Process of post-wash removing microorganism from garments

Abstract

To provide a process of post-wash removing microorganism from garments.SOLUTION: A process of post-wash removing microorganism from garments comprises the steps of: a) providing an article of clothing in a washing machine; and b) contacting the article of clothing during a wash sub-cycle of the washing machine with a liquid detergent composition comprising from 2 wt.% to 60 wt.% of the composition of a surfactant system and from 0.01 wt.% to 1 wt.% of the composition of an anti-microbial agent that is a specific hydroxyl diphenyl ether, wherein the surfactant system comprises: from 50.1 wt.% to 60 wt.% of the surfactant system of C6 to C20 linear alkylbenzene sulfonates; from 10 wt.% to 49.9 wt.% of the surfactant system of C6 to C20 alkyl alkoxy sulfates; and from 0.5 wt.% to 10 wt.% of the surfactant system of C10 to C18 alkyl ethoxylates.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a liquid detergent composition comprising: a) providing a clothing item in a washing machine; and b) treating the clothing item during a wash subcycle of the washing machine with a surfactant system and an antimicrobial agent selected from the group consisting of diphenyl ethers, wherein the surfactant system comprises C6-C 20 and contacting the laundry with a liquid detergent composition comprising linear alkyl benzene sulfonate (LAS). [Background technology]

[0002] Consumer products have been developed to address the consumer need for antimicrobial benefits in addition to their original intended functions. For example, antimicrobial laundry detergent products are desired by consumers because they have antimicrobial benefits for fabrics while washing the fabrics. Currently, various antimicrobial agents are known for use in consumer product formulations to provide antimicrobial benefits, such as bleach, chloroxylenol (PCMX), benzalkonium chloride (BKC), diphenyl ether, etc. Antimicrobial agents include two main types, one type functions as an agent for removing microorganisms during washing (e.g., bleach, PCMX, BKC), and the other type functions as an agent for preventing microorganisms during storage or use (e.g., diphenyl ether).

[0003] However, it remains difficult to achieve the desired antibacterial effect. In particular, no antibacterial detergent product is known that can provide post-wash microbial removal during storage or use of the garment. In particular, antibacterial agents that function as microbial removers cannot be attached to the garment and can only function during washing. On the other hand, diphenyl ether can function as a means of preventing microbial growth during use of the garment after being attached to the garment by washing, but is not effective in removing microorganisms already present on the garment. However, it is desirable for consumers to provide an antibacterial detergent product that can provide the benefit of post-wash microbial removal as well as post-wash microbial prevention. Summary of the Invention [Problem to be solved by the invention]

[0004] Thus, there remains a need for laundry detergent compositions that can provide effective benefits for post-wash removal of microorganisms from clothing. [Means for solving the problem]

[0005] C6-C as the main surfactant in liquid detergent formulations 20 It is a surprising and unexpected discovery of the present invention that a combination of a surfactant system including a linear alkyl benzene sulfonate (LAS) and an antimicrobial agent selected from the group consisting of diphenyls can provide effective utility for removing microorganisms from clothing after washing.

[0006] In particular, the present invention relates to a liquid detergent composition comprising from 2% to 60% by weight of the composition of a surfactant system and from 0.01% to 1% by weight of the composition of a surfactant of formula (I):

[0007] [ka] (In the formula, each Y is independently selected from chlorine, bromine, or fluorine; each Z is independently selected from SO2H, NO2, or C1-C4 alkyl; r is 0, 1, 2, or 3; o is 0, 1, 2, or 3; p is 0, 1, or 2; m is 1 or 2; and n is 0 or 1; and The surfactant system contains C6 to C 20 A liquid detergent composition is provided that includes a linear alkylbenzene sulfonate (LAS).

[0008] Correspondingly, the present invention in one aspect provides a method for post-wash removal of microorganisms from clothing, comprising the steps of: a) providing clothing items in a washing machine; b) contacting the clothing items with a liquid detergent composition according to the present disclosure during a wash subcycle of the washing machine; The present invention relates to a method comprising the steps of:

[0009] In another aspect, the present invention relates to the use of a liquid detergent composition according to the present disclosure for removing microorganisms from clothing items after washing.

[0010] Preferably the composition comprises from 4% to 50%, preferably from 6% to 40%, more preferably from 10% to 30% by weight of the composition of a surfactant system.

[0011] Preferably, the surfactant system is a C6-C 20 Alkyl sulfate (AS), C6-C 20 Alkyl alkoxy sulfate (AAS), C6-C 20 Methyl ester sulfonate (MES), C6-C 20 an additional anionic surfactant selected from the group consisting of alkyl ether carboxylates (AECs), and any combination thereof, and / or a nonionic surfactant selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters, and alkoxylated derivatives of sorbitan esters, and any combination thereof.

[0012] Preferably, C6 to C 20 The linear alkylbenzene sulfonate (LAS) is present as the majority surfactant in the composition.

[0013] Preferably the surfactant system comprises: 1) 50.1% to 90% by weight, preferably 51% to 70% by weight, more preferably 52% to 60% by weight, of the surfactant system, e.g., 52% by weight, 53% by weight, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 65% by weight, or any range therebetween, C6 to C 20 Linear alkylbenzene sulfonate (LAS), 2) 10% to 49.9% by weight, preferably 30% to 49% by weight, more preferably 40% to 45% by weight, of the surfactant system, for example 35% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight, or any range therebetween, of C6 to C 20 Alkyl alkoxy sulfate (AAS), 3) 0.5% to 10% by weight, preferably 1% to 8% by weight, more preferably 2% to 6% by weight, of the surfactant system, for example 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, or any range therebetween. 10 ~C 18 Alkyl ethoxylates, Includes.

[0014] Preferably, the composition comprises from 0.01% to 0.1% by weight of the composition, preferably from 0.01% to 0.05%, more preferably from 0.01% to 0.04%, and most preferably from 0.02% to 0.03% by weight of the composition of the antibacterial agent, preferably selected from the group consisting of 4-4'-dichloro-2-hydroxydiphenyl ether, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and combinations thereof, more preferably the antibacterial agent is 4-4'-dichloro-2-hydroxydiphenyl ether.

[0015] Preferably, the composition further comprises from 0.1% to 10%, preferably from 0.2% to 5%, more preferably from 0.3% to 2% by weight of the composition of a polyamine, preferably a polyethyleneimine, more preferably an alkoxylated polyethyleneimine.

[0016] In some preferred embodiments, the composition comprises: a) a surfactant system of 15% to 30% by weight of the composition, comprising 52% to 60% by weight of the surfactant system of C6-C 20 Linear alkylbenzene sulfonate (LAS) and 40% to 45% by weight of C6-C surfactant system 20 Alkyl alkoxy sulfate (AAS) and 2% to 6% by weight of C in the surfactant system 10 ~C 18 a surfactant system comprising an alkyl ethoxylate; b) 0.01% to 0.04% by weight of the composition of 4,4'-dichloro-2-hydroxydiphenyl ether; c) 0.3% to 2% by weight of the composition of an alkoxylated polyethyleneimine; Includes.

[0017] In another aspect, the present invention relates to a liquid detergent composition as described above for use in the post-wash removal of microorganisms from clothing.

[0018] The advantage of the liquid detergent composition according to the present disclosure is that it can improve the removal of microorganisms. In particular, the liquid detergent composition according to the present disclosure can significantly reduce the amount of microorganisms from fabrics during use and / or storage after washing. In the context of the present disclosure, removing microorganisms is intended to mean reducing the amount of viable microorganisms, including but not limited to killing, inactivating, and / or eliminating microorganisms. In particular, removing microorganisms after washing is intended to mean reducing the amount of viable microorganisms during use and / or storage of clothes after washing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] definition As used herein, articles such as "a" and "an," when used in a claim, are understood to mean one or more of what is claimed or described.

[0020] As used herein, the terms "comprise, comprise, comprising," "include, includes, including," "contain, contains, containing" are intended to be open-ended, i.e., other steps and other ingredients can be added that do not affect the end result. The above terms include the terms "consisting of" and "consisting essentially of."

[0021] As used herein, when a composition is "substantially free" of a particular component, it means that the composition contains less than a certain amount of the particular component, or less than 0.1% by weight of the composition, or less than 0.01% by weight, or 0.001% by weight.

[0022] As used herein, the term "laundry detergent composition" refers to a composition for laundering soiled materials, including fabrics. Such compositions can be used as a laundry pre-treatment, laundry post-treatment, or can be added during the rinse or wash cycle of a laundry operation. The laundry detergent composition composition may have a form selected from liquid, powder, single-phase or multi-phase unit dose, pouch, tablet, gel, paste, bar, or flake. Preferably, the laundry detergent composition is liquid. The term "liquid laundry detergent composition" herein refers to a composition that is in a form selected from the group consisting of pourable liquid, gel, cream, and combinations thereof. The liquid laundry detergent composition may be either aqueous or non-aqueous, and may be anisotropic, isotropic, or combinations thereof.

[0023] As used herein, the term "antimicrobial agent" refers to a compound whose principal intended function is to kill bacteria and / or prevent the growth or reproduction of bacteria. Conventional antimicrobial agents include cationic antimicrobial agents (e.g., certain ammonium chlorides), nonionic antimicrobial agents, and the like. The diphenyl ether compounds used in the present invention are nonionic antimicrobial agents.

[0024] As used herein, the term "primary surfactant" refers to a surfactant that is present in a composition in an amount greater than any other surfactant contained by such composition.

[0025] As used herein, the term "majority surfactant" refers to a surfactant present in a composition in an amount that is at least 50% by weight of the total surfactant content in such composition.

[0026] As used herein, the term "alkyl" means a hydrocarbyl moiety that is branched or unbranched, substituted or unsubstituted. The term "alkyl" includes the alkyl portion of an acyl group.

[0027] As used herein, the term "washing liquor" refers to an aqueous solution in the amount typically used for one laundry wash cycle, preferably 1 L to 50 L, or alternatively 1 L to 20 L for manual wash and 20 L to 50 L for machine wash.

[0028] As used herein, the term "soiled fabric" is used non-specifically and may refer to any type of natural or man-made fiber, including natural, man-made, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations.

[0029] Liquid detergent composition The liquid detergent composition of the present invention comprises from 2% to 60% by weight of the composition of a surfactant system and from 0.01% to 1% by weight of the composition of a compound of formula (I):

[0030] [ka] (In the formula, each Y is independently selected from chlorine, bromine, or fluorine; each Z is independently selected from SO2H, NO2, or C1-C4 alkyl; r is 0, 1, 2, or 3; o is 0, 1, 2, or 3; p is 0, 1, or 2; m is 1 or 2; and n is 0 or 1; and The surfactant system contains C6 to C 20 A liquid detergent composition comprising a linear alkylbenzene sulfonate (LAS).

[0031] It has surprisingly been found that by combining a surfactant system containing LAS as the primary surfactant with diphenyl ether, superior post-wash microbial removal benefits can be achieved, a result that is unexpected since such benefits have not previously been observed in liquid detergent compositions.

[0032] Preferably the composition comprises from 4% to 50%, preferably from 6% to 40%, more preferably from 10% to 30% by weight of the composition of a surfactant system.

[0033] Preferably, the surfactant system is a C6-C 20 Alkyl sulfate (AS), C6-C 20 Alkyl alkoxy sulfate (AAS), C6-C 20 Methyl ester sulfonate (MES), C6-C 20 an additional anionic surfactant selected from the group consisting of alkyl ether carboxylates (AECs), and any combination thereof, and / or a nonionic surfactant selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters, and alkoxylated derivatives of sorbitan esters, and any combination thereof.

[0034] Preferably, C6 to C 20The linear alkylbenzene sulfonate (LAS) is present as the majority surfactant in the composition.

[0035] The laundry detergent composition herein provides a elimination effect against gram-positive bacteria (e.g., Staphylococcus aureus). In one embodiment, the laundry detergent composition exhibits a microbial elimination value of at least 1.0 log reduction, preferably 1.5 log reduction, more preferably 2.0 log reduction, even more preferably 2.5 log reduction, and most preferably 3.0 log reduction, against gram-positive bacteria 18 hours after inoculation, as compared to the time of inoculation. Preferably, the composition exhibits at least 2.2 log reduction, preferably 2.5 log reduction, against Staphylococcus aureus 18 hours after inoculation, as measured by Test 1 described below. More preferably, the composition exhibits at least 3.0 log reduction against Staphylococcus aureus. Of note, Staphylococcus aureus is frequently found on human skin, and therefore fabrics (especially those fabrics during wear) are in particular need of antimicrobial effect against Staphylococcus aureus.

[0036] The laundry detergent composition may have any suitable viscosity depending on factors such as the ingredients incorporated and the purpose of the composition. In one embodiment, the composition has a high shear viscosity of about 200 to about 3,000 cP, alternatively about 300 to about 2,000 cP, alternatively about 500 to about 1,000 cP at a shear rate of 20 / sec and a temperature of 21° C., and a low shear viscosity of about 500 to about 100,000 cP, alternatively about 1000 to about 10,000 cP, alternatively about 1,500 to about 5,000 cP at a shear rate of 1 / sec and a temperature of 21° C.

[0037] Surfactant Systems Preferably, the composition comprises from 4% to 50%, preferably from 6% to 40%, more preferably from 10% to 30% by weight of the composition of a surfactant system. In particular, the surfactant system may comprise, in addition to the LAS, additional anionic and non-ionic surfactants.

[0038] Suitable anionic surfactant systems for the compositions of the present invention are C6-C 20Linear Alkylbenzene Sulfonate (LAS), C6~C 20 Alkyl sulfate (AS), C6-C 20 Alkyl alkoxy sulfate (AAS), C6-C 20 Methyl ester sulfonate (MES), C6-C 20 For example, the laundry detergent composition may be selected from the group consisting of C6 to C7 alkyl ether carboxylates (AECs), and any combination thereof. 20 Alkyl alkoxy sulfate (AA x S) (wherein x is about 1 to 30, preferably about 1 to 15, more preferably about 1 to 10, and most preferably about 1 to 3). x The alkyl chain in S may be either linear or branched, with mid-chain branched AA x Particularly preferred are S surfactants. Preferred group AA x S is C, where x is about 1 to 3. 12 ~C 14 Alkyl alkoxy sulfates are included.

[0039] Suitable nonionic surfactant systems for the compositions of the present invention may be selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combination thereof. Non-limiting examples of nonionic surfactants suitable for use herein include C ... 12 ~C 18 Alkyl ethoxylate; C6~C 12 Alkylphenol alkoxylates (wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units); C with ethylene oxide / propylene oxide blocked alkyl polyamine ethoxylates such as Pluronic® available from BASF; 12 ~C 18 Alcohol and C6-C12 Alkylphenol condensate; C 14 ~C 22 Included in the nonionic surfactants herein are alkoxylated ester surfactants, such as those of the formula R 1 C(O)O(RO)nR 3 [In the formula, R 1 Linear and branched C6-C 22 selected from an alkyl or alkylene moiety; R 2 is selected from C2H4 and C3H6 moieties, R 3 Also useful are alkoxylated ester surfactants having a C6 to C7 moiety, wherein n has a value of from about 1 to about 20. Such alkoxylated ester surfactants include fatty methyl ester ethoxylates (MEEs), which are well known in the art. In some embodiments, the alkoxylated nonionic surfactants included in the laundry detergent compositions of the present invention include C6 to C7 moieties. 20 Alkoxylated alcohols, preferably C8-C 18 Alkoxylated alcohols, more preferably C 10 ~C 16 Alkoxylated alcohol. C6~C 20 The alkoxylated alcohol is preferably an alkyl alkoxylated alcohol having an average alkoxylation degree of about 1 to about 50, preferably about 3 to about 30, more preferably about 5 to about 20, and even more preferably about 5 to about 9.

[0040] In some embodiments, the composition is 20 Linear alkylbenzene sulfonate surfactants (LAS), preferably C 10 ~C 16 LAS, more preferably C 12 ~C 14 Includes LAS.

[0041] Preferably, C6 to C 20 The linear alkylbenzene sulfonate (LAS) is present as the majority surfactant in the composition.

[0042] Preferably the surfactant system comprises: 1) 50.1% to 90% by weight, preferably 51% to 70% by weight, more preferably 52% to 60% by weight of C6 to C7 20 Linear alkylbenzene sulfonate (LAS), 2) 10% to 49.9% by weight, preferably 30% to 49% by weight, more preferably 40% to 45% by weight of C6 to C 20 Alkyl alkoxy sulfate (AAS), 3) 0.5% to 10% by weight, preferably 1% to 8% by weight, more preferably 2% to 6% by weight of C in the surfactant system 10 ~C 18 and alkyl ethoxylates.

[0043] The laundry detergent composition of the present invention may further comprise a cationic surfactant. Non-limiting examples of cationic surfactants include quaternary ammonium salt surfactants (which may have up to 26 carbon atoms, including alkoxylated quaternary ammonium (AQA) surfactants), dimethylhydroxyethyl quaternary ammonium; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants, and amine surfactants (e.g., amidopropyldimethylamine (APA)).

[0044] Diphenyl ether antibacterial agents The diphenyl ether-based antibacterial agent of the present invention is a non-ionic compound. It has been found in the present invention that the antibacterial agent of the present invention, due to its non-ionic nature, can provide a stable liquid detergent composition.

[0045] Preferably, the antibacterial agent is a hydroxyl diphenyl ether. The antibacterial agents herein can be either halogenated or non-halogenated, but are preferably halogenated. In one embodiment, the antibacterial agent is represented by the following formula (I):

[0046] [ka] (In the formula, each Y is independently selected from chlorine, bromine, or fluorine, preferably chlorine or bromine, more preferably chlorine; each Z is independently selected from SO2H, NO2, or C1-C4 alkyl; r is 0, 1, 2 or 3, preferably 1 or 2; o is 0, 1, 2 or 3, preferably 0, 1 or 2; p is 0, 1 or 2, preferably 0; m is 1 or 2, preferably 1; n is 0 or 1, preferably 0).

[0047] In the above definition of formula (I), 0 means nothing. For example, when p is 0, Z does not exist in formula (I). Each Y and each Z can be the same or different. In one embodiment, o is 1, r is 2, and Y is chlorine or bromine. In this embodiment, one chlorine atom can be bonded to a benzene ring while a bromine atom and another chlorine atom can be bonded to another benzene ring, or a bromine atom can be bonded to a benzene ring while two chlorine atoms can be bonded to another benzene ring.

[0048] More preferably, the antimicrobial agent is selected from the group consisting of 4-4'-dichloro-2-hydroxydiphenyl ether ("diclosan"), 2,4,4'-trichloro-2'-hydroxydiphenyl ether ("triclosan"), and combinations thereof. Most preferably, the antimicrobial agent is 4-4'-dichloro-2-hydroxydiphenyl ether, commercially available from BASF under the trade name Tinosan® HP100.

[0049] In addition to diphenyl ether, other antimicrobial agents may also be present, provided they are not present at concentrations that would destabilize the formulation. Among the useful additional antimicrobial agents are chelating agents, which are particularly useful in reducing the resistance of gram-negative microorganisms in hard water. Acidic biocides may also be present.

[0050] Polyamines The laundry detergent compositions herein may further comprise from 0.1% to 10%, preferably from 0.2% to 5%, more preferably from 0.3% to 2% by weight of the composition of a polyamine, preferably a polyethyleneimine, more preferably an alkoxylated polyethyleneimine.

[0051] Polyamines suitable for the laundry detergent compositions herein may have a molecular weight (Mw) greater than 400 g / mol. A preferred class of polyamines is polyethyleneimine (PEI) and its derivatives, such as ethoxylated PEI polymers, propoxylated PEI polymers, polyamines, polyquats, polyglycerol quats, and other PEI derivatives, their salts, or mixtures thereof. In some preferred embodiments, the PEI is a branched, globular polymeric amine, and the molecular weight of the PEI or PEI salt used is from about 800 Daltons to about 2 million Daltons. Furthermore, in some preferred embodiments, the charge density of the PEI or PEI salt used is from about 15 meq / g to about 25 meq / g, more preferably from about 16 meq / g to about 20 meq / g. Examples of such preferred PEIs include LUPASOL WF (25,000 Daltons, 16-20 meq / g) and Lupasol® FG (800 Daltons, 16-20 meq / g) from BASF, and the SOKALAN® family of polymers available from BASF, such as SOKALAN® HP20, and SOKALAN® HP22G.

[0052] Supplementary ingredients The laundry detergent composition described herein may also include auxiliary ingredients.Suitable auxiliary materials include, but are not limited to, builders, chelating agents, rheology modifiers, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersants, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, photobleaching agents, perfumes, perfume microcapsules, structural elastomers, fabric softeners, carriers, hydrotropes, processing aids, solvents, hueing agents, structurants, and / or pigments.The exact nature and concentration of these auxiliary ingredients in the laundry detergent composition depends on the physical form of the composition and the nature of the washing operation in which the composition is used.

[0053] In one embodiment, the compositions herein include a rheology modifier (also called a "structuring agent" under certain conditions) that functions to adjust the viscosity of the composition to make it suitable for group packaging. The rheology modifier herein can be any known component capable of suspending particulates in a liquid composition and / or adjusting the rheology. Preferably, the rheology modifier is a hydroxy-containing crystalline material, a polyacrylate, a polysaccharide, a polycarboxylate, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkanol ammonium salt, a C 12 ~C 20 The rheology modifier is selected from the group consisting of aliphatic alcohols, dibenzylidene polyol acetal derivatives (DBPA), gallic acid diamide, cationic polymers comprising a first structural unit derived from methacrylamide and a second structural unit derived from diallyldimethylammonium chloride, and combinations thereof.Preferably, the rheology modifier is a hydroxy-containing crystalline material (typically characterized as crystalline), such as castor oil and castor oil derivatives, hydroxyl-containing fatty acids, aliphatic esters, and aliphatic waxes.More preferably, the rheology modifier is hydrogenated castor oil (HCO).

[0054] Preparation of the Composition The laundry detergent compositions of the present invention are generally prepared by conventional methods known in the art of manufacturing laundry detergent compositions, which typically include mixing the essential and optional ingredients in any desired order to a relatively homogeneous state, with or without heating, cooling, application of vacuum, etc., thereby providing a laundry detergent composition containing the ingredients in the requisite concentrations.

[0055] How to use Another aspect of the present invention relates to a method of using a laundry detergent composition for treating fabrics with microbial removal and optionally microbial inhibition benefits. The method comprises dispensing 5g to 120g of the above laundry detergent composition into a laundry wash tub containing water to form a wash liquor. The wash liquor in the laundry wash tub herein preferably has a volume of 1L to 50L, alternatively 1L to 20L for manual wash and 20L to 50L for machine wash. Preferably, the post-wash microbial removal benefit herein is measured by the method described in Test 1 (i.e., GB / T 20944.2-2007 Adsorption Method). The temperature of the laundry wash liquor is preferably in the range of 5°C to 60°C.

[0056] Dosage amounts in the methods herein may vary depending on the wash type. In one embodiment, the method comprises administering about 5 g to about 60 g of the laundry detergent composition to a manual wash tub (e.g., about 2-4 L). In an alternative embodiment, the method comprises administering about 5 g to about 100 g, preferably about 10 g to about 65 g of the laundry detergent composition to a washing machine (e.g., about 30-45 L).

[0057] Preferably, the method herein further comprises contacting the soiled fabric with a wash liquor. For example, gram-positive and / or gram-negative bacteria are suspected to be present on the fabric. The step of contacting the soiled fabric with the wash liquor is preferably after the step of administering the laundry detergent composition into the laundry wash tub. The method may further comprise the step of contacting the fabric with the laundry detergent composition before the step of administering the laundry detergent composition into the laundry wash tub, i.e., pre-treating the fabric with the laundry detergent composition for a period of time, preferably 1 minute to 10 minutes.

[0058] Test Method Test 1: Microbial removal effect after cleaning (GB / T 20944.2-2007 adsorption method). The post-wash microbial removal efficacy of the laundry detergent composition is measured by the following method defined in GB / T 20944.2-2007 adsorption method.

[0059] 1. Preparation of Microorganisms: A. Aseptically add a volume of nutrient broth into a freeze-dried culture of S. aureus, E. coli, or K. pneumoniae. Dissolve and suspend the culture in the nutrient broth to obtain a suspension. Streak a loop of the suspension onto a nutrient agar plate and incubate at 37°C for 24 hours to obtain a first generation subculture of the bacterial suspension. Transfer a loop of the first generation subculture of the bacterial suspension into 20 mL of nutrient broth with shaking and incubate at 37°C for 24 hours to obtain a second generation subculture of the bacterial suspension. Transfer 0.4 mL of the second generation subculture of the bacterial suspension into another 20 mL of nutrient broth with shaking and incubate at 37°C for 3±1 hours to obtain a third generation subculture of the bacterial suspension. B. Dilute the third generation subculture of the bacterial suspension to 1 x 105 CFU / mL to 3 x 105 CFU / mL by 1 / 20 dilution nutrient broth to obtain the working culture. C. Working cultures are stored at 4° C. Working cultures cannot be stored overnight.

[0060] 2. Fabric cleaning: A. Two pieces of fabric (32 yarns / cm x 32 yarns / cm, 100% plain weave cotton), each with a width of 1 m and a length of 3 m, are boiled in 5 L of solution for 1 hour. The solution is prepared with 2.5 g of non-ionic dip agent, 2.5 g of sodium carbonate, and 5000 mL of distilled water. The non-ionic dip agent is prepared with 5.0 g of alkylphenol ethoxylate, 5 g of sodium carbonate, and 1000 mL of distilled water. The pieces are rinsed in boiling deionized water for 5 minutes. The pieces are placed in cold deionized water for 5 minutes and allowed to dry indoors. One piece is used as the test piece for the following steps 2B-2I, and the other piece is used as the control (not subjected to steps 2B-2I). B. One end of the test fabric piece obtained from step 2A is fixed to a stainless steel spindle at an outer position along the horizontal extension of the stainless steel spindle. The stainless steel spindle has three horizontal stands connected to each other. The test fabric piece is wrapped around the three horizontal stands of the stainless steel spindle with sufficient tension to obtain a fabric-wrapped spindle with 12 wraps of fabric. The other end of the test fabric piece is fixed to the outer wrap of the 12 wraps of fabric with a pin. The fabric-wrapped spindle is sterilized in pressurized steam at 121°C for 15 minutes. C. 5.903 g of calcium chloride dihydrate and 2.721 g of magnesium chloride hexahydrate are dissolved in 100 mL of distilled water, and then the mixture is sterilized with pressurized steam at 121° C. for 20 minutes. 1 mL of the mixture is added to 1 L of distilled water to obtain a hard water solution. D. Add a sufficient amount of sample specimen to 1 L of the hardness solution obtained from step 2C to obtain a solution having a concentration of 1055 ppm. Mix this solution with a magnetic stirrer for 4 minutes. Dispense 250 mL of the mixed solution into the exposure chamber to obtain the cleaning solution. Place the exposure chamber in a water bath to obtain the test temperature of (25±1)°C. E. The fabric-wrapped spindle from step 2B is aseptically immersed in the cleaning solution in an exposure chamber and the exposure chamber is closed with a lid. F. The exposure chamber is secured onto the tumbler. The tumbler is rotated for 10 minutes. The spindle with the fabric wrapped around it is then removed from the exposure chamber. The spindle with the fabric wrapped around it is placed in a Haier iwash-1p top load washing machine and spin-dried for 2 minutes. G. Discard the wash solution from the exposure chamber and then add 250 mL of sterile distilled water to the exposure chamber. Immerse the spindle with the fabric after spinning into the freshly added distilled water in the exposure chamber. Rotate the tumbler for 3 minutes and spin for 2 minutes. H. Repeat step 2G. I. Aseptically remove the fabric-wrapped spindle from the exposure chamber and remove the test fabric strip from the spindle. Allow the test fabric strip to air dry overnight.

[0061] 3. Fabric incubation: A. Cut the washed test fabric pieces from step 2I into square pieces with sides measuring 2 cm. Three sets of 0.4 g fabric pieces are used as samples for the following steps. B. Each set of samples is placed in a vial, and then the samples are sterilized with pressurized steam at 121° C. for 15 minutes. After sterilization, the samples are dried in a clean bench for 1 hour without capping. C. Inoculate each dried sample with 0.2 mL of the working culture from step 1C. Incubate the vials containing the inoculated samples at 37° C. for 18 hours. D. Extract the surviving bacteria from the incubated samples, plate them on nutrient agar, and incubate at 37°C for 24-48 hours. Count the total colony forming units (CFU) for each set of samples and obtain the average result for the triplicates. The log10 value of the CFU value is taken as Mb. E. In steps 3A to 3D, the piece of fabric obtained from step 2A (which did not undergo steps 2B to 2I) is used as a control. The log10 value of the CFU value is designated as Ma. F. In step 3C, parallel vials of each inoculated sample were taken immediately after inoculation for cell concentration measurement. Viable bacteria on the incubated samples were extracted, plated on nutrient agar, and incubated at 37°C for 24-48 hours. The total colony forming units (CFU) of each set of samples were counted and the average results of the triplicates were obtained. The log10 value of the CFU values ​​was designated as Mc.

[0062] 4. Calculation of bacteriostatic activity value and post-wash microbial removal activity value: Bacteriostatic activity value = Ma-Mb Post-cleaning microbial removal activity value = Mc-Mb

[0063] A bacteriostatic activity value of 2.0 or greater indicates acceptable antimicrobial efficacy, a bacteriostatic activity value of 2.5 or greater indicates good antimicrobial efficacy, and a bacteriostatic activity value of 3.0 or greater indicates excellent antimicrobial efficacy. A bacteriostatic activity value of less than 2.0 indicates unacceptably poor antimicrobial efficacy.

[0064] A bacteriostatic activity value of at least 1.0 indicates acceptable post-wash microbial removal efficacy, at least 2.0 indicates good post-wash microbial removal efficacy, and at least 3.0 indicates excellent post-wash microbial removal efficacy.

[0065] Test 2: Antibacterial fabric adhesion test The antimicrobial agents are extracted from the treated fabrics by using a methanol-based accelerated solvent extraction (ASE) method described below. The resulting extracts are then subjected to gradient reversed-phase high performance liquid chromatographic (HPLC) separation on a C18 column and quantified by tandem mass spectrometry (MS / MS) operating under multiple reaction monitoring (MRM) conditions in negative mode.

[0066] As a first step, about 3 grams of treated fabric is accurately weighed and then loaded into a steel ASE tube. The extraction protocol is carried out using methanol as the extraction solvent at an elevated temperature of about 100° C. and a pressure of about 2000 pounds per square inch (psi) for about 5 minutes. The resulting extract is collected and transferred to a 25 mL flask, which is then filled to capacity with methanol. The resulting solution is then diluted about 25 times using a 50:50 mixture of water and methanol and used as the injection sample for subsequent LC-MS / MS analysis.

[0067] Next, about 5ul of the above injection sample is injected and separated on a Water Acquity UPLC C18 column with a gradient of about 70% mobile phase A (1% formic acid solution) / 30% mobile phase B (0.1% formic acid in methanol) to 5% mobile phase A / 95% mobile phase B for about 3 minutes, with the final gradient held for another 3 minutes. Antimicrobial agents, such as Tinosan® HP100, are detected in negative MRM mode. The ion pair with m / z 253>142 is used as the quantification transition, and the m / z of 253>125 is used for identification.

[0068] Subsequently, spiked matrix standards ranging from 0.5 mg / mL to 500 ng / mL are injected to generate a calibration curve. The concentration of the antimicrobial agent, e.g., Tinosan® HP100, in the injected sample is weighted (1 / x 2 ) is determined by extrapolation using quadratic regression. EXAMPLES

[0069] Example 1: Comparative study demonstrating effective post-wash microbial removal with liquid detergent compositions containing surfactant systems and diphenyl ether Liquid laundry detergent compositions were prepared containing the components shown in Table 1 below, with inventive Sample 1 comprising a surfactant system containing LAS as the primary surfactant and diphenyl ether, and comparative Sample 2 comprising a surfactant system containing NI as the primary surfactant and diphenyl ether.

[0070] [Table 1] aC 11~13 LAS b C available from Shell 12~14 AE 1~3 S c C ethoxylated with an average of 7 moles of ethylene oxide, available from Shell, as a nonionic surfactant. 12 ~C 15 Alcohol Neodol® 25-7 d Tinosan® HP100 is 4-4′-dichloro-2-hydroxydiphenyl ether available from BASF e Ethoxylated or ethoxylated and propoxylated polyethyleneimine (PEI) polymers available from BASF

[0071] The post-wash microbial removal efficacy of the above samples at a dosage of 1000 ppm of final product was then measured according to Test 1: Post-Wash Microbial Removal Efficacy using Staphylococcus aureus, ATCC 6538. The results are shown below.

[0072] [Table 2]

[0073] As shown in the data above, it is surprising and completely unexpected that the combination of a surfactant system containing LAS as the main surfactant with diphenyl ether can provide a very strong post-wash microbial removal effect (i.e., a log reduction value of more than 3). In other words, the inventive sample 1 can remove more than 99.9% of microorganisms in the microbial removal test. In contrast, the combination of a different surfactant system in combination with diphenyl ether (comparative sample 2) does not show a significant post-wash microbial removal effect (i.e., a log reduction value of even less than 0).

[0074] Example 2: Exemplary Formulations of Liquid Laundry Detergent Compositions The following liquid laundry detergent compositions shown in Table 3 were made containing the listed ingredients in the listed percentages (by weight).

[0075] [Table 3]

[0076] Dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0077] All documents cited herein, including any cross-referenced or related patents or patent applications, and any patent applications or patents to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest or disclose such invention, either alone or in combination with any other reference(s). Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

[0078] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. 1. A method for post-wash removal of microorganisms from clothing, comprising: a) providing a garment in a washing machine; b) during a wash sub-cycle of the washing machine, washing the clothes with a liquid detergent composition comprising from 2% to 60%, by weight of the composition, of a surfactant system and from 0.01% to 1%, by weight of the composition, of a compound of formula (I): 【Chemistry 1】 (In the formula, each Y is independently selected from chlorine, bromine, or fluorine; Each Z is independently SO ２ H, NO ２ , or C １ ~C ４ alkyl, r is 0, 1, 2, or 3; o is 0, 1, 2, or 3; p is 0, 1, or 2; m is 1 or 2; n is 0 or 1. and an antimicrobial agent which is a hydroxyl diphenyl ether of The surfactant system comprises C as the primary surfactant ６ ~C ２０ contacting the composition with a liquid detergent composition comprising a linear alkyl benzene sulfonate (LAS); The method includes:

2. the composition comprises from 4% to 50%, preferably from 6% to 40%, more preferably from 10% to 30% by weight of the composition of said surfactant system; Preferably, the surfactant system comprises ６ ~C ２０ Alkyl sulfate (AS), C ６ ~C ２０ Alkyl alkoxy sulfate (AAS), C ６ ~C ２０ Methyl ester sulfonate (MES), C ６ ~C ２０ 2. The method of claim 1, comprising an additional anionic surfactant selected from the group consisting of alkyl ether carboxylates (AECs), and any combination thereof, and / or a nonionic surfactant selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters, and alkoxylated derivatives of sorbitan esters, and any combination thereof.

3. Said C ６ ~C ２０ 3. The method of claim 1 or 2, wherein linear alkylbenzene sulfonate (LAS) is present as the majority surfactant in the composition.

4. The surfactant system comprises: 1) 50.1% to 90%, preferably 51% to 70%, more preferably 52% to 60% C by weight of the surfactant system ６ ~C ２０ Linear alkylbenzene sulfonate (LAS), 2) 10% to 49.9% by weight of the surfactant system, preferably 30% to 49% by weight, more preferably 40% to 45% by weight of C ６ ~C ２０ Alkyl alkoxy sulfate (AAS), 3) 0.5% to 10%, preferably 1% to 8%, more preferably 2% to 6% by weight of the surfactant system １０ ~C １８ Alkyl ethoxylates, The method according to any one of claims 1 to 3, comprising:

5. 5. The method of any one of claims 1 to 4, wherein the composition comprises 0.01% to 0.1%, preferably 0.01% to 0.05%, more preferably 0.01% to 0.04%, and most preferably 0.02% to 0.03% by weight of the composition of said antimicrobial agent, preferably selected from the group consisting of 4-4'-dichloro-2-hydroxydiphenyl ether, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and combinations thereof, more preferably the antimicrobial agent is 4-4'-dichloro-2-hydroxydiphenyl ether.

6. 6. The method of any one of claims 1 to 5, wherein the composition further comprises from 0.1% to 10%, preferably from 0.2% to 5%, more preferably from 0.3% to 2% by weight of the composition of a polyamine, preferably a polyethyleneimine, more preferably an alkoxylated polyethyleneimine.

7. The composition, a) from 15% to 30% by weight of the composition of said surfactant system, said surfactant system comprising from 52% to 60% C ６ ~C ２０ Linear alkylbenzene sulfonate (LAS) and 40% to 45% by weight of the surfactant system ６ ~C ２０ Alkyl alkoxy sulfate (AAS) and 2% to 6% by weight of the surfactant system １０ ~C １８ the surfactant system comprising an alkyl ethoxylate; b) 0.01% to 0.04% by weight of the composition of 4,4'-dichloro-2-hydroxydiphenyl ether; c) 0.3% to 2%, by weight of the composition, of an alkoxylated polyethyleneimine; and The method of claim 1 , comprising:

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