Antibacterial liquid detergent composition

Abstract

Diphenyl ether antibacterial agent, organic acid, and C6-C 20 and an anionic surfactant comprising a linear alkyl benzene sulfonate (LAS), wherein the antibacterial laundry detergent composition has an undiluted pH of 1.5 to 5.0.

Description

[Technical Field]

[0001] The present invention relates to antimicrobial liquid detergent compositions. [Background technology]

[0002] Consumer products have evolved to address consumer needs for antimicrobial benefits in addition to their intended functions. For example, antimicrobial laundry detergent products are desired by consumers because they provide antimicrobial benefits to fabrics while simultaneously laundering the fabrics. Currently, various antimicrobial agents, such as bleach, chloroxylenol (PCMX), benzalkonium chloride (BKC), and diphenyl ether, are known for use in consumer product formulations to provide antimicrobial benefits. Antimicrobial agents include two major types: one type functions as an agent for eliminating 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, achieving the desired antimicrobial efficacy in liquid detergent products remains challenging. In one aspect, applicable solutions remain needed for antimicrobial agents that function as agents for removing microorganisms during the wash, because known actives cannot function in liquid detergent products (e.g., PCMX and BKC) or cannot be incorporated into liquid detergent products (e.g., bleach) due to negative interactions with surfactants. In another aspect, improved efficacy is also needed for antimicrobial agents that function as agents for preventing microorganisms during storage or use. Specifically, most of the antimicrobial agent ultimately washes away with the wash solution during the wash cycle. As such, only a small amount of antimicrobial agent can be deposited on washed fabrics, and therefore the actual microbial prevention efficacy of these laundry detergents is severely limited. Accordingly, liquid detergent products typically require larger amounts of antimicrobial agent to compensate for such low deposition rates and ensure the resulting product has the desired antimicrobial efficacy. Such increased amounts of antimicrobial agent in liquid detergent products inevitably increase the manufacturing cost and processing complexity of such products. Summary of the Invention [Problem to be solved by the invention]

[0004] Thus, there is a need for liquid detergent compositions that provide improved antimicrobial efficacy, preferably in both microbial removal and microbial prevention aspects. [Means for solving the problem]

[0005] It is a surprising and unexpected discovery of the present invention that the antimicrobial liquid detergent compositions according to the present disclosure can meet the above needs, i.e., that the antimicrobial liquid detergent compositions according to the present disclosure can provide both improved efficacy of microbial removal and improved efficacy of microbial prevention.

[0006] Specifically, the antimicrobial liquid detergent compositions according to the present disclosure (i.e., low pH formulations) exhibit significantly improved microbial prevention efficacy compared to typical liquid detergent compositions (i.e., neutral or high pH formulations). What is even more surprising is that, in addition to microbial prevention, the antimicrobial liquid detergent compositions according to the present disclosure can also provide microbial removal efficacy (i.e., removing microorganisms from clothing).

[0007] Accordingly, the present invention provides in one aspect an antimicrobial liquid detergent composition comprising: a) 0.01% to 3% by weight of the composition of an antibacterial agent selected from the group consisting of diphenyl ethers and combinations thereof; b) 4.5% to 40% by weight of the composition of an organic acid; c) 4% to 60% by weight of the composition of a surfactant system; the surfactant system comprises an anionic surfactant selected from the group consisting of C6-C20 linear alkylbenzene sulfonates (LAS), C6-C20 alkyl sulfates (AS), C6-C20 alkyl alkoxy sulfates (AAS), C6-C20 methyl ester sulfonates (MES), C6-C20 alkyl ether carboxylates (AEC), and combinations thereof; The composition relates to an antimicrobial liquid detergent composition having an undiluted pH of 1.5 to 5.0.

[0008] Preferably, the composition may have an undiluted pH of 1.6 to 4.5, preferably 1.7 to 4.0, more preferably 1.8 to 3.5, most preferably 1.9 to 3.1. Surprisingly, when the undiluted pH of the liquid detergent composition according to the present invention is within the preferred ranges, the efficacy of microbial removal may be further improved.

[0009] Preferably, the pH of the through-the-wash (TTW) during the wash sub-cycle may be 2.5 to 6.0, preferably 3.0 to 5.0, more preferably 3.2 to 4.0, and most preferably 3.3 to 3.8.

[0010] Specifically, the composition may contain from 0.01% to 1%, preferably from 0.02% to 0.5%, by weight of the composition, of a compound of formula (I):

[0011] [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; n is 0 or 1), Preferably, the hydroxydiphenyl ether is selected from the group consisting of 4-4'-dichloro-2-hydroxydiphenyl ether, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and combinations thereof, and more preferably 4-4'-dichloro-2-hydroxydiphenyl ether.

[0012] Preferably, the composition may contain 5.5% to 30% by weight, preferably 6% to 20% by weight, more preferably 6.5% to 18% by weight of the organic acid. Specifically, the organic acid may be a hydroxycarboxylic acid, and preferably, the organic acid may be selected from the group consisting of citric acid, lactic acid, tartaric acid, malic acid, and any combination thereof.

[0013] 10. An antibacterial liquid detergent composition according to any one of the preceding claims, wherein the surfactant system is preferably present in an amount in the range 5% to 50%, preferably 6% to 40%, more preferably 10% to 30% by weight of the composition.

[0014] Preferably, the surfactant system may further comprise a non-ionic surfactant, preferably 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.

[0015] Anionic surfactants suitable for the compositions herein may be selected from the group consisting of C6-C20 linear alkyl benzene sulfonates (LAS), C6-C20 alkyl sulfates (AS), C6-C20 alkyl alkoxy sulfates (AAS), C6-C20 methyl ester sulfonates (MES), C6-C20 alkyl ether carboxylates (AEC), and any combination thereof.

[0016] Suitable nonionic surfactant systems for the composition 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.

[0017] The ratio of anionic surfactant to nonionic surfactant can be from 0.01 to 100, preferably from 0.05 to 20, more preferably from 0.1 to 10, and most preferably from 0.2 to 5, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 2, 3, 4, 5, or any range therebetween. In some preferred embodiments, the ratio of anionic surfactant to nonionic surfactant can be from 0.2 to 1.5, preferably from 0.3 to 1.2.

[0018] In some embodiments, the composition comprises from 2% to 35%, preferably from 3% to 30%, more preferably from 4% to 25%, and most preferably from 5% to 20%, e.g., 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, or any range therebetween, of C6 to C8 20 In some preferred embodiments, the composition may contain an anionic surfactant, including a linear alkyl benzene sulfonate (LAS). In some preferred embodiments, the composition contains 2% to 35%, preferably 3% to 30%, more preferably 4% to 25%, and most preferably 5% to 20%, by weight of the composition, of a C6-C7 alkyl benzene sulfonate, such as 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, or any range therebetween. 20 It may include linear alkylbenzene sulfonate (LAS).

[0019] In some embodiments, the composition comprises 2% to 35%, preferably 3% to 30%, more preferably 5% to 25%, and most preferably 7% to 20%, by weight of the composition, of C6 to C8 20In some preferred embodiments, the composition may comprise a C6-C7 nonionic surfactant, including an alkoxylated alcohol, in an amount of 2% to 35%, preferably 3% to 30%, more preferably 5% to 25%, and most preferably 7% to 20%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, or any range therebetween, by weight of the composition. 20 It may include an alkoxylated alcohol.

[0020] Specifically, the composition contains 0.1% to 5% by weight, preferably 0.2% to 2% by weight of the composition, of C 10 ~C 16 It may further comprise an amphoteric surfactant preferably selected from the group consisting of alkyl dimethyl amine oxides and combinations thereof, and preferably the amphoteric surfactant is selected from the group consisting of dodecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide, and combinations thereof.

[0021] Preferably, the total surfactant in the composition may be present in an amount ranging from 4% to 50% by weight of the composition, preferably from 6% to 40% by weight, more preferably from 10% to 30% by weight.

[0022] Specifically, the composition may further comprise 0.1% to 10%, preferably 0.5% to 5% by weight of the composition of a polyamine, preferably polyethyleneimine, more preferably alkoxylated polyethyleneimine.

[0023] In some specific embodiments of the present invention, an anionic surfactant may be present in the composition as the primary surfactant, preferably as the majority surfactant. Preferably, the ratio of anionic surfactant to nonionic surfactant may be 1.05 to 100, preferably 1.1 to 20, more preferably 1.2 to 10, and most preferably 1.3 to 5. Specifically, the anionic surfactant may include a C6 to C20 linear alkyl benzene sulfonate (LAS).

[0024] In some specific embodiments of the present invention, a nonionic surfactant may be present in the composition as the primary surfactant, preferably as the majority surfactant. Preferably, the ratio of anionic surfactant to nonionic surfactant may be 0.01 to 0.95, preferably 0.05 to 0.9, more preferably 0.1 to 0.85, and most preferably 0.2 to 0.8. Specifically, the nonionic surfactant may comprise a C6 to C20 alkoxylated alcohol.

[0025] In certain embodiments of the present invention, the composition comprises: a) 0.02% to 0.5% by weight of the composition of 4,4'-dichloro-2-hydroxydiphenyl ether; b) 6.5% to 18% by weight of the composition of citric acid; c) 5% to 20% by weight of the composition of a C10 to C16 linear alkylbenzene sulfonate; d) 7% to 20% by weight of the composition of a C12 to C18 alkyl ethoxylate; The composition has an undiluted pH of 1.9 to 3.1.

[0026] In another aspect, the present invention relates to the liquid detergent composition described above for use in removing microorganisms from fabrics.

[0027] In another aspect, the present invention relates to a method of pre-treating or treating soiled fabrics, comprising contacting the soiled fabrics with the liquid detergent composition described above.

[0028] In another aspect, the present invention relates to a method for removing a biofilm on a biofilm-affected surface, the method comprising contacting the biofilm-affected surface with the liquid detergent composition described above. Specifically, the biofilm-affected surface is in a washing machine. More specifically, the biofilm-affected surface is the inner surface of a washing machine drum.

[0029] In another aspect, the present invention provides a method for removing biofilm on a biofilm-affected surface, comprising: a) providing a biofilm affected surface in a washing machine; b) contacting the biofilm affected surface with a liquid detergent composition comprising from 2% to 60% of a surfactant system and from 4.5% to 40% of an organic acid by weight of the composition; The composition has an undiluted pH of 1.5 to 5.0.

[0030] It is an advantage of the liquid detergent compositions according to the present disclosure that they may provide improved microbial protection. In the context of the present disclosure, eliminating microorganisms includes, but is not limited to, preventing the growth or proliferation of microorganisms.

[0031] Another advantage of the liquid detergent compositions according to the present disclosure is that they can improve microbial removal. Specifically, the liquid detergent compositions according to the present disclosure can significantly remove microorganisms from fabrics during washing. In the context of the present disclosure, removing microorganisms includes, but is not limited to, killing, inactivating, eliminating, and / or washing away microorganisms. DETAILED DESCRIPTION OF THE INVENTION

[0032] 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.

[0033] As used herein, the terms "comprise," "comprises," "comprising," "include," "includes," "including," and "contain," "contains," and "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 encompass the terms "consisting of" and "consisting essentially of."

[0034] As used herein, when a composition is "substantially free" of a particular component, it means that the composition contains less than a trace amount of the particular component, or less than 0.1%, or less than 0.01%, or less than 0.001% by weight of the composition.

[0035] As used herein, the term "liquid detergent composition" refers to a composition in a form selected from the group consisting of pourable liquid, gel, cream, and combinations thereof. Liquid detergent compositions may be either aqueous or non-aqueous, and may be anisotropic, isotropic, or combinations thereof.

[0036] As used herein, the term "antibacterial agent" refers to a compound whose principal intended function is to kill bacteria and / or prevent the growth or reproduction of bacteria. Conventional antibacterial agents include cationic antibacterial agents (e.g., certain ammonium chlorides), non-ionic antibacterial agents, etc. The diphenyl ether compounds used in the present invention are non-ionic antibacterial agents.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] As used herein, the term "washing liquor" refers to the typical amount of aqueous solution used for one laundry wash cycle, preferably 1 L to 50 L, or alternatively 1 L to 20 L for hand washing and 20 L to 50 L for machine washing.

[0041] 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.

[0042] Liquid detergent composition The liquid detergent compositions of the present invention comprise a surfactant system and an organic acid, and the compositions have an undiluted pH of 1.5 to 5.0, preferably 1.6 to 4.5, more preferably 1.7 to 4.0, and most preferably 1.8 to 3.6. Furthermore, the liquid detergent compositions of the present invention may comprise an antimicrobial agent, preferably a diphenyl ether. Surprisingly, it has been discovered that by combining a surfactant system with an organic acid, superior efficacy in removing microorganisms can be achieved. This effect is unexpected, since neither a similar surfactant system nor an acid solution alone can provide such efficacy.

[0043] Preferably, the composition may contain 5.5% to 30% by weight, preferably 6% to 20% by weight, more preferably 6.5% to 18% by weight of the organic acid. Specifically, the organic acid may be a hydroxycarboxylic acid, and preferably, the organic acid may be selected from the group consisting of citric acid, lactic acid, tartaric acid, malic acid, and any combination thereof.

[0044] In laundry wash solutions, the pH of the through-the-wash (TTW) during the wash sub-cycle may preferably be between 2.5 and 6.0, preferably between 3.0 and 5.0, more preferably between 3.2 and 4.0.

[0045] The composition may further comprise an antimicrobial agent that is a hydroxyl diphenyl ether. Preferably, the antimicrobial agent may be selected from the group consisting of 4,4'-dichloro-2-hydroxydiphenyl ether, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and combinations thereof.

[0046] The laundry detergent compositions herein provide efficacy for removing gram-positive bacteria (e.g., Staphylococcus aureus) and / or gram-negative bacteria (e.g., E. coli). In one embodiment, the laundry detergent composition provides a microbial removal value of at least a 1.0 log reduction, preferably at least a 1.5 log reduction, more preferably at least a 2.0 log reduction, even more preferably a 2.5 log reduction, even more preferably a 3.0 log reduction, and most preferably a 3.5 log reduction for gram-positive and / or gram-negative bacteria, comparing treated fabrics to untreated fabrics.

[0047] Furthermore, the composition preferably provides improved microbial prevention efficacy to fabrics treated with the composition. Without being bound by any theory, it is believed that antimicrobial agents can be more effectively deposited on fabrics during the wash cycle by using a liquid detergent composition according to the present invention, and the deposited (i.e., residual) antimicrobial agent can then more effectively prevent bacterial growth on the fabrics during drying, storage, or wear. In one embodiment, the laundry detergent composition provides a bacteriostatic activity value of at least a 1.0 log reduction, preferably at least a 1.5 log reduction, more preferably at least a 2.0 log reduction, and even more preferably a 2.5 log reduction, against Gram-negative and / or Gram-positive bacteria, comparing treated fabrics to untreated fabrics. Preferably, the composition provides at least a 1.0 log reduction, preferably at least a 1.5 log reduction, more preferably at least a 2.0 log reduction, and even more preferably a 2.5 log reduction against Escherichia coli, Staphylococcus aureus, and / or Klebsiella pneumoniae after 10 minutes of contact in a 1055 ppm aqueous solution as determined by the JIS L 1902 method (described below). More preferably, the composition provides at least a 1.0 log reduction, preferably at least a 1.5 log reduction, more preferably at least a 2.0 log reduction, even more preferably at least a 2.5 log reduction, even more preferably at least a 3.0 log reduction, and most preferably a 3.5 log reduction against Staphylococcus aureus.

[0048] The laundry detergent composition may have any suitable viscosity depending on factors such as the ingredients used and the purpose of the composition. In one embodiment, the composition has a high shear viscosity of about 100 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 s and a temperature of 21° C., and a low shear viscosity of about 500 to about 100,000 cP, alternatively about 1,000 to about 10,000 cP, alternatively about 1,500 to about 5,000 cP at a shear rate of 1 s and a temperature of 21° C.

[0049] surfactant system The composition according to the present disclosure comprises a surfactant system. The surfactant system comprises an anionic surfactant. Preferably, the surfactant system may further comprise a nonionic surfactant.

[0050] Anionic surfactant systems suitable for the compositions of the present invention include C6-C 20 Linear alkylbenzene sulfonate (LAS), C6-C 20 Alkyl sulfate (AS), C6-C 20 Alkyl alkoxy sulfates (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 C8 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 S surfactants are particularly preferred. Preferred group AA x S is C, where x is about 1 to 3. 12 ~C 14 In some embodiments, the composition comprises from 1% to 30%, preferably from 2% to 25%, more preferably from 3% to 20%, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 16%, 18%, 20%, or any range therebetween, of anionic surfactant by weight of the composition.

[0051] Suitable nonionic surfactant systems for the compositions 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 alkoxylated nonionic surfactants, such as Neodol® nonionic surfactants available from Shell. 12 ~C 18 Alkyl ethoxylate; C6~C 12 Alkylphenol alkoxylates (where the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units); C with ethylene oxide / propylene oxide block alkyl polyamine ethoxylates such as Pluronic® available from BASF 12 ~C 18 Alcohols and C6-C 12 Alkylphenol condensate; C 14 ~C 22 Included herein are medium-chain branched alkyl alkoxylates (BAEx, where x is from about 1 to about 30); alkyl polysaccharides, specifically alkyl polyglycosides; polyhydroxy fatty acid amides, and ether-end-capped poly(oxyalkylated) alcohol surfactants. Nonionic surfactants herein also include alkoxylated ester surfactants, such as those of formula R 1 C(O)O(RO)nR 3 [In the formula, R 1 is a linear and branched C6-C 22 selected from alkyl or alkylene moieties, R 2 is selected from C2H4 and C3H6 moieties, R 3Also useful are alkoxylated ester surfactants having a C6-C7 moiety, wherein n is selected from H, CH3, C2H5, and C3H7 moieties, and 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 particular embodiments, the alkoxylated nonionic surfactant contained by the laundry detergent compositions of the present invention is a C6-C7 20 Alkoxylated alcohols, preferably C8-C 18 Alkoxylated alcohols, more preferably C 10 ~C 16 Alkoxylated alcohols. C6-C 20 The alkoxylated alcohol is preferably an alkyl alkoxylated alcohol having an average degree of alkoxylation of from about 1 to about 50, preferably from about 3 to about 30, more preferably from about 5 to about 20, and even more preferably from about 5 to about 9. In some embodiments, the composition comprises from 1% to 30%, preferably from 2% to 25%, more preferably from 3% to 20%, e.g., 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 16%, 18%, 20%, or any range therebetween, by weight of the composition, of a nonionic surfactant.

[0052] The ratio of anionic surfactant to nonionic surfactant can be from 0.01 to 100, preferably from 0.05 to 20, more preferably from 0.1 to 10, and most preferably from 0.2 to 5.

[0053] In some embodiments, the anionic surfactant is a C6-C 20 Linear alkylbenzene sulfonate surfactants (LAS), preferably C 10 ~C 16 LAS, and more preferably C 12 ~C 14 Includes LAS.

[0054] In some specific embodiments of the present invention, an anionic surfactant may be present in the composition as the primary surfactant, preferably as the majority surfactant. Preferably, the ratio of anionic surfactant to nonionic surfactant may be 1.05 to 100, preferably 1.1 to 20, more preferably 1.2 to 10, and most preferably 1.3 to 5. Specifically, the anionic surfactant may be a C6 to C8 20 It may include linear alkylbenzene sulfonate (LAS).

[0055] In some specific embodiments of the present invention, a nonionic surfactant may be present in the composition as the primary surfactant, preferably as the majority surfactant. Preferably, the ratio of anionic surfactant to nonionic surfactant may be 0.01 to 0.95, preferably 0.05 to 0.9, more preferably 0.1 to 0.85, and most preferably 0.2 to 0.8. Specifically, the nonionic surfactant may be a C6 to C8 20 It may include an alkoxylated alcohol.

[0056] 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)).

[0057] The laundry detergent compositions of the present invention may further comprise another amphoteric surfactant (i.e., other than AO). Non-limiting examples of other amphoteric surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Preferred examples include alkyl dimethyl betaines and coco dimethylamidopropyl betaines, sulfo and hydroxy betaines (where the alkyl group is C8 to C9).18 or C 10 ~C 14 and betaines, including N-alkyl-N,N-dimethylamino-1-propanesulfonates, which may be

[0058] Diphenyl ether antibacterial agents The diphenyl ether antimicrobial agents of the present invention are non-ionic compounds. It has been found that the non-ionic nature of the antimicrobial agents of the present invention allows for stable liquid detergent compositions.

[0059] 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):

[0060] [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).

[0061] In the definition of formula (I) above, 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 may be bonded to the benzene ring, while a bromine atom and another chlorine atom may be bonded to the other benzene ring, or a bromine atom may be bonded to the benzene ring, while two chlorine atoms may be bonded to the other benzene ring.

[0062] 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.

[0063] 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 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.

[0064] Amphoteric surfactants (AO) Amphoteric surfactants suitable for use in the present invention include C6-C 20 The amine may be selected from the group consisting of alkyldimethyl amine oxides (AO) and combinations thereof.

[0065] Preferably, the amine oxide surfactant has the following structure:

[0066] [ka] [In the formula, R 1 is C 6~20 Alkyl, C 6~20Hydroxyalkyl, or C 6~20 alkylphenyl group, and each R 2 is C 2~5 Alkylene, or C 2~5 hydroxyalkylene group, x is 0 to about 3, and each R 3 is C 1~3 Alkyl, C 1~3 hydroxyalkyl, or polyethylene oxide containing about 1 to about 3 ethoxyl (EO) units. Preferably, the amine oxide surfactant is C 8~18 Alkyl dimethyl amine oxide, preferably C 10~16 It may also be an alkyldimethylamine oxide.

[0067] Preferably, the amphoteric surfactant is selected from the group consisting of dodecyldimethylamine oxide, tetradecyldimethylamine oxide, and combinations thereof. More preferably, the amphoteric surfactant comprises dodecyldimethylamine oxide having the following formula (II):

[0068] [ka]

[0069] Such a compound is also known as lauryldimethylamine oxide or dodecyldimethylamine-N-oxide (DDAO), which is commercially available from Huntsman under the trade name Oxamin® LO.

[0070] Polyamines The laundry detergent compositions herein may further comprise from 0.1% to 10%, preferably from 0.5% to 5% by weight of the composition of a polyamine, preferably polyethyleneimine, more preferably alkoxylated polyethyleneimine.

[0071] Polyamines suitable for the laundry detergent compositions herein may have a Mw greater than 400 g / mol. A preferred class of polyamines is polyethyleneimines (PEI) and its derivatives, such as ethoxylated PEI polymers, propoxylated PEI polymers, polyamines, polyquats, polyglycerolquats, and other PEI derivatives, salts thereof, or mixtures thereof. In some preferred embodiments, the PEI is a branched, spherical 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 the BASF products LUPASOL WF (25 kDa; 16-20 meq / g) and Lupasol® FG (800 Daltons; 16-20 meq / g), as well as the SOKALAN® group of polymers available from BASF, such as SOKALAN® HP20 and SOKALAN® HP22G.

[0072] Supplementary ingredients The laundry detergent compositions described herein may contain adjunct ingredients. Suitable adjunct 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 adjunct ingredients in the laundry detergent composition will depend on the physical form of the composition and the nature of the laundry operation for which the composition is to be used.

[0073] In one embodiment, the compositions herein include a rheology modifier (sometimes referred to as a "structuring agent" in certain circumstances) that functions to adjust the viscosity of the composition so that it is more applicable to the packaging assembly. The rheology modifier herein can be any known component capable of suspending particulates and / or adjusting the rheology of a liquid composition. 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 alkanolammonium 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 containing 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, such as castor oil and castor oil derivatives, generally characterized as a crystalline hydroxyl-containing fatty acid, aliphatic ester, and aliphatic wax. A more preferred rheology modifier is hydrogenated castor oil (HCO).

[0074] In one embodiment, the composition may further comprise 0.1% to 5%, preferably 0.2% to 2%, by weight of the composition of a chelating agent, preferably diethylene triamine penta-acetic acid (DTPA) and / or glutamic acid diacetate (GLDA).

[0075] 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 involve 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 at the requisite concentrations.

[0076] How to use Another aspect of the present invention relates to a method of using a laundry detergent composition to treat fabrics with microbial removal benefit and, optionally, microbial prevention benefit. The method comprises dispensing 1 g to 200 g of the above-described 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 1 L to 50 L, alternatively 1 L to 20 L for manual washes and 20 L to 50 L for machine washes. Preferably, the microbial removal benefit herein is determined by the method described in Test 1 (D&S FTC Jokin Method), and the microbial prevention benefit herein is determined by the method described in Test 2 (i.e., JISL 1902 Method). The temperature of the laundry wash liquor preferably ranges from 5°C to 60°C.

[0077] Dosage amounts in the methods herein may vary depending on the wash type. In one embodiment, the method comprises administering about 1 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 1 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).

[0078] Preferably, the method herein further comprises contacting soiled fabrics with a wash liquor. For example, gram-positive and / or gram-negative bacteria are suspected to be present on the fabrics. The step of contacting the soiled fabrics with the wash liquor preferably occurs after the step of administering a laundry detergent composition into a laundry wash tub. The method may further comprise contacting the fabrics with the laundry detergent composition before the step of administering the laundry detergent composition into the laundry wash tub, i.e., pretreating the fabrics with the laundry detergent composition for a period of time, preferably 1 to 10 minutes.

[0079] Test Method Test 1: Microbial Elimination Efficacy (D&S FTC Jokin) The microbial elimination efficacy of laundry detergent compositions is determined by the method defined in the D&S FTC Jokin method described below.

[0080] 1. Preparation of Microorganisms: A. Subculture the microorganisms onto nutrient agar by transferring at least once a day while incubating at 35±2°C. B. The day before testing, transfer the cells to a separate plate of nutrient agar and incubate agar-side down at 35±2°C for 18-24 hours. C. Remove the growth from the agar plate using 3 mL of dilution fluid and 5 sterile glass beads to suspend the growth. Normalize the culture to approximately 10 per mL. 8 Colony forming units (CFU) of Staphylococcus aureus and 10 9 Obtain CFU / mL of Klebsiella pneumoniae and E. coli. D. To each inoculum of working culture, horse serum (5% v / v) is added as a stain challenge.

[0081] 2. Fabric and Spindle Preparation A. Wash the test fabric by boiling approximately 300 g of material in 3 L of distilled or deionized water containing 1.5 g of sodium carbonate and 1.5 g of a non-ionic wetting agent for 1 hour. Rinse the fabric first in boiling water and then in cold water until all visible traces of the wetting agent (i.e., sudsing) are gone. Remove as much water as possible from the fabric. B. Air dry at ambient room temperature for at least 24 hours to ensure the material is completely dry. C. Cut the washed, dry fabric into strips each 2 inches (5 cm) wide and weighing 15 ± 0.1 g each. Puncture one end of the 15 g test fabric strip and secure it on the outer horizontal extension of a stainless steel spindle. Wrap the strip around the three horizontal extensions with enough tension to obtain 12 wraps instead of 13, using the entire 15 6 0.1 g fabric. Staples, pins, or autoclavable fabric tags may be used to secure the fabric. D. Cut approximately 1 x 1.5 inch fabric carriers from the remaining washed fabric. You may mark the edges of each carrier using a non-toxic permanent marker. E. For each challenge organism, prepare at least three fabric carriers and one fabric-wrapped spindle for each active test formulation / product and control / count control.

[0082] 3. Steps: A. Inoculate three sterile fabric carriers (in a single sterile Petri dish) with 0.020 mL of the prepared inoculum per carrier. Distribute the inoculum over an area of ​​approximately 1 x 1.5 inches on each carrier, avoiding markers, staples, or safety pins. Dry the carriers in an incubator at 35±2°C, 80% RH until the carriers are visibly dry, but for no more than 30 minutes. B. Using sterile forceps, aseptically place two inoculated dry carriers in an upright position on the 9th and 10th folds of a single wound spindle, and one carrier between the 10th and 11th folds. Secure each piece of fabric by pressing it deeply into the pre-formed "pocket." Do not overlap the inoculated carriers. Markers, staples, safety pins, or autoclavable fabric tags can be easily removed at the end of the procedure. C. Aseptically place the spindle into a sterile exposure chamber to mimic a washing machine. D. Add 250 mL of test samples (diluted active test formulations and controls). E. Close the exposure chamber tightly. F. Place the exposure chamber on the agitator for the specified exposure period (25° C., 10 minutes, 60 rpm). G. Using large sterile forceps or sterile gloves, remove the spindles from the exposure chamber, squeeze out the solution, and aseptically remove each fabric carrier into a separate wide-mouth tube containing 10 mL of neutralizing broth. H. All tubes containing the fabric carriers are mixed in a vortex mixer for approximately 10 seconds. Alternatively, other methods such as the foot arc technique or sonication may be used to extract viable microorganisms from the fabric pieces. I. Serial dilutions of neutralizing broth containing a single carrier are made in or on agar containing neutralizing agent as needed. -1 ~10 -4 Plate duplicate 1.0 mL of each dilution. Incubate plates at 35±2°C for 48±2 hours. To determine surviving organisms, count colonies and record as CFU / plate. Average duplicate plates and multiply by the dilution factor to arrive at CFU / carrier. This average count is then multiplied by the log 10 The CFU value must be converted to log 10 Let the value be Nb. J. (Count Control) Instead of the test formulation, use 0.05% Tween 80 and follow the above steps in the same manner as the test formulation. The logarithm of the CFU value for the count control 10 The value is Na.

[0083] 4. Calculation of microbial elimination activity value: Microbial removal activity (LogR)=Na-Nb A microbial elimination activity value of 2.0 or greater indicates acceptable microbial elimination efficacy, and a microbial elimination activity value below 2.0 indicates unacceptably poor microbial elimination efficacy.

[0084] Test 2: Antimicrobial efficacy (JIS L1902) The microbial efficacy of laundry detergent compositions is determined by the method defined in JIS L1902 as follows:

[0085] 1. Preparation of Microorganisms: A. Aseptically add a volume of nutrient broth to a lyophilized culture of Staphylococcus aureus, Escherichia coli, or Klebsiella 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 colony of the first-generation subculture of the bacterial suspension to 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 to 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. Third generation subculture of bacterial suspension to 1 x 10 by 1 / 20 dilution of nutrient broth 5 cfu / mL ~3x10 5 Dilute to a concentration of cfu / ml to obtain the working culture. C. Store working cultures at 4°C and use within 4 hours.

[0086] 2. Fabric cleaning: A. Two fabric strips (32 yarns / cm x 32 yarns / cm, 100% plain weave cotton), each 1 m wide and 3 m long, are boiled in 5 L of solution for 1 hour. The solution is prepared with 2.5 g of non-ionic dip, 2.5 g of sodium carbonate, and 5000 mL of distilled water. The non-ionic dip is prepared with 5.0 g of alkylphenol ethoxylate, 5 g of sodium carbonate, and 1000 mL of distilled water. The fabric strips are rinsed in boiling deionized water for 5 minutes. The fabric strips are placed in cold deionized water for 5 minutes and allowed to dry indoors. B. One end of the test fabric strip 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 strip 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 strip is fixed with a pin to the outer wrap of the 12 wraps of fabric. The fabric-wrapped spindle is sterilized in pressurized steam at 121°C for 15 minutes. C. Dissolve 5.903 g of calcium chloride dihydrate and 2.721 g of magnesium chloride hexahydrate in 100 mL of distilled water, and then sterilize this mixture with pressurized steam at 121° C. for 20 minutes. Add 1 mL of the mixture to 1 L of distilled water to obtain a hard water solution. D. Add a sufficient amount of sample to 1 L of the hard water solution obtained from step 2C to obtain a solution with a concentration of 1055 ppm. Mix this solution on 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. Aseptically immerse the fabric-wrapped spindle from step 2B in the cleaning solution within the exposure chamber and close the exposure chamber with the lid. F. The exposure chamber is secured onto a 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, then add 250 mL of distilled water to the exposure chamber. Immerse the spindle with the fabric after dehydration into the newly 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.

[0087] 3. Fabric incubation: A. Cut the washed test fabric strips obtained from step 2I into square pieces with sides measuring 2 cm. Six test samples with a mass of 0.40 g±0.05 g are obtained 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 without caps for 1 hour. C. Inoculate 0.2 mL of the working culture obtained from step 1B into each dried sample. Immediately after inoculation, extract the bacteria from the three test samples, plate them on nutrient agar, and incubate at 37°C for 24 to 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 values ​​is designated as TO. Incubate the other three vials containing the inoculated samples at 37°C for 18 to 24 hours. D. Extract the surviving bacteria from the incubated samples, plate them on nutrient agar, and incubate them 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 triplicate sets. Calculate the log10 value of the CFU values ​​as T. t Let's say. E. In steps 3A-3D, the fabric strip obtained from step 2A (which has not undergone steps 2B-2I) is used as a control. Therefore, the log10 values ​​of the CFU values ​​are calculated for C0 and C1. t Let's say.

[0088] 4. Calculation of bacteriostatic activity value: Bacteriostatic activity value = (C t -C0)-(T t -T0) A bacteriostatic activity value of 2.0 or greater indicates acceptable antimicrobial efficacy, a bacteriostatic activity value of 3.0 or greater indicates excellent antimicrobial efficacy, and a bacteriostatic activity value below 2.0 indicates unacceptable or insufficient antimicrobial efficacy.

[0089] Test 3: Fabric adhesion test for antimicrobial agents The antimicrobial agents are extracted from the treated fabrics 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.

[0090] As a first step, approximately 3 grams of treated fabric is accurately weighed and then loaded into a steel ASE tube. The extraction protocol is carried out at an elevated temperature of approximately 100°C and a pressure of approximately 2000 pounds per square inch (psi) for approximately 5 minutes using methanol as the extraction solvent. The resulting extract is collected and transferred to a 25 mL flask, which is then filled to its maximum capacity with methanol. The resulting solution is then diluted approximately 25 times using a 50:50 mixture of water and methanol and used as the injection sample for subsequent LC-MS / MS analysis.

[0091] Approximately 5 μl of the injected sample is then injected and separated on a Water Acquity UPLC C18 column with a gradient of approximately 70% mobile phase A (1% formic acid in water) / 30% mobile phase B (0.1% formic acid in methanol) to 5% mobile phase A / 95% mobile phase B over approximately 3 minutes, with the final gradient held for an additional 3 minutes. Antimicrobial agents, such as Tinosan® HP100, are detected in negative MRM mode. The ion pair m / z 253>142 is used as the quantification transition, and m / z 253>125 is used for identification.

[0092] 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 calculated based on the weighted (1 / x) of the calibration curve. 2) is determined by extrapolation using quadratic regression.

[0093] Test 4: Biofilm formation (ASTM E2562) and biofilm removal test including removal in a washing machine 1. Culture Preparation Pseudomonas aeruginosa is the organism used in this study. Isolated colonies from the R2A plates are aseptically removed and placed in 100 mL of sterile TSB (300 mg / L). The bacterial suspension is incubated in an environmental shaker at 36 ± 2°C for 22 ± 2 hours. The viable bacterial density is 10 8 It should be equivalent to CFU / mL and can be confirmed by serial dilution and plating.

[0094] 2. Reactor Preparation A. Sonicate the test specimen in soapy tap water, then rinse and sonicate the specimen in reagent grade water until no soap remains on the specimen. B. Place a test specimen into each hole in the reactor rod and tighten the set screws. Place the rod loosely in the top of the reactor. C. Invert the reactor top and place the baffle on the glass rod centered on the reactor top. D. Invert the reactor beaker and place it on the assembled top. Turn the reactor upside down so that the reactor top is upright. E. Connect the bacterial air vent by fitting the vent to a small section of appropriately sized tubing and attach it to one of the rigid tubes at the top of the reactor. F. Attach the glass flow break to the feed tube line near the top of the reactor. G. Place reactor top securely in beaker before sterilization. Do not place rod alignment pin in notch during sterilization to allow pressure to escape. H. Cover the end of the feeding tube that connects to the feeding carboy and the end of the overflow (waste) tube with aluminum foil. Cover any extra openings on the top of the reactor with aluminum foil to maintain sterility after autoclaving. I. Prepare batch culture medium by dissolving bacterial liquid growth medium (300 mg / L TSB) in 500 mL of reagent grade water in an autoclavable container. J. Sterilize the reactor system and isolate the batch culture medium on the liquid cycle of a steam sterilizer for 20 min.

[0095] 3. Procedure A. With the overflow (waste) line clamped, aseptically add the chilled batch culture medium to the chilled reactor. B. Place the reactor on a stir plate. C. Clamp the flow break in an upright position. Clamp the other tubing and leave the foil attached. D. Secure the rod alignment pin into the reactor top notch. E. Inoculate the reactor with 1 mL of bacteria from the previously prepared culture (see 2I). Aseptically pipette the inoculum into the reactor through one of the available rigid reactor top tubes. F. Turn on the magnetic stir plate. Set the rotation speed to 125±5 r / min. Incubate the reactor system in batch mode at room temperature (21±2° C.) for 24 hours. G. Prepare a continuous-flow nutrient broth of 100 mg / L TSB. Dissolve the broth in a smaller volume to prevent caramelization and sterilize. Aseptically pour the concentrated broth into a carboy of sterile reagent-grade water for a total volume of 20 L. H. Aseptically connect the feeding tube line to the carboy containing the continuous flow nutrient broth. I. Pump a continuous stream of nutrients into the reactor at a flow rate determined by dividing the reactor volume by the 30-minute residence time. Attach tubing from the drain to a waste carboy and remove the clamp. The drain on the beaker creates an overflow to maintain a constant bacterial liquid growth broth concentration of 100 mg / L in the reactor while in CSTR (continuously stirred tank reactor) mode. J. Operate the reactor in SCTR mode for 24 hours.

[0096] 4. Product Processing A. Stop the growth medium flow and baffled stir bar. B. A randomly selected rod containing a biofilm-bearing specimen is aseptically removed from the CDC biofilm reactor by pulling it straight up and out of the reactor. C. Rinse the test specimen to remove any floating cells. Orient the rod in a vertical position directly above a 50 mL conical tube containing 30 mL of sterile buffered water. In one continuous motion, immerse the rod in the buffered water with minimal to no bouncing, then immediately remove it. Use a new 50 mL conical tube with 30 mL of sterile buffered water for each rod. D. Prepare a product solution in hard water at the recommended dosage (1000 ppm). E. Place the two rods in a customized beaker with a top that can hold the rods vertically. Transfer 350 ml of product solution into the beaker. F. Place the beaker on a magnetic stir plate and stir at 350 rpm for 10 minutes. Then discard the product solution and add 350 mL of fresh water to rinse the specimen at 350 rpm for 3 minutes. Repeat the rinse once more. G. Apply six cycles of product treatment to each specimen for each sample (Steps 4E-4F). H. For the control, 0.05% Tween 80 is used to replace the product solution and the same treatment is followed. I. Remove the appropriate number of test strips for testing in individual tubes. Obtain a set of 5 test strips for each treatment and a set of 3 test strips for the control. J. Add 3 ml of PBS solution to each tube containing one treated specimen. K. Vortex each tube at the highest setting, ensuring thorough vortexing for 30 ± 5 seconds. L. Sonicate the tube at 45 ± 5 kHz for 30 ± 5 seconds at room temperature (21 ± 2 °C) (if the sonicator has adjustable settings, use normal mode). M. Vortex each tube at the highest setting, ensuring thorough vortexing for 30 ± 5 seconds. N. Sonicate the tube at 45 ± 5 kHz for 30 ± 5 seconds at room temperature (21 ± 2 °C) (if the sonicator has changeable settings, use normal mode). 0. Vortex each tube at the highest setting, ensuring thorough vortexing for 30 ± 5 seconds. These tubes are the 100 dilution. P. Dilute and count the amount of bacteria on each specimen and calculate the logarithm of the value. 10 and the control and product treated specimens are averaged.

[0097] 5. Calculation of biofilm removal efficacy Logarithmic reduction value = log 10 Mean (control specimen) -log 10 Average (product-treated specimens). [Example]

[0098] Example 1: Comparative study demonstrating effective microbial removal by a low pH liquid detergent composition containing a surfactant system and an organic acid Seven (7) sample liquid laundry detergent compositions were prepared containing the ingredients shown in Table 1 below, with Samples 1-4 containing a surfactant system containing a non-ionic (NI) surfactant and an anionic (AI) surfactant, and a relatively high level of citric acid (CA) (i.e., at least 7%), resulting in a low product pH (i.e., from about 2 to about 3.2); Samples 5 and 6 containing a surfactant system similar to Samples 1-4, but containing low levels of CA (i.e., less than 4%), resulting in a relatively high product pH (i.e., from about 3.7 to about 8); and Sample 7 containing a high level of citric acid, resulting in a low pH, but no surfactant.

[0099] [Table 1] a C 11~13 LAS b Neodol® 25-7 is a C ethoxylated nonionic surfactant with an average of 7 moles of ethylene oxide. 12 ~C 15 It is an alcohol and is available from Shell. cTinosan® HP100 is 4-4′-dichloro-2-hydroxydiphenyl ether and is available from BASF. d Ethoxylated or ethoxylated and propoxylated polyethyleneimine (PEI) polymers, available from BASF.

[0100] The efficacy of microbial removal for the above samples at a final product dose of 1000 ppm was then determined according to Test 1: Efficacy of microbial removal using the Gram-negative bacteria Escherichia coli. The results are shown below.

[0101] [Table 2]

[0102] As shown in the data presented above, it is surprising and entirely unexpected that the combination of a surfactant system with a relatively high level of organic acid (i.e., corresponding to a low pH) can result in very strong microbial removal efficacy (i.e., log reductions of greater than 3, and even greater than 4). In other words, Samples 1-4 are able to remove greater than 99.9% of microorganisms in microbial removal tests (greater than 99.99% for Samples 1 and 3). In contrast, the surfactant system alone (Samples 5 and 6) or the organic acid alone (Sample 7) does not demonstrate significant microbial removal efficacy (i.e., log reductions of approximately 0).

[0103] Example 2: Comparative study demonstrating effective microbial prevention with low pH liquid detergent compositions containing surfactant systems and organic acids

[0104] [Table 3] a C 11~13 LAS b Neodol® 25-7 is a C ethoxylated nonionic surfactant with an average of 7 moles of ethylene oxide. 12 ~C 15 It is an alcohol and is available from Shell. c Tinosan® HP100 is 4-4′-dichloro-2-hydroxydiphenyl ether and is available from BASF. d Ethoxylated or ethoxylated and propoxylated polyethyleneimine (PEI) polymers, available from BASF.

[0105] The efficacy of microbial elimination for the above samples at a final product dose of 1000 ppm is then determined according to Test 2: Efficacy of microbial elimination using the Gram-negative bacterium Klebsiella pneumoniae. The results are shown below.

[0106] [Table 4]

[0107] It is quite surprising from the data presented above that the microbial prevention efficacy is significantly improved in the low pH liquid detergent composition compared to the high pH liquid detergent composition (i.e., 3.5 vs. 2.4 and 3.8 vs. 2.8). In other words, the introduction of a significant amount of organic acid (i.e., citric acid) results in an order of magnitude reduction in CFU (i.e., bacterial count) on fabrics treated with the low pH liquid detergent composition compared to the high pH liquid detergent composition. Without being bound by any theory, it is believed that the antimicrobial agent (i.e., Tinosan in this example) can be more effectively deposited on fabrics during the wash cycle by using the low pH liquid detergent composition according to the present invention, and the deposited (i.e., residual) antimicrobial agent then more effectively prevents bacterial growth on the fabrics during drying, storage, or wear. Furthermore, even more improved microbial prevention efficacy can be obtained when a higher level of anionic surfactant is present. Without being bound by any theory, it is believed that the antimicrobial agent (i.e., Tinosan) is more effectively deposited on fabrics during the wash cycle in the presence of higher levels of anionic surfactant (i.e., LAS).

[0108] Example 3: Comparative study demonstrating effective biofilm removal by a low pH liquid detergent composition containing a surfactant system and an organic acid Three sample liquid laundry detergent compositions were prepared containing the ingredients shown in Table 5 below, with Samples 12 and 13 containing a surfactant system containing an anionic (AI) surfactant and a nonionic (NI) surfactant, and a relatively high level of citric acid (CA) (i.e., at least 14.1% or 10.0%), resulting in a low product pH (i.e., about 2.4 to about 2.6), while Sample 14 contained a surfactant system similar to Samples 12 and 13, but with a low level of CA, resulting in a relatively high product pH (i.e., greater than 8).

[0109] [Table 5] a C 11~13 LAS b Neodol® 25-7 is a C ethoxylated nonionic surfactant with an average of 7 moles of ethylene oxide. 12 ~C 15 It is an alcohol and is available from Shell. c Tinosan® HP100 is 4-4′-dichloro-2-hydroxydiphenyl ether and is available from BASF. d Ethoxylated or ethoxylated and propoxylated polyethyleneimine (PEI) polymers, available from BASF.

[0110] The biofilm removal efficacy of the above samples at a final product dosage of 1000 ppm is then determined according to Test 4: Biofilm Formation (ASTM E2562) and Biofilm Removal Test including Removal in a Washing Machine Using Gram-Negative Bacteria Pseudomonas aeruginosa. The results are shown below.

[0111] [Table 6]

[0112] It is quite surprising from the data presented above that the biofilm removal efficacy is significantly improved in the low pH liquid detergent compositions compared to the high pH liquid detergent compositions (i.e., 2.43 or 2.54 vs. 0.89).

[0113] Example 4: Exemplary Formulations of Liquid Laundry Detergent Compositions The following liquid laundry detergent compositions shown in Table 7 are made containing the listed ingredients in the listed proportions (by weight).

[0114] [Table 7]

[0115] The liquid laundry detergent compositions A to F of Example 4 were a) mixing a combination of NaOH (if added) and water in a batch vessel by applying a shear force of 200 rpm; b) Citric acid (if added), boric acid (if added), and C 11 ~C 13 adding the LAS to the batch vessel and continuing to mix by applying a shear force of 200 rpm; c) allowing the mixture obtained in step b) to cool to 25°C; d) C 12~14 AE 1~3 S, Na-DTPA (if added), Neodol® 25-7, dodecyldimethylamine oxide, C 12 ~C 18 adding the fatty acid, 1,2 propanediol (if added), monoethanolamine (if added), calcium chloride (if added), sodium cumene sulfonate (if added), silicone emulsion (if added), sodium polyacrylate (if added), and Tinosan® HP100 to a batch vessel and mixing by applying shear at 250 rpm until the mixture is uniformly mixed and adjusting the pH to 8; e) adding the whitening agent (if added), the protease (if added), the amylase (if added), the dye (if added), and the perfume oil (if added) to a batch vessel and mixing by applying a shear force of 250 rpm, thereby forming the liquid laundry detergent composition; Each component in the composition is present at the level specified for compositions A-F in Example 4.

[0116] 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."

[0117] 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.

[0118] 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. An antimicrobial liquid laundry detergent composition for removing biofilms, comprising: a) 0.01% to 0.2%, by weight of the composition, of an antimicrobial agent selected from the group consisting of diphenyl ethers and combinations thereof; b) 4.5% to 40% by weight of the composition of an organic acid; c) 4% to 60% by weight of the composition of a surfactant system; The surfactant system is C ６ ~C ２０ Linear alkylbenzene sulfonate (LAS), C 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 alkyl ether carboxylates (AECs), and combinations thereof; the composition has an undiluted pH of 1.5 to 3.5; The antibacterial agent is 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; An antimicrobial liquid laundry detergent composition wherein the surfactant system further comprises a nonionic surfactant, and the ratio of the anionic surfactant to the nonionic surfactant is from 0.2 to 5.

2. 10. The antimicrobial liquid laundry detergent composition of claim 1 having an undiluted pH of from 1.6 to 3.

1.

3. 3. The antimicrobial liquid laundry detergent composition of claim 1 or 2, wherein the through-the-wash (TTW) pH during the wash sub-cycle is from 2.5 to 6.

0.

4. The antimicrobial liquid laundry detergent composition of any one of claims 1 to 3, wherein the antimicrobial agent is present in an amount ranging from 0.02% to 0.2% by weight of the composition.

5. The antimicrobial liquid laundry detergent composition of any one of claims 1 to 4, wherein the organic acid is present in an amount ranging from 5.5% to 30% by weight of the composition.

6. 6. The antimicrobial liquid laundry detergent composition of any one of claims 1 to 5, wherein the surfactant system is present in an amount ranging from 5% to 50% by weight of the composition.

7. 2% to 35% by weight of the composition ６ ~C ２０ Contains linear alkylbenzene sulfonate (LAS), 2% to 35% by weight of the composition ６ ~C ２０ The antimicrobial liquid laundry detergent composition of any one of claims 1 to 6, comprising an alkoxylated alcohol.

8. 8. The antimicrobial liquid laundry detergent composition of any one of claims 1 to 7, further comprising from 0.1% to 5% by weight of the composition of an amphoteric surfactant.

9. 9. The antimicrobial liquid laundry detergent composition of any one of claims 1 to 8, wherein the total surfactants are present in an amount ranging from 4% to 50% by weight of the composition.

10. 10. The antimicrobial liquid laundry detergent composition of any one of the preceding claims, further comprising from 0.1% to 10% by weight of the composition of a polyamine.

11. The antimicrobial liquid laundry detergent composition of any one of claims 1 to 10, further comprising from 0.1% to 5% by weight of the composition of a chelating agent.

12. a) 0.02% to 0.2% by weight of the composition of 4,4'-dichloro-2-hydroxydiphenyl ether; b) 6.5% to 18% citric acid by weight of the composition; and c) 5% to 20% by weight of the composition １０ ~C １６ a linear alkylbenzene sulfonate; d) 7% to 20% by weight of the composition １２ ~C １８ alkyl ethoxylates, 10. The antimicrobial liquid laundry detergent composition of claim 1, wherein the composition has an undiluted pH of from 1.9 to 3.1.

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