Liquid laundry detergent composition

Abstract

To provide a liquid laundry detergent composition that is useful for treating fabrics with improved malodor control benefit.SOLUTION: There is provided a liquid laundry detergent composition which contains: (a) from 0.001 wt.% to 5 wt.% of a hindered phenol antioxidant as an ester of 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-benzenepropanoic acid; (b) from 10 wt.% to 40 wt.% of one or more nonionic surfactants; and (c) from 5 wt.% to 30 wt.% of one or more anionic surfactants selected from the group consisting of a C10 to C20 linear alkyl benzene sulphonate and a C10 to C20 linear or branched alkylethoxy sulfate having a weight average degree of ethoxylation ranging from 0.1 to 5.0, where a weight ratio of the one or more nonionic surfactants to the one or more anionic surfactants ranges from 1.5 to 8.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to cleaning compositions, particularly liquid laundry detergent compositions useful for treating fabrics, with improved malodor control benefits. [Background technology]

[0002] Laundry cleaning methods are designed to remove soils and stains from fabrics. Some soils and stains can produce malodors on the fabric. In some instances, these malodors can persist even after the laundry cleaning operation. Summary of the Invention [Problem to be solved by the invention]

[0003] There is a continuing need to provide laundry detergent products with improved malodor control and reduction benefits without increasing the total surfactant content or expanding their environmental "footprint." [Means for solving the problem]

[0004] A surprising discovery of the present invention is that when a liquid laundry detergent composition employs a hindered phenol antioxidant in combination with a particular surfactant system, i.e., one containing both nonionic (NI) and anionic (AI) surfactants at a relatively high NI to AI weight ratio, the resulting malodor control and reduction benefits are further improved compared to a liquid laundry detergent composition containing the same hindered phenol antioxidant but in a different surfactant system (e.g., at a lower NI to AI weight ratio). Furthermore, the presence of a hindered phenol antioxidant in the liquid laundry detergent composition of the present invention may further improve perfume release from such compositions.

[0005] In one aspect, the present invention provides a method for producing a pharmaceutical composition comprising: (a) about 0.001% by weight to about 5% by weight of a hindered phenol antioxidant; (b) about 5% to about 60% by weight of one or more nonionic (NI) surfactants; (c) about 1% to about 45% by weight of one or more anionic (AI) surfactants; Including, On the other hand, the present invention relates to a liquid laundry detergent composition having an NI to AI weight ratio in the range of 1-20.

[0006] In a particularly preferred embodiment, the present invention comprises: (1) about 0.02% by weight to about 0.5% by weight of C1-C3 of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid 22 a hindered phenol antioxidant selected from the group consisting of linear alkyl esters and mixtures thereof; (2) about 10% by weight to about 40% by weight of C8-C8 ethoxylates having a weight average degree of ethoxylation ranging from about 7 to about 10; 18 a nonionic surfactant (NI) selected from the group consisting of alkyl ethoxylated alcohols and mixtures thereof; (3) about 5% by weight to about 20% by weight of C 10 ~C 20 Linear alkylbenzene sulfonate (LAS) and C having a weight average degree of ethoxylation ranging from about 1 to about 3 10 ~C 20 a linear or branched alkyl ethoxy sulfate (AES); Including, The present invention relates to a liquid laundry detergent composition having a weight ratio of NI to LAS+AES ranging from about 1.5 to about 8.

[0007] The present invention may also relate to the use of the above-mentioned liquid laundry detergent composition for treating fabrics.

[0008] These and other features of the present invention will become apparent to those skilled in the art from a review of the following detailed description taken in conjunction with the appended claims. DETAILED DESCRIPTION OF THE INVENTION

[0009] As used herein, the articles "a" and "an," when used in a claim, are understood to mean one or more of what is claimed or described.

[0010] As used herein, the terms "comprising," "comprises," "include," "includes," and "including" are meant to be open-ended.

[0011] As used herein, the terms "substantially free of" or "substantially free from" mean that the indicated substance is present in an amount of about 5% by weight or less, preferably about 2% by weight or less, and more preferably about 1% by weight or less.

[0012] As used herein, the terms "essentially free of" or "essentially free from" mean that the designated substance is present in such small amounts that it has not been intentionally added to the composition, or preferably is not present in such compositions at concentrations detectable by analysis. Compositions may be included in which the designated substance is present only as an impurity of one or more substances intentionally added to such compositions.

[0013] As used herein, the term "liquid" refers to a liquid at 25°C and 20 seconds -1 The viscosity at a shear rate of about 1 to about 2000 mPa * In some embodiments, the viscosity of the liquid is 20 sec-s at 25°C. 1 At a shear rate of about 200 to about 1000 mPa * In some embodiments, the viscosity of the liquid may range from 20 s to 100 s at 25°C. 1 At a shear rate of about 200 to about 500 mPa * It may be in the range of s.

[0014] Unless otherwise specified, as used herein, the term "molecular weight" refers to the weight average molecular weight (MWw) of the polymer chains in a polymer composition, and can be calculated using the following formula: MWw=(Σi Ni Mi 2 ) / (Σi Ni Mi) where Ni is the number of molecules with molecular weight Mi.

[0015] Unless otherwise indicated, as used herein, the term "alkyl" means a hydrocarbyl moiety which may be straight or branched, substituted or unsubstituted.

[0016] As used herein, the term "hydrocarbyl" is defined herein as any organic unit or moiety composed of carbon and hydrogen atoms. Included in the definition of "hydrocarbyl" are aromatic (aryl) and non-aromatic carbocycles. The term hydrocarbyl further includes heterocycles. The term "heterocycle" includes both aromatic (heteroaryl) and non-aromatic heterocycles.

[0017] All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. All measurements herein are made at 25°C and atmospheric pressure unless otherwise specified. In all embodiments of the present invention, all percentages are by weight of the total composition unless otherwise specified. All percentages are by weight unless otherwise specified.

[0018] It will be understood that the values ​​of each of the parameters of Applicants' invention described and claimed herein must be measured using the test methods disclosed in the Test Methods section of this application.

[0019] Hindered phenol antioxidants The liquid laundry detergent compositions of the present invention preferably contain at least one hindered phenol antioxidant in an amount sufficient to provide an antioxidant concentration in the treatment liquor of at least 25 ppb, more preferably at least 100 ppb, even more preferably at least 250 ppb, even more preferably at least 500 ppb, and most preferably at least 1000 ppb. Without wishing to be bound by theory, it is believed that the hindered phenol antioxidant can help improve the malodor control performance of liquid laundry detergent compositions, especially in combination with surfactant systems having a relatively high content of nonionic surfactants according to the present disclosure.

[0020] As used herein, the term "hindered phenol" refers to a compound that contains a phenol group having a substituent in the ortho position relative to at least one phenolic -OH group. Preferably, the hindered phenol antioxidant used in the present invention has (a) at least one C3-C6 substituent in the ortho position relative to the at least one phenolic -OH group. 22 or (b) at least one phenolic —OH group having a branched alkyl; or (b) substitutions at each ortho position relative to the at least one phenolic —OH group, the substitutions being independently selected from hydroxy, C1-C6 alkoxy, C1-C 22 and combinations thereof.

[0021] Examples of such hindered phenol antioxidants include 2,6-bis(1-methylpropyl)phenol; 2,6-bis(1,1-dimethylethyl)-4-methyl-phenol (also known as hydroxybutylated toluene or "BHT"); 2-(1,1-dimethylethyl)-1,4-benzenediol; 2,4-bis(1,1-dimethylethyl)-phenol; 2,6-bis(1,1-dimethylethyl)-phenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, methyl ester; 2-(1,1-dimethylethyl)- 2-(1,1-dimethylethyl)-4,6-dimethyl-phenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 1,1'-[2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl] ester; 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, octadecyl ester, 2,2'-methylenebis[6-(1,1-dimethylethyl)-4-methylphenol 2,4,6-Tris(1,1-dimethylethyl)-phenol;4,4'-Methylenebis[2,6-bis(1,1-dimethylethyl)-phenol;4,4',4''-[(2,4,6-trimethyl-1,3,5-benzenetriyl)tris(methylene)]tris[2,6-bis(1,1-dimethylethyl)-phenol];N,N'-1,6-Hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanamide;3,5-bis(1,1-dimethylethyl)-4 -Hydroxybenzoic acid, hexadecyl ester;P-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylphosphonic acid, diethyl ester;1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione;3,5-bis(1,1-5dimethylethyl)-4-hydroxybenzenepropanoic acid, 2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]hydrazide;3-(1,1-dimethylethyl)-4-hydroxy-5-methylbenzenepropanoic acid, 1,1'-[1,2-ethanediylbis(oxy-2,1-ethanediyl)] ester; 4-[(dimethylamino)methyl]-2,6-bis(1,1-dimethylethyl)phenol; 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)phenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 1,1'-(thiodi-2,1-ethanediyl) 3,5-Bis(1,1-dimethylethyl)-4-hydroxybenzoic acid, 2,4-bis(1,1-dimethylethyl)phenyl ester;3,5-Bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 1,1'-(1,6-hexanediyl) ester;3-(1,1-Dimethylethyl)-4-hydroxy-5-methylbenzenepropanoic acid, 1,1'-[2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2,2-dimethyl-2,1-ethanediyl)] ester;3-(1,1 -dimethylethyl)-b-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-b-methylbenzenepropanoic acid, 1,1'-(1,2-ethanediyl) ester;2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioic acid, 1,3-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester;3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 1-[2-[3-[3,5-bis(1,1-dimethylethyl) -4-Hydroxyphenyl]-1-oxopropoxy]ethyl]-2,2,6,6-tetramethyl-4-piperidinyl ester;3,4-Dihydro-2,5,7,8-tetramethyl-2-[(4R,8R)-4,8,12-trimethyltridecyl]-(2R)-2H-1-benzopyran-6-ol;2,6-Dimethylphenol;2,3,5-Trimethyl-1,4-benzenediol;2,4,6-Trimethylphenol;2,3,6-Trimethylphenol;4,4'-(1-Methylethylidene)-bis[2,6-dimethylphenol];These may include, but are not limited to, 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; 4,4'-methylenebis[2,6-dimethylphenol]; and mixtures thereof.

[0022] Additional antioxidants may be used. Examples of suitable additional antioxidants include, but are not limited to, α-, β-, γ-, δ-tocopherol, ethoxyquin, 2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butylhydroquinone, tert-butylhydroxyanisole, lignosulfonic acid and its salts, and mixtures thereof. Note that ethoxyquin (1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) is sold under the name Raluquin™ by the Raschig™ company. Other types of antioxidants that can be used in the composition are 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox™) and 1,2-benzisothiazolin-3-one (Proxel GXL™). Antioxidants such as tocopherol sorbate, butylated hydroxylbenzoic acid and its salts, gallic acid and its alkyl esters, uric acid and its salts, sorbic acid and its salts, and dihydroxyfumaric acid and its salts may also be useful. Other useful antioxidants may include tannins, such as tannins selected from the group consisting of gallotannins, ellagitannins, complex tannins, condensed tannins, and combinations thereof.

[0023] Preferably, the hindered phenol antioxidant comprises at least one phenolic -OH group having at least one C3-C6 branched alkyl in the ortho position relative to the at least one phenolic -OH group. For example, the hindered phenol antioxidant may be 2,6-bis(1,1-dimethylethyl)-4-methyl-phenol (BHT).

[0024] More preferably, the hindered phenol antioxidant is an ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid, most preferably a C1-C6 ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid. 22 It is a linear alkyl ester. Commercially available C1-C of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid 22 Linear alkyl esters include RALOX® from Raschig USA (Texas, USA), which is the methyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid, and TINOGARD® from BASF (Ludwigshafen, Germany), which is the octadecyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid.

[0025] Hindered phenol antioxidants can also help reduce yellowing that can be associated with amines, allowing for the incorporation of relatively high levels of amines. In this regard, it may be preferable to use non-yellowing hindered phenol antioxidants. Antioxidants that form yellow by-products are undesirable, as they can lead to perceptible negative attributes in the consumer experience (e.g., the deposition of yellow by-products on fabrics). Those skilled in the art can make informed decisions regarding the selection of antioxidants to use. Furthermore,

[0026] The hindered phenol antioxidants may be present in the liquid laundry detergent compositions of the present invention in an amount ranging from about 0.001% to about 5% by weight, preferably from about 0.005% to about 2% by weight, more preferably from about 0.01% to about 1% by weight, and most preferably from about 0.02% to about 0.5% by weight.

[0027] In a particularly preferred embodiment, the liquid laundry detergent composition comprises from about 0.02% to about 0.5% by weight of a C1-C 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid. 22Contains linear alkyl esters.

[0028] surfactant system In addition to the above-described hindered phenol antioxidants, the liquid laundry detergent compositions of the present invention also include a surfactant system comprising one or more surfactants selected from the group consisting of anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants, and combinations thereof. The total surfactant content of such liquid laundry detergent compositions may range from about 10% to about 90%, preferably from about 10% to about 80%, and more preferably from about 15% to about 60%, by total weight of the composition.

[0029] It is an important feature of the present invention that the surfactant system of the liquid laundry detergent composition comprises both a nonionic (NI) surfactant and an anionic (AI) surfactant at a specific NI to AI weight ratio ranging from about 1 to about 20, preferably from about 1.1 to about 15, more preferably from about 1.2 to about 10, and most preferably from about 1.5 to about 8. The total amount of NI surfactant and AI surfactant in the liquid laundry detergent composition may range from about 6% to about 90% by weight, preferably from about 10% to about 80% by weight, and more preferably from about 12% to about 60% by weight.

[0030] The nonionic surfactants that may be included in the liquid laundry detergent compositions of the present invention may be any conventional nonionic surfactant, including, but not limited to, alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, etc. Preferred nonionic surfactants are those represented by the formula R 1 (OC2H4) n OH (in the formula, R 1 is C8~C 18 (n is an alkyl or alkylphenyl group, and n is from about 1 to about 80). Particularly preferred are C8-C9 nonionic surfactants having a weight average degree of ethoxylation of from about 1 to about 20, preferably from about 5 to about 15, and more preferably from about 7 to about 10, such as NEODOL® nonionic surfactants available from Shell. 18 It is an alkyl ethoxylated alcohol.

[0031] Other non-limiting examples of nonionic surfactants useful herein include C6-C alkoxylates in which the alkoxylate units can be ethyleneoxy units, propyleneoxy units, or mixtures thereof. 12 Alkylphenol alkoxylate; C 12 ~C 18 C6-C with alcohol and ethylene oxide / propylene oxide block polymer 12 Alkylphenol condensates (such as Pluronic® (BASF)); C 14 ~C 22 Medium-chain branched alcohol (BA); C 14 ~C 22 Medium-branched alkyl alkoxylate, BAE x (wherein x is 1 to 30); alkyl polysaccharides, particularly alkyl polyglycosides; polyhydroxy fatty acid amides; and ether-terminated poly(oxyalkylated) alcohol surfactants. Suitable nonionic surfactants also include those sold by BASF under the trade name Lutensol®.

[0032] The nonionic surfactant may be provided in the liquid laundry detergent compositions of the present invention at a concentration ranging from about 5% to about 60% by weight, preferably from about 8% to about 50% by weight, more preferably from about 9% to about 45% by weight, and most preferably from about 10% to about 40% by weight. In one particularly preferred embodiment, the liquid laundry detergent composition comprises from about 10% to about 40% by weight of a C8-C9 nonionic surfactant having a weight average degree of ethoxylation ranging from about 7 to about 10. 18 Contains alkyl ethoxylated alcohols.

[0033] The anionic surfactants used in the liquid laundry detergent compositions of the present invention are preferably non-soap synthetic anionic surfactants such as the water-soluble salts, preferably alkali metal and / or ammonium salts, of organic sulfonic acid reaction products having from about 10 to about 20 carbon atoms in their molecular structure and alkyl groups containing sulfonic acid / phosphonic acid or sulfate / phosphate ester groups (the alkyl portion of the acyl group is included in the term "alkyl"). Examples of suitable synthetic anionic surfactants include C 10 ~C 20 Linear alkylbenzene sulfonate, C 10 ~C 20 Linear or branched alkyl sulfates, C with a weight average degree of ethoxylation ranging from 0.1 to 5.0 10 ~C 20 Linear or branched alkyl ethoxy sulfate, C 10 ~C 20 Linear or branched alkyl ester sulfate, C 10 ~C 20 Linear or branched alkyl sulfonates, C 10 ~C 20 Linear or branched alkyl ester sulfonates, C 10 ~C 20 Linear or branched alkyl phosphate, C 10 ~C 20 Linear or branched alkyl phosphonates, C 10 ~C 20 These include, but are not limited to, linear or branched chain alkyl carboxylates, and combinations thereof, including sodium, potassium, and / or ammonium salts thereof.

[0034] Particularly preferred for the practice of the present invention are 10 ~C 20 Linear alkylbenzene sulfonate (LAS) and C having a weight average degree of ethoxylation ranging from about 0.1 to about 5, preferably from about 0.5 to about 4, more preferably from about 1 to about 3. 10 ~C 20It is an anionic surfactant containing a linear or branched alkyl ethoxy sulfate (AES). In a particularly preferred embodiment of the present invention, the liquid laundry detergent composition comprises both an LAS and an AES.

[0035] The anionic surfactant may be provided in the liquid laundry detergent compositions of the present invention at a concentration ranging from about 1% to about 45% by weight, more preferably from about 2% to about 30% by weight, more preferably from about 3% to about 25% by weight, and most preferably from about 5% to about 20% by weight. In a particularly preferred embodiment, the liquid laundry detergent composition contains from about 5% to about 20% by weight of LAS and AES, while the AES has a weight average degree of ethoxylation ranging from about 1 to about 3. The weight ratio of LAS to AES is preferably in the range of 1:2 to 8:1, preferably 1:1 to 5:1, more preferably 1.5:1 to 4:1. Most preferably, the weight ratio of NI to (LAS+AES) is in the range of about 1.5 to about 8.

[0036] Other surfactants useful herein include amphoteric surfactants, zwitterionic surfactants, and cationic surfactants. Such surfactants are well known for use in laundry detergents and are typically present at concentrations of 0.1%, 0.2%, or 0.5% to about 5%, 10%, or 20% by weight.

[0037] In a preferred, but not required, embodiment of the present invention, the liquid laundry detergent composition further contains from about 0.2% to about 10% by weight of one or more amphoteric and / or zwitterionic surfactants.

[0038] Preferred amphoteric surfactants are selected from the group consisting of amine oxide surfactants, such as alkyl dimethyl amine oxide or alkyl amidopropyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide, especially coco dimethyl amine oxide. The amine oxide may have a linear or mid-chain branched alkyl moiety. Typical linear amine oxides are characterized by the formula R1-N(R2)(R3)-O, where R1 is C 8-18alkyl, and R and R are independently C, such as methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. 1~3 Alkyl and C 1~3 hydroxyalkyl. As used herein, "mid-chain branched" means that the amine oxide has one alkyl moiety with n1 carbon atoms, and one alkyl branch on the alkyl moiety has n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching of amine oxides is also known in the art as internal amine oxides. The sum of n1 and n2 is about 10 to about 24, preferably about 12 to about 20, and more preferably about 10 to about 16 carbon atoms. The number of carbon atoms in one alkyl moiety (n1) should be approximately the same as the number of carbon atoms in one alkyl branch (n2), so that one alkyl moiety and one alkyl branch are symmetrical. As used herein, "symmetric" means that in at least about 50% by weight, more preferably at least about 75% to about 100% by weight of the mid-chain branched amine oxides used herein, |n1-n2| is 5 or less, preferably 4, and most preferably 0 to 4 carbon atoms. Particularly preferred amphoteric surfactants are C 10 ~C 14 It is an alkyldimethylamine oxide.

[0039] Preferred zwitterionic surfactants are betaine surfactants, such as alkyl betaines, alkylamido betaines, amidazolinium betaines, sulfobetaines (also called sultaines), and phosphobetaines. A particularly preferred betaine is cocoamidopropyl betaine.

[0040] Water-soluble salts of higher fatty acids, i.e., "soaps," are also useful anionic surfactants in the liquid laundry detergent compositions of the present invention; however, such soaps are not considered when calculating the NI to AI weight ratio in the present invention. Suitable soaps include alkali metal salts (such as sodium, potassium, ammonium, and alkylammonium salts) of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. However, the liquid laundry detergent compositions of the present invention preferably contain soap at relatively low levels, e.g., not more than about 6% by weight, more preferably not more than about 2% or 1% by weight, and most preferably, the liquid laundry detergent compositions are substantially or essentially free of soap.

[0041] Liquid laundry detergent composition The liquid laundry detergent compositions of the present invention are suitable for automatic machine or hand washing of fabrics or fabric cleaning applications that include cleaning aids such as bleaches, rinse aids, additives, or pre-treatment types.

[0042] The liquid laundry detergent composition may be a fully formulated laundry detergent product. Liquid compositions contained in enclosed and / or unitized dose products include compositions containing two or more separate but co-dispensable portions. Preferably, the liquid laundry detergent composition contains water as the aqueous carrier, and may contain either water alone or a mixture of water and an organic solvent as the carrier. Suitable organic solvents are linear or branched lower C1-C8 alcohols, diols, glycerol, or glycols; lower amine solvents such as C1-C4 alkanolamines, and mixtures thereof. Representative organic solvents include 1,2-propanediol, ethanol, glycerol, monoethanolamine, and triethanolamine. The carrier is typically present at a concentration ranging from about 0.1% to about 98%, preferably from about 10% to about 95%, and more preferably from about 25% to about 75% of the total weight of the liquid laundry detergent composition. In some embodiments, water is about 85% to about 100% by weight of the carrier. In other embodiments, water is absent, and the composition is anhydrous. Highly preferred compositions obtained according to the present invention are clear, isotropic liquids.

[0043] The liquid laundry detergent compositions of the present invention have a viscosity of about 1 to about 2000 centipoise (1 to 2000 mPa·s), or about 200 to about 800 centipoise (200 to 800 mPa·s), as determined using a Brookfield viscometer, spindle #2, at 60 RPM / s and 25°C.

[0044] The liquid laundry detergent compositions of the present invention are preferably characterized by a pH value of 9 or less, preferably 8.7 or less, and more preferably 8.5 or less. Such pH value is measured using the liquid laundry detergent composition as a neat (i.e., undiluted) product. If the pH value of the liquid laundry detergent composition is too high, the hindered phenol antioxidant may be destabilized, resulting in yellow by-products that can cause an undesirable color change in the composition.

[0045] In addition to the above ingredients, the liquid laundry compositions of the present invention may also contain an external structurant, which may be present in an amount ranging from about 0.001% to about 1.0%, preferably from about 0.05% to about 0.5%, and more preferably from about 0.1% to about 0.3%, by total weight of the composition. A particularly preferred external structurant in the practice of the present invention is hydrogenated castor oil, also known as trihydroxyl stearin, and available commercially under the trademark Thixin®.

[0046] In addition to the above components, the balance of the liquid laundry cleaning compositions of the present invention typically contains from about 5% to about 70% by weight, or from about 10% to about 60% by weight, of adjunct ingredients. Suitable adjunct ingredients for laundry detergent products include builders, chelating agents, dye transfer inhibitors, dispersants, rheology modifiers, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, pre-formed peracids, polymeric dispersants, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, photobleaches, structure-stretching agents, fabric softeners, carriers, hydrotropes, processing aids, solvents, hueing agents, antimicrobial agents, perfumes (including undiluted perfume oils and / or perfume microcapsules), and / or pigments. The exact nature and concentration of these adjunct ingredients in a liquid laundry detergent composition will depend on factors such as the specific type of composition and the nature of the cleaning task for which the composition is to be used.

[0047] The liquid laundry detergent compositions of the present invention can be formed by any suitable method, such as by combining the above-described ingredients simultaneously or sequentially. In a preferred embodiment, the hindered phenol antioxidant is added as part of an emulsified premix formed by combining the hindered phenol antioxidant with an emulsifier. Additionally, it may be desirable to add a small amount of a weak acid to the premix to stabilize the hindered phenol antioxidant and protect it against alkalinity during the manufacturing process.

[0048] Methods of Using Liquid Laundry Detergent Compositions In one aspect, the present invention is directed to a method of using the liquid laundry detergent composition described above to treat fabrics, the method comprising the steps of: (i) providing the liquid laundry detergent composition described above; (ii) forming a wash liquor by diluting the liquid laundry detergent composition with water; (iii) washing the fabrics in the wash liquor; and (iv) rinsing the fabrics with water.

[0049] The machine washing method may involve treating soiled fabrics with an aqueous wash solution in a top-load or drum-type automatic or semi-automatic washing machine into which an effective amount of the liquid laundry detergent composition according to the present invention has been dissolved or dispensed. An "effective amount" of liquid laundry detergent composition means that about 10 g to about 300 g of product is dissolved or dispersed in a wash solution volume of about 5 L to about 65 L. The water temperature may range from about 5°C to about 100°C. The water to soiled fabric ratio may be from about 1:1 to about 30:1. The liquid laundry detergent composition may be used at a concentration of about 200 ppm to about 15,000 ppm in solution. The detergent dosage concentration may vary depending on the type and severity of the soils and stains, as well as the temperature of the wash water, the volume of the wash water, and the type of washing machine (e.g., top-load, drum, vertical axis Japanese automatic washing machine).

[0050] The liquid laundry detergent compositions herein can be used to launder fabrics at low wash temperatures. These methods of laundering fabrics include delivering the liquid laundry detergent composition to water to form a wash liquor and adding fabrics to be laundered to the wash liquor, wherein the temperature of the wash liquor is from about 0° C. to about 20° C., or from about 0° C. to about 15° C., or from about 0° C. to about 9° C. The fabrics may be contacted with water before, after, or simultaneously with contacting the liquid laundry detergent composition with water.

[0051] Also included are hand wash / soak methods and combination hand wash using semi-automatic washing machines.

[0052] Test Method A. Sensory Testing for Odor Reduction / Elimination To evaluate the intensity of malodor and freshness, a sensory test is performed as follows: The sensory panel consists of at least five panelists. The panel must wear safety glasses, laboratory coats, and disposal gloves. The panelists' noses must not directly touch the test fabric during the evaluation. Panelists must follow appropriate rules to avoid nasal saturation and maintain good evaluation quality.

[0053] (1) Preparing the fabric The test fabric is a 100% cotton terry cloth towel measuring 30cm x 30cm. The test fabric is confirmed to be free of any stains and is a new towel before the test. The fabric is then washed as a stripping operation to remove starch from the towel. The stripping wash test has two steps: the first step is washing with powder detergent (without microencapsulated perfume detergent) at the test condition of 40°C and rinsing three times, and then the second step is washing with water at 40°C and rinsing three times.

[0054] (2) Preparation of 0.15% malodorous stain solution A 0.15% malodor stain solution is made by mixing the malodor cocktail with artificial body soil (ABS) according to this ratio (105 mL of 1% malodor cocktail, 14.525 mL of ABS solution, and 581 mL of ethanol, for a total of 700 mL per test).

[0055] The malodor cocktail is prepared by dissolving the malodorous substances in ethanol (CAS No. 64-17-,5) having the following composition: Artificial body soil (ABS) is commercially available from Accurate Product Development (2028 Bohlke Blvd, Fairfield, OH 45014). Work should be done in a fume hood.

[0056] [Table 1]

[0057] (3) Application of the malodorous stain solution to the test fabric This method is performed in a fume hood. Test towel fabric is cut into quarters for the test specimens. Excess water is removed by immersing the towels in tap water and spin-drying them in a washing machine for 3 minutes. For test specimens (quarter-size fabric), 5 mL of the mixture solution (0.15% malodor-stain solution) is applied to the front of the specimen, and 5 mL is applied to the back of the specimen with a pipette. For ballast malodor-loaded towels (whole-size fabric), 20 mL of the mixture solution (0.15% malodor-stain solution) is applied to the front and 20 mL to the back. The test specimens are wrapped in aluminum sheeting, and the edges of the aluminum sheet are folded over to seal (four test specimens wrapped together). The aluminum-wrapped test specimens are tapped for 5 minutes. The wrapped towels are placed in plastic bags, stored in a plastic case, and incubated at 40°C in a CTCH or calibrated incubator at 40°C for 7 days. The aluminum sheet is then removed and the towel is allowed to dry in a fume hood for approximately 3-4 hours. After drying for 3-4 hours, check the fabric for any odors. It is ready to use.

[0058] (4) Washing process and sensory evaluation of test fabrics Test fabric pieces (towels cut into quarters) are washed with detergent to assess the malodor reduction / elimination effect. In the test section (usually three sections), three test fabric pieces (three quarter sizes) are used for malodor evaluation, three whole towels are applied with the malodor solution for ballast, and the remaining pieces are 3 kg of clean T-shirts. In the control section, 15 test fabric pieces (fifteen quarter sizes) are used for malodor evaluation, and the remaining pieces are 3 kg of clean T-shirts. The wash test is conducted in a washing machine under standard test conditions.

[0059] A reference laundry detergent is also included in the above method. The reference can be one of the laundry detergents being tested. The malodor score of the sample versus the reference is determined by the panel according to the following sensory scale (9-point scale):

[0060] [Table 2]

[0061] Test fabrics are evaluated by at least five qualified DoD panelists. Each pair (three pairs of different fabrics) can be evaluated in triplicate by up to three panelists. After the first panelist completes their evaluation, the second panelist begins their evaluation. All test fabrics are held securely in a plastic bag until the second panelist completes their evaluation. Panelists must complete their evaluation within 20 minutes. If a panelist is unable to complete the evaluation of all pairs within 20 minutes, they must take a break of at least 20 minutes and then evaluate the remaining pairs. There are three time points for evaluating fabrics: post-wash, which is within 1-2 hours after washing; post-dry, which is within the next day after drying; and re-wet, which is within the same day after the dry evaluation and within 1-2 hours after spraying water on the test fabric. Re-wet refers to the application of water to a dry test fabric, simulating wiping wet hands on a towel.

[0062] B. Quantitative Testing for Odor Reduction The following method is used to test the malodor reducing effectiveness of the compositions.

[0063] Add the fatty acids and malodor markers according to Table C to a 100 mL glass jar with a Teflon-lined cap and mix well using a vortex.

[0064] [Table 3]

[0065] The body soil malodor composition is then prepared by placing the specific amount of each material listed in Table D into a 200 mL glass bottle with a Teflon-lined cap. Artificial body soil (ABS) is commercially available from Accurate Product Development (2028 Bohlke Blvd, Fairfield, OH 45014).

[0066] [Table 4]

[0067] Next, 16 malodor test fabrics per wash load are prepared by applying 300 μL of the body soil malodor composition described in Table D to 2 x 5 inch white polycotton 50 / 50 (PCW50 / 50) swatches. Approximately 51 grams of each liquid laundry detergent to be tested (e.g., see Example 2, Table 3) is placed in a National Japanese-made, top-load automatic washing machine set to a normal cycle: a 68°F wash cycle, followed by a 68°F rinse cycle. Soft water from Cincinnati, Ohio, USA, is mixed with hard water in a known ratio to meet the hardness target. This is done automatically by interfacing the washing machine with a coded algorithm. The malodor test fabrics are washed in 3 gpg wash water using 2.7 kg, 50 x 50 cm clean cotton and polycotton ballast, then dried for 20 minutes in a Maytag tumble dryer set to low heat. The dried fabrics are placed in a Mylar bag and sealed for 24 hours.

[0068] Malodor reduction was then quantitatively determined by gas chromatography-mass spectrometry using an Agilent gas chromatograph 7890B equipped with a mass-selective detector (5977B), a Chemstation quantitative package, and a Gerstel multipurpose sampler equipped with a solid-phase microextraction (SPME) probe, using an ABS / squalene malodor sensor. Calibration standards of 6-methyl-5-hepten-2-one (CAS 110-93-0), trans-2-heptenal (18829-55-5), and 3-methyl-2-butenal (107-86-8) were prepared by dissolving known weights of these materials in light mineral oil (CAS 8020-83-5) (each available from Sigma-Aldrich). The fabric was cut into uniform 2" x 2.5" pieces and placed in a 10 mL headspace crimp vial. Vials are equilibrated for more than 12 hours prior to analysis. The following settings are used for the autosampler: 80°C incubation temperature, 90 minute incubation time, VT32-10 sample tray type, 22 mm vial penetration, 20 minute extraction time, 54 mm injection penetration, and 300 second desorption time. The following settings are used for the Front Split / Splitless inlet helium: split mode, 250°C temperature, 12 psi pressure, 79.5 mL / min total flow rate, 3 mL / min septum purge flow rate, 50:1 split ratio, and 22.5 minute GC run time. The following settings are used for the oven: 40°C initial temperature, 12°C / min heating program, 250°C temperature, and 5 minute hold time. Based on the partition coefficients of each component (K at 80°C), calculate the total nmoles / L of 6-methyl-5-hepten-2-one (K = 3353), trans-2-heptenal (K = 3434), and 3-methyl-2-butenal (K = 1119).

[0069] These three measurements (nmol / L) are added together to give the total ABS / Squalene marker (nmol / L) for a given test section.

[0070] The % reduction in malodor of oxidation products is expressed as a percentage comparing the reduction in the amount of selected malodor markers provided by the test composition compared to the reference composition (without antioxidant). Values ​​are determined as follows: % Reduced Oxidation Products = (Markersref - Markerstest) x 100 / Markersref

[0071] The values ​​of Markersref and Markerstest are defined as follows: Markersref = total ABS / squalene markers (nmol / L) for fabrics washed with a formulation containing no antioxidants (e.g., a reference or control formulation) Markerstest = total ABS / squalene markers (nmol / L) of fabrics washed with the formulations with the tested antioxidants

[0072] Since the measured oxidation products are typically considered to be malodors, the higher the percent reduction in oxidation products provided by the composition, the more likely the treated fabric will have reduced malodors. Thus, higher percent reduction in oxidation products malodors is typically preferred. The compositions and processes of the present disclosure can provide a percent reduction in oxidation products malodors of at least about 10%, or at least about 20%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%.

[0073] Malodor reduction may also be reported as the difference between Markersref and Markerstest, thereby showing the absolute difference (eg, delta ABS / squalene oxidation).

[0074] C. Fragrance Headspace Test Method The total fragrance intensity of the fabric headspace is assayed using gas chromatography-mass spectrometry (GC-MS) using an Agilent Technologies Gas Chromatograph 7890B system equipped with an Agilent Technologies 5977B Mass Selective Detector and an Agilent® J&W® DB-5ms Ultra Inert Column (30 m long x 0.25 mm inner diameter x 0.25 μm film thickness). The fabric is cut into 5 x 8 cm pieces and slid into a 20 mL headspace vial. After pressing three times with a 2 kg weight, the headspace vial is conditioned in air on the bench for 1 hour and immediately sealed before analysis.

[0075] The following settings were used on the multipurpose autosampler MPS (GERSTEL): 65 °C incubation temperature, 15 min incubation time, VT15-20-CVM sample tray type, 2 cm DVB / CAR / PDMS-coated gray notched SPME fiber (Supelco 57299-U), 30 mm vial penetration, 5 min extraction time, 43 mm injection penetration, and 180 s desorption time. The following settings were used for the front split / splitless inlet helium: splitless mode, heating at 270 °C, 12.9 psi pressure, 1.6 mL / min flow rate. The following settings were used for the oven: 40 °C initial temperature and 0.5 min hold time, 17 °C / min heating program, 270 °C and 1 min hold time. The following settings were used for the MSD: full scan mode in the m / z range of 35 to 300. [Example]

[0076] Example 1: Improved Malodor Reduction Efficacy of Antioxidant-Containing Liquid Laundry Detergent Compositions Four liquid laundry detergent compositions, A-D, are provided, all of which contain approximately 22.0 wt. % surfactants, including both an NI surfactant and two AI surfactants (LAS and AES). Compositions A and C contain approximately 0.075 wt. % hindered phenol antioxidant, while Compositions B and C contain no such antioxidant. The NI to AI weight ratios in these liquid laundry detergent compositions vary: Compositions A and B have a ratio of approximately 1.5, while Compositions C and D have a ratio of approximately 0.5. The following is a detailed compositional breakdown of liquid laundry detergent compositions A-D.

[0077] [Table 5] 1 Methyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid. 2 C with a weight average ethoxylation degree of 7 12 ~C 14 Alkyl ethoxylated alcohols. 3 C 11 ~C 12 Linear alkylbenzene sulfonate. 4 C with a weight average degree of ethoxylation of about 3 12~14 Alkyl ethoxylated sulfates.

[0078] To demonstrate the malodor reducing effect of hindered phenol antioxidants in different surfactant systems with different NI to AI ratios, malodor sensory testing was performed on liquid detergent compositions A-D according to Test Method A: Sensory Test for Malodor Reduction / Elimination. Composition A was used as a reference and the malodor scores of compositions B-D versus composition A were determined by a panel. The results of the malodor sensory testing are shown in the table below.

[0079] [Table 6]

[0080] It is clearly shown that the addition of a hindered phenolic antioxidant can result in improved malodor reduction efficacy at different NI to AI ratios, i.e., composition A containing a hindered phenolic antioxidant is better than composition B without a hindered phenolic antioxidant, and composition C containing a hindered phenolic antioxidant is better than composition D without a hindered phenolic antioxidant. More surprisingly, the malodor reduction efficacy is further improved under high NI backgrounds (i.e., at relatively high NI to AI weight ratios) because composition A, with an NI to AI weight ratio of 1.5, is better than composition C, with an NI to AI weight ratio of 0.5, and the addition of Ralox® results in greater malodor reduction under high NI backgrounds (i.e., 0.2 after washing and 0.7 after drying / rewetting, A vs. B) compared to low NI backgrounds (i.e., 0 after washing and 0.2 or 0.3 after drying / rewetting, C vs. D).

[0081] Example 2: Comparative Example Demonstrating the Effect of Various NI to AI Weight Ratios on the Malodor-Reducing Efficacy of Antioxidant-Containing Liquid Laundry Detergent Compositions Seven liquid laundry detergent compositions E-K are provided, all of which contain about 0.075 wt. % hindered phenol antioxidant and about 22.0 wt. % surfactants, including both an NI surfactant and two AI surfactants (LAS and AES). The NI to AI weight ratios in these liquid laundry detergent compositions vary from about 0.5 to about 5, e.g., about 0.5, 0.8, 1, 1.2, 1.5, 2, and 5. Below is a detailed compositional breakdown of liquid laundry detergent compositions E-K.

[0082] [Table 7] 1 Methyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid. 2 C with a weight average ethoxylation degree of 7 12 ~C 14 Alkyl ethoxylated alcohols. 3 C 11 ~C 12 Linear alkylbenzene sulfonate. 4 C with a weight average degree of ethoxylation of about 3 12~14 Alkyl ethoxylated sulfates.

[0083] To demonstrate the malodor reducing effect of hindered phenol antioxidants in different surfactant systems having different NI to AI ratios, liquid detergent compositions E-K are tested for their % malodor reducing oxidation product values ​​(i.e., reduced compositions versus control compositions containing the same ingredients but no hindered phenol antioxidant) according to Test Method B disclosed hereinabove.

[0084] Example 3: Exemplary Liquid Laundry Detergent Compositions Liquid laundry detergent compositions 1-6 are made by mixing the listed ingredients together in the proportions shown.

[0085] [Table 8] 1 Methyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid. 2 Octadecyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid. 3 C12-C14 alkyl ethoxylated alcohol with a weight average degree of ethoxylation of 7. 4 C12-C14 alkyl ethoxylated alcohol with a weight average degree of ethoxylation of 9. 5 C 11 ~C 12 Linear alkylbenzene sulfonate. 6 C with a weight average degree of ethoxylation of about 3 12~14 Alkyl ethoxylated sulfates.

[0086] 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."

[0087] 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.

[0088] 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 liquid laundry detergent composition comprising: (a) 0.001% to 5% by weight of a hindered phenol antioxidant which is an ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid; (b) 10% to 40% by weight of one or more nonionic surfactants; (c) 5% to 30% by weight of C １０ ~C ２０ Linear alkylbenzene sulfonate and C having a weight average degree of ethoxylation in the range of 0.1 to 5.0 １０ ~C ２０ one or more anionic surfactants selected from the group consisting of linear or branched alkyl ethoxy sulfates; Including, wherein the weight ratio of the one or more nonionic surfactants to the one or more anionic surfactants is in the range of 1.5 to 8; A liquid laundry detergent composition wherein the one or more nonionic surfactants comprise a C 8 -C 18 alkyl ethoxylated alcohol having a weight average degree of ethoxylation in the range of 1-20.

2. The hindered phenol antioxidant is a C １ ~C ２２ 10. The liquid laundry detergent composition of claim 1, wherein the ester is a linear alkyl ester.

3. 3. A liquid laundry detergent composition according to claim 1 or 2, wherein the hindered phenol antioxidant is present in the liquid laundry detergent composition in an amount ranging from 0.005% to 2% by weight.

4. The one or more anionic surfactants are selected from the group consisting of C １０ ~C ２０ Linear alkylbenzene sulfonate and C having a weight average degree of ethoxylation in the range of 0.1 to 5 １０ ~C ２０ A liquid laundry detergent composition according to any one of claims 1 to 3, comprising a linear or branched alkyl ethoxy sulphate.

5. 5. A liquid laundry detergent composition according to any one of claims 1 to 4, wherein the one or more anionic surfactants are present in the liquid laundry detergent composition in an amount ranging from 5% to 25% by weight.

6. A liquid laundry detergent composition according to any one of claims 1 to 5, characterized by a pH value of 9 or less.

7. 1. A liquid laundry detergent composition comprising: (1) 0.02 wt% to 0.5 wt% of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid C １ ~C ２２ a hindered phenol antioxidant selected from the group consisting of linear alkyl esters and mixtures thereof; (2) C having a weight average ethoxylation degree ranging from 7 to 10, from 10% to 40% by weight ８ ~C １８ a nonionic surfactant (NI) selected from the group consisting of alkyl ethoxylated alcohols and mixtures thereof; (3) 5% by weight to 20% by weight of C １０ ~C ２０ Linear alkylbenzene sulfonate (LAS) and C having a weight average degree of ethoxylation ranging from 1 to 3 １０ ~C ２０ a linear or branched alkyl ethoxy sulfate (AES); Including, A liquid laundry detergent composition, wherein the weight ratio of NI to LAS+AES is in the range of 1.5 to 8.

8. Use of a liquid laundry detergent composition according to any one of claims 1 to 7 for treating fabrics.

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