078] Detergent base 1 and detergent base 2 were prepared according to the components and dosages shown in Table 1.

[0079] Table 1. Components and dosage of detergent base Preparation of a long-acting antibacterial agent composed of copper amine complex: Antibacterial agent 1 (copper sulfate-monoethanolamine complex) Take 12.5g of copper sulfate solid powder and dissolve it in 70mL of pure water. Slowly add about 15mL of monoethanolamine to the copper sulfate solution, stirring continuously and observing the process. With the addition of monoethanolamine, a blue precipitate first forms in the solution, then gradually dissolves, finally forming a homogeneous blue solution. Add pure water until the total mass of the solution is 100g, thus obtaining a long-acting antibacterial agent formulation containing 5% copper by mass of a copper sulfate-monoethanolamine complex.

[0080] Antibacterial agent 2 (copper sulfate-diethanolamine complex) Referring to the preparation method of antibacterial agent 1, monoethanolamine was replaced with diethanolamine to prepare a long-acting antibacterial agent formulation containing 5% copper sulfate-diethanolamine complex.

[0081] Antibacterial agent 3 (copper sulfate-triethanolamine complex) Following the preparation method of antibacterial agent 1, monoethanolamine was replaced with triethanolamine to prepare a long-acting antibacterial agent formulation containing 5% copper sulfate-triethanolamine complex.

[0082] Antibacterial agent 4 (copper sulfate-ammonia complex): Following the preparation method of antibacterial agent 1, monoethanolamine was replaced with ammonia to prepare a copper sulfate-ammonia complex preparation containing 5% copper by mass.

[0083] Antibacterial agent 5 (ethanolamine-modified ultrafine copper powder): Ultrafine copper powder was prepared using ethanolamine as a reducing agent, according to the method disclosed in CN121554733A (used as a comparative example).

[0084] Antibacterial agent 6 (zinc sulfate-monoethanolamine complex): Following the preparation method of antibacterial agent 1, copper sulfate was replaced with zinc sulfate to prepare a zinc sulfate-monoethanolamine complex preparation containing 5% zinc by mass (used as a comparative example).

[0085] Antibacterial agent 7 (zinc acetate-monoethanolamine complex): Following the preparation method of antibacterial agent 1, copper sulfate was replaced with zinc acetate to prepare a zinc acetate-monoethanolamine complex preparation containing 5% zinc by mass (used as a comparative example).

[0086] (a) Testing of copper content in fabrics The binding capacity of copper amine complexes to fabrics under washing conditions was analyzed based on copper content. The effect of pH on the binding capacity of copper amine complexes to fabrics was analyzed, and the optimal pH range for the use of copper amine complexes as antibacterial agents for clothing was determined accordingly.

[0087] Test method: Select cotton fabric samples, pre-clean to remove auxiliaries and dry to constant weight, then soak in a copper-containing amine complex sample solution under set conditions: Prepare copper-containing sample solution (using Cu... 2+ The sample solution contained 0.1% Cu by mass. 2+ (As determined by product design), dilute the detergent matrix sample. Use citric acid or monoethanolamine as a pH adjuster to adjust the pH of the sample solution to the target pH range. Add cotton fabric sample, soak at room temperature for 20 min, mechanically stir or oscillate; after soaking, rinse twice with deionized water (1-3 min each time) to remove as much unbound free copper as possible, and then air dry indoors to constant weight.

[0088] Weigh approximately 0.5-1.0 g of dried fabric into a porcelain or quartz crucible that has been ignited to constant weight. First, carbonize it at a low temperature on a hot plate to prevent splashing, then place it in a muffle furnace for ashing: raise the temperature to (180-220) °C and hold for about 30 min to remove volatiles, then raise the temperature to (500-550) °C at 10 °C / min and hold for 3-4 h until a uniform white or light gray ash is obtained (without visible black carbon); remove the crucible and place it in a desiccator to cool to room temperature, recording the ash mass if necessary.

[0089] Add 5-10 mL of analytical grade nitric acid (65-68%) to the crucible (if there is still a small amount of unresolved carbon, add 1-2 mL of 30% hydrogen peroxide). Heat gently in a fume hood until the ash is completely dissolved. After cooling, quantitatively transfer the solution and rinsing solution (with a small amount of 2% nitric acid) to a 50 or 100 mL volumetric flask and dilute to volume with 2% nitric acid. Simultaneously prepare a reagent blank and a full-process method blank. Copper content was determined using inductively coupled plasma optical emission spectrometry (ICP-OES) or intramolecular plasma mass spectrometry (ICP-MS): A series of copper standards ranging from 0-1000 µg / L (or covering the expected range of the sample) were prepared using national traceable standards. The matrix was matched with 2% nitric acid, and an internal standard element (such as Y or Sc, 10-50 µg / L) was added if necessary. An analytical line free from spectral interference was selected (Cu 324.754 nm or 327.395 nm can be selected for ICP-OES). The plasma power, gas flow, and integration time were set according to the instrument's recommended conditions. Multiple readings were performed, and background correction was applied. The copper content in the fabric (in mg / kg) was calculated using the following formula after blank subtraction using a reagent / method blank: Where Csample and Cblank represent the mass concentration (mg / L) of copper in the test solution and blank, respectively, V represents the final volume (L), and m represents the sample weight (kg), which are converted in conjunction with the dilution factor.

[0090] Prepare the sample solutions for each experimental group as shown in Table 2 to investigate the deposition amount of copper amine complex on cotton fabrics under different pH conditions. It should be noted that the content of antibacterial agent 1 listed in Table 2 refers to the percentage of divalent copper ions from the antibacterial agent 1 (copper sulfate-monoethanolamine complex) in the total mass of the sample solution, rather than the amount of antibacterial agent 1 itself added.

[0091] Table 2. Sample solution composition for the copper content test of fabrics The experimental groups were tested according to the aforementioned method for testing the copper content of fabrics, and the results are shown in Table 3.

[0092] Table 3. Copper content of cotton fabrics under different pH conditions Table 3 shows that pH significantly affects the deposition ability of copper-monoethanolamine complexes on fabrics. The deposition amount of copper-monoethanolamine complexes on cotton fabrics reaches its peak (921.2–1676.3 mg / kg) at pH 8.5–9.0, far exceeding that under other pH conditions. At pH below 8.5 or above 9.0, the deposition amount of copper decreases sharply. These results indicate that the optimal pH range for using copper-monoethanolamine complexes as a long-acting antibacterial agent is 8.5–9.0.

[0093] (ii) Long-lasting antibacterial test The long-lasting antibacterial test method specifically includes the following test steps: 1. Preparation of the test bacterial suspension: Take freshly cultured bacteria or fungi from the slant agar, pipette 5.0 mL of the bacterial suspension preparation solution into the slant tube, and repeatedly pipette to wash off the bacterial growth. Then, transfer all the washings to another sterile test tube and mix with an electric mixer for 20 seconds, or tap the tube 80 times on the palm of your hand to ensure the bacterial suspension is homogeneous. The initial bacterial suspension should be prepared with a concentration of 1 × 10⁻⁶. 5 CFU / mL up to 3×10 5 CFU / mL. The bacteria may be one or more of Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Moraxella osloi, Staphylococcus epidermidis, Staphylococcus albus, Staphylococcus hominis, Corynebacterium pseudodiphtheriae; the fungus may be Candida albicans.

[0094] 2. Fabric preparation: Cut the fabric sample into fabric pieces of a predetermined size, degrease, sterilize under high pressure, and then dry. The fabric sample refers to cotton fabric conforming to GB / T 7568.2-2008. The "predetermined size" refers to each fabric piece being a small square piece with a side length of 43mm. Degreasing treatment involves weighing approximately 30g of fabric pieces and adding them to 300mL of degreasing solution (fabric-to-liquid ratio 1:10), and boiling for 1 hour. Remove the cotton fabric, rinse it in 1L of boiled distilled water for 5 minutes, then remove the cotton fabric again and rinse it in 1L of room temperature distilled water for 5 minutes to remove any residual pretreatment solution. Finally, allow the cotton fabric to air dry naturally for later use. The degreasing solution is a pure aqueous solution of 0.00025% fatty alcohol polyoxyethylene ether (9) and 0.5% sodium carbonate.

[0095] The fabric was washed with the detergent composition according to the specified steps, with hard water of a specified hardness as a negative control. Each test group included a control group and a test group. The control group corresponded to the fabric washed with hard water, and the test group contained at least one test subgroup. Each test subgroup corresponded to the fabric treated with one detergent composition.

[0096] The washing steps are as follows: 1-1) Prepare 100g of a 0.3% hard aqueous solution of the detergent composition in a 250mL long-necked beaker. The hardness of the hard aqueous solution is 342ppm (calculated as CaCO3, with a molar ratio of calcium ions to magnesium ions of 3:2). Autoclave at 121°C for 20min before use.

[0097] 1-2) 100g of hard water with a hardness of 350ppm (calculated as CaCO3, with a molar ratio of calcium to magnesium ions of 3:2) was used as a negative control. The hard water was autoclaved at 121℃ for 20min before use.

[0098] 1-3) Add a 6cm diameter magnetic stirring rotor to each long-necked beaker containing liquid from step 1-2), and add cloth sheets of the specified size. Place 15 to 17 cloth sheets in each long-necked beaker, so that the weight ratio of cloth sheets to liquid in each long-necked beaker is 3:100 to 3.5:100. Place the long-necked beakers on the magnetic stirrer and stir and wash at 300rpm for 20min; then pour off the liquid.

[0099] 1-4) Rinsing: After steps 1-3), remove the cloth from each long-necked beaker and transfer it to a 2L beaker. Each 2L beaker corresponds to one long-necked beaker. Add 1L of sterile distilled water to each 2L beaker, scrub the cloth by hand for 1 minute, then squeeze out the water from the cloth; rinse twice.

[0100] 1-5) Air drying in the cabinet: After steps 1-4), remove the rinsed cloth from each flask and place it in a sterile petri dish. Each beaker corresponds to one sterile petri dish. Open the lids of each sterile petri dish in the biosafety cabinet and allow it to air dry.

[0101] The control group (1-6) refers to the group of fabric sheets washed with 100g of hard water with a hardness of 350ppm (calculated as CaCO3, with a molar ratio of calcium ions to magnesium ions of 3:2). The hard water was autoclaved at 121℃ for 20min before use.

[0102] (1-7) The test subgroup refers to the group of fabric pieces washed with a hard aqueous solution containing 0.3% detergent composition. The hard aqueous solution has a hardness of 342 ppm (calculated as CaCO3, and the molar ratio of calcium ions to magnesium ions is 3:2), and is autoclaved at 121°C for 20 min before use.

[0103] 3. Sample inoculation: For each test group, take two cloth samples of the same sample and two control samples, and stack them in two empty sterile petri dishes. Add 0.2 mL of the above bacterial suspension, ensuring the bacterial suspension is spread as evenly as possible on the sample. Each test group contains two parallel test subgroups. Each test subgroup includes one set of cloth samples treated with the detergent composition (hereinafter referred to as test samples) and one set of cloth samples treated with the control (hereinafter referred to as control samples), which are used for immediate elution and testing after inoculation and for elution and testing after further incubation, respectively.

[0104] 4. Washing immediately after inoculation: Use sterile tweezers to pick up one group of test samples and one group of control samples that have just been inoculated with bacteria, and put them into two homogenization bags containing 10g of sterile bacterial eluent. Homogenize them in a homogenizer for 1 minute to wash the bacteria off the samples.

[0105] 5. Continued Incubation and Elution of Inoculated Fabric Patches: Cover two sterile petri dishes containing the inoculated bacterial suspension (one containing the inoculated test sample and the other containing the inoculated control sample) with their lids and seal with plastic wrap to prevent evaporation of the liquid on the carrier. Incubate at 36°C for one day, maintaining a relative humidity above 85%. After the incubation period, transfer each test sample and control sample to a homogenizing bag containing 10g of sterile bacterial eluent. Homogenize in a homogenizer for 1 minute to elute the bacteria from the samples.

[0106] 6. Viable Bacterial Count Determination: Using a pipette, transfer 1 mL of the eluent (from steps 4 and 5 above) into a test tube containing 9 mL of phosphate-buffered saline (PBS) and shake thoroughly. From this test tube, transfer 1 mL of the sample solution into another test tube containing 9 mL of PBS and shake thoroughly. Repeat this process, performing 10-fold serial dilutions of the eluent from steps 4 and 5 above. Use a different pipette tip for each dilution. Using a pipette, transfer 1 mL of the sample solution from each of the serially diluted test tubes into a Petri dish, then add 15 mL to 20 mL of tryptone-soy agar (TSA) medium at 45°C to 46°C. Cap the dish and allow it to solidify at room temperature. Then, invert the Petri dish and incubate at 36°C for 72 hours. Count the colonies. Steps 3 to 6 above should be performed at least three times in parallel.

[0107] 7. Evaluation of experimental validity: The average bacterial colony count of the control sample washed immediately after inoculation should be less than 1×10⁻⁶. 5 CFU / mL up to 9×10 5 CFU / mL, count the bacterial growth value F according to formula (2), and when F is greater than or equal to 1.5, the test is considered valid.

[0108] F = lgC t -lgC0………………………………………Equation (1); F: Logarithmic growth value of viable bacteria in the control sample; C0: Viable bacteria count of the control sample immediately after inoculation, C t The number of viable bacteria obtained after the control sample has been cultured for time t.

[0109] 8. Calculation of long-acting antibacterial rate: The long-acting antibacterial rate is calculated according to formula (2), and the result is rounded to two decimal places.

[0110] ………………………………………Equation (2); Ct: The number of bacteria measured after the control sample is inoculated and cultured for a period of time; Tt: The number of bacteria measured after the test sample is inoculated and cultured for a period of time.

[0111] When the relative standard deviation between three parallel test results is less than 15%, the mathematical average of the test results is taken as the long-lasting antibacterial rate of the sample. When the calculated value is negative, it is represented as "0.00". A long-lasting antibacterial rate ≥90.00% indicates that the fabric treated with the sample has a long-lasting antibacterial effect, that is, the sample has a long-lasting antibacterial effect.

[0112] The detergent compositions of each embodiment and comparative example were prepared as shown in Table 4. It should be noted that in Table 4, the amount of antibacterial agent added in Examples 1-3 and Comparative Example 1 refers to the percentage of divalent copper ions from the corresponding antibacterial agent in the total mass of the detergent composition, not the amount of the antibacterial agent itself; the amount of antibacterial agent added in Comparative Example 2 is the percentage of ultrafine copper powder in the total mass of the detergent composition; the amount of antibacterial agent added in Comparative Examples 3 and 4 refers to the percentage of zinc ions from the corresponding antibacterial agent in the total mass of the detergent composition; the amount of antibacterial agent added in Comparative Example 6 refers to the percentage of copper ions from the corresponding antibacterial agent (copper sulfate) in the total mass of the detergent composition; and the amount of antibacterial agent added in Comparative Examples 7 and 8 refers to the percentage of 1227 and monoethanolamine raw materials themselves in the total mass of the detergent composition.

[0113] Table 4. Components and dosages of detergent compositions in Examples 1-3 and Comparative Examples 1-8 Following the aforementioned long-lasting antibacterial test method, Escherichia coli ATCC25922, Klebsiella pneumoniae ATCC4352, and Candida albicans ATCC10231 were used as test bacteria to test the long-lasting antibacterial rate of the detergent compositions of each example and comparative example for 72 hours. The results are shown in Table 5.

[0114] Table 5. Long-lasting antibacterial effects of each example and comparative example. As can be seen from the test results in Table 5 above, the detergent compositions of Examples 1-3 of the present invention, using the technical solution of the present invention, can impart good long-lasting antibacterial effects to fabrics under washing conditions against the above three microorganisms, indicating that the detergent compositions of the present invention have a broad long-lasting antibacterial spectrum and excellent long-lasting antibacterial ability. Comparative Example 1 can also achieve a long-lasting antibacterial effect, but the effect is slightly reduced, and the copper-ammonia complex has poor stability in the detergent, and precipitation will occur after long-term storage. Comparative Example 2 uses an ethanolamine-modified ultrafine copper powder antibacterial agent, which also has a certain long-lasting antibacterial effect, but the antibacterial rate against Klebsiella pneumoniae does not reach more than 90%, and due to the physical properties of its solid copper powder, it needs to be used in conjunction with a suspension system, and there are problems with the appearance of the detergent. Comparative Examples 3-4 use zinc salt complexes as antibacterial agents. The results show that zinc salt, as a metal ion with antibacterial activity, performs significantly worse in long-lasting antibacterial action in the detergent compared to copper, possibly due to the poor binding ability of the zinc-ethanolamine complex to the fabric. The washing compositions of Comparative Examples 6-8 used copper salt, the cationic antibacterial agent dodecylbenzyldimethylammonium chloride, and ethanolamine as antibacterial agents, respectively. Under the same conditions, none of them achieved an effective long-lasting antibacterial effect against the three microorganisms. This may be because copper ions and dodecylbenzyldimethylammonium chloride, as antibacterial agents, cannot effectively adhere to the fabric during the washing process and cannot produce an antibacterial effect for a long time. The washing composition of Comparative Example 5 has a certain antibacterial effect against Candida albicans because the sulfonic acid surfactant in the washing agent has a weak antibacterial ability.

[0115] (III) Long-lasting antibacterial effect in different detergent bases The detergent compositions of Examples 4 and 5 were formulated as shown in Table 6 to investigate the adaptability of the copper amine complex antibacterial agent in different detergent bases. In Table 6, the amount of antibacterial agent added in Examples 4 and 5 refers to the percentage of divalent copper ions from the corresponding antibacterial agent to the total mass of the detergent composition, rather than the amount of the antibacterial agent itself added.

[0116] Table 6. Components and dosages of different detergent bases in the examples The test was conducted according to the aforementioned long-acting antibacterial test method, and the results are shown in Table 7.

[0117] Table 7. Long-lasting antibacterial effect of different detergent bases As shown in Tables 7 and 5, both the copper sulfate-monoethanolamine complex antibacterial agent and the copper sulfate-triethanolamine complex antibacterial agent exhibit excellent long-lasting antibacterial properties in detergent base 1 and detergent base 2, indicating that the copper amine complex long-lasting antibacterial agent of the present invention has good formulation adaptability and compatibility.

[0118] (iv) Investigation of the minimum effective dosage of antibacterial agents The detergent compositions of Examples 6-9 were prepared as shown in Table 8, and the long-lasting antibacterial effect of the copper amine complex antibacterial agent at different addition amounts was investigated. In Table 8, the amount of antibacterial agent added in Examples 6-9 refers to the percentage of divalent copper ions from the corresponding antibacterial agent to the total mass of the detergent composition, rather than the amount of the antibacterial agent itself added.

[0119] Table 8 Examples of different amounts of antibacterial agent: components and dosage The test was conducted according to the aforementioned long-acting antibacterial test method, and the results are shown in Table 9.

[0120] Table 9. Long-lasting antibacterial effect of different amounts of antibacterial agent As shown in Table 9, the copper amine complex long-acting antibacterial agent can exert excellent long-acting antibacterial performance at extremely low addition levels (0.06% to 0.08% based on copper ions), with high efficiency and significant cost advantages.

[0121] (v) Antibacterial spectrum expansion test Using Examples 1 and 3 as examples, the long-lasting antibacterial effect of the copper amine complex detergent composition on a wider range of bacterial species was investigated. The expanded bacterial species included Staphylococcus aureus, Staphylococcus hominis, Staphylococcus epidermidis, Corynebacterium pseudodiphtheriae, and Moraxella osloi. The test results are shown in Table 10.

[0122] Table 10. Long-lasting antibacterial effect of extended bacterial strains As shown in Table 10, the detergent composition of the present invention has excellent 72-hour long-lasting antibacterial effect against a variety of Gram-positive and Gram-negative bacteria, with a broad antibacterial spectrum and broad application prospects.

[0123] (vi) Long-lasting antibacterial effect on fabrics of different materials Using the composition of Example 1 as an example, the long-lasting antibacterial performance of the copper amine complex antibacterial agent on fabrics of different materials was investigated. Test fabrics included cotton, linen, polyamide (nylon), polyester, viscose, and a 20% cotton + 80% polyester blend. The tested bacteria were *Escherichia coli* and *Candida albicans*. The results are shown in Table 11.

[0124] Table 11 Long-lasting antibacterial effect on fabrics of different materials As shown in Table 11, the composition of Example 1 exhibited excellent long-lasting antibacterial effects (antibacterial rate ≥90%) on cotton fabrics, viscose fabrics, and cotton-based blended fabrics (20% cotton + 80% polyester). On linen fabrics, it showed good antibacterial effect against Escherichia coli (97.50%), but its antibacterial rate against Candida albicans (87.00%) was slightly below 90%. The long-lasting antibacterial effect on polyamide and polyester fabrics was relatively poor.

[0125] The above results are consistent with the inventors' hypothesis regarding the binding mechanism of copper amine complexes with fabric fibers: copper amine complexes have a strong interaction with free hydroxyl groups on the fiber surface, thus exhibiting higher affinity and better long-lasting antibacterial effects on cotton fibers, viscose fibers, and other fibers with hydroxyl-rich surfaces. For synthetic fibers with lower surface hydroxyl content (such as polyester and polyamide), the deposition efficiency of copper amine complexes decreases, and the long-lasting antibacterial effect weakens accordingly.

[0126] The detergent composition with long-lasting antibacterial efficacy provided by the present invention uses a copper amine complex as a long-lasting antibacterial agent, and has the following beneficial effects: (1) It has good compatibility with conventional anionic surfactant systems (especially sulfonic acid anionic surfactant systems), overcoming the technical problem of inactivation when existing cationic antibacterial agents are combined with anionic surfactants.

[0127] (2) By pre-forming a complex between copper salt and organic amine, copper ions can be efficiently deposited on the fabric surface under washing conditions, thus realizing the breakthrough application of copper-based antibacterial agents in the field of fabric washing.

[0128] (3) By optimizing the pH value of the detergent composition to 8.5-9.0, the deposition efficiency of copper amine complex on the fabric surface was significantly improved, thereby obtaining excellent long-lasting antibacterial effect.

[0129] (4) It has a broad-spectrum and long-lasting antibacterial effect against a variety of bacteria and fungi. At a certain concentration, the long-lasting antibacterial rate can reach more than 99% for 72 hours.

[0130] (5) The preparation process of copper amine complex is simple, the raw materials are widely available and the cost is low, making it suitable for large-scale industrial production and application.

[0131] In summary, this invention provides a long-lasting antibacterial detergent composition that is simple to process, cost-controllable, has excellent antibacterial effect, and good compatibility with existing detergent systems, and has good industrial application prospects and market promotion value.

[0132] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present invention, and these modifications or substitutions should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A detergent composition with long-lasting antibacterial efficacy, characterized in that, It contains a copper amine complex as a long-acting antibacterial agent; the copper amine complex is generated by the reaction of divalent copper ions with organic amines and / or ammonia in an aqueous solution.

2. The detergent composition according to claim 1, characterized in that, In the copper-amine complex, the molar ratio of divalent copper ions to organic amines is 1:(3.1-3.5).

3. The detergent composition according to claim 1 or 2, characterized in that, The divalent copper ions are derived from one or more of copper sulfate, copper chloride, and copper acetate; the organic amine is selected from one or more of monoethanolamine, diethanolamine, and triethanolamine.

4. The detergent composition according to claim 1, characterized in that, The content of divalent copper ions derived from the long-acting antibacterial agent is 0.06% to 0.2% based on the total mass of the detergent composition.

5. The detergent composition according to claim 1, characterized in that, The detergent composition also contains a pH adjuster, and the pH of the detergent composition is 8.5 to 9.

0.

6. The detergent composition according to claim 5, characterized in that, The pH adjuster is citric acid and / or monoethanolamine.

7. The detergent composition according to claim 1, characterized in that, It consists of the following components by mass percentage: 0.06% to 0.2% divalent copper ions derived from the long-acting antibacterial agent; 0.5% to 60% surfactant; and the balance being detergent additives.

8. The detergent composition according to claim 7, characterized in that, The surfactant is selected from one or more of anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants, or a mixture thereof.

9. The detergent composition according to claim 8, characterized in that, The surfactant includes sulfonic acid anionic surfactants.

10. The detergent composition according to claim 9, characterized in that, The sulfonic acid anionic surfactant is selected from one or more of alkyl sulfonates, alkylbenzene sulfonates, fatty acid alkyl ester sulfonates, succinate sulfonates, alkyl alcohol polyoxyethylene ether sulfonates, sulfonyl esters of fatty acids, or sulfonyl alkyl amides of fatty acids; the cationic portion of the salt is selected from sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines.

11. The detergent composition according to claim 7, characterized in that, The detergent additives include one or more of the following: solvents, fillers, excipients, softeners, binders, suspending agents, chelating agents, polymers, enzymes, pH adjusters, viscosity adjusters, preservatives, colorants, fluorescent whitening agents, and fragrances.

12. The detergent composition according to claim 1, characterized in that, The long-acting antibacterial agent is a copper amine complex solution, wherein the mass percentage of copper ions in the copper amine complex solution is 3% to 7%.

13. The use of a detergent composition according to any one of claims 1 to 12 in the washing of fabrics, characterized in that, Fabrics treated with the detergent composition exhibit a 72-hour long-lasting antibacterial rate of not less than 90% against bacteria and / or fungi.

14. The application according to claim 13, characterized in that, The bacteria include Escherichia coli and Klebsiella pneumoniae; the fungi include Candida albicans.

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