Ways to Reduce Bad Odors on Fabrics

Abstract

The present invention relates to a method for reducing malodor on fabrics using a detergent composition containing an antioxidant and the use of the antioxidant and the method.

Description

Technical Field

[0001] The present invention relates to a method for reducing malodor on fabrics using a detergent composition containing an antioxidant and the use of the antioxidant and the method. Background Art

[0002] Laundry washing processes are designed to remove soils from fabrics. Some soils can cause malodors on fabrics, and in some cases, these malodors can persist even after the laundry operation.

[0003] Therefore, there is a continuing need for methods of reducing malodor on fabrics.

[0004] Surprisingly it was found that the method according to the present invention reduces malodour on fabrics.

[0005] Without being bound by theory, it is believed that the specifically selected combination of antioxidant and metal ion combination according to the present invention provides malodor reduction benefits on fabrics through the wash. Summary of the Invention

[0006] A first aspect of the present invention is a method for reducing malodor on fabrics, the method comprising the steps of:

[0007] a. combining a fabric with a wash liquor, wherein the fabric comprises at least one malodor source, and wherein the wash liquor comprises a metal ion source, preferably Cu 2+ , and wherein the wash liquor is prepared by diluting the laundry detergent composition in water by a factor between 100 times and 3000 times, preferably between 300 times and 900 times;

[0008] b. washing the fabric in the wash liquid using an automatic washing operation, a manual washing operation or a mixture thereof, preferably an automatic washing operation;

[0009] c. separating the fabric and the wash liquid from each other;

[0010] d. drying the fabric;

[0011] wherein the laundry detergent composition comprises between 0.01% and 5%, by weight of the laundry detergent composition, of an antioxidant, wherein the antioxidant is an alkylated phenol.

[0012] A second aspect of the present invention is the use of an antioxidant for reducing malodor on fabric, wherein the fabric comprises at least one malodor source and the antioxidant is a hindered phenol.

[0013] A third aspect of the present invention is the use of a method according to the invention for reducing malodour on textiles in a wash liquor, and wherein the textiles comprise at least one malodour source, and wherein the wash liquor comprises metal ions, preferably Cu 2+ . BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 is a water-soluble unit dose preparation according to the present invention. DETAILED DESCRIPTION

[0015] method

[0016] The present invention relates to a method for reducing malodor on fabrics.

[0017] 'Mad odour' in the context of the present invention is an undesirable or undesirable odour on a fabric. Those skilled in the art will appreciate what is an undesirable odour as compared to a desirable odour.

[0018] The method comprises the following steps:

[0019] a. combining a fabric with a wash liquor, wherein the fabric comprises at least one malodor source, and wherein the wash liquor comprises a metal ion source, preferably Cu 2+ , and wherein the wash liquor is prepared by diluting the laundry detergent composition in water by a factor between 100 and 3000 times, preferably between 300 and 900 times. The fabric may be any suitable fabric. The so-called fabric preferably refers to a textile or cloth comprising a network of natural or synthetic fibers. Those skilled in the art will know suitable fabrics. The fabric may be selected from cotton, polyester, cotton / polyester blends, polyamide, lycra, rayon, or mixtures thereof.

[0020] The fabric comprises at least one malodor source. Suitable malodor sources will be known to those skilled in the art. The malodor source may include chemical decomposition products of body soil. The malodor source may include body soil or degradation products thereof, for example, 6-methyl-5-heptan-2-one, trans-2-heptanal, 3-methyl-2-butenal, decanoic acid, undecanoic acid, undecanedial, or mixtures thereof.

[0021] Those skilled in the art will know how to prepare this wash liquor.Without being bound by theory, the addition of a laundry detergent composition to water will cause the laundry detergent composition to dissolve and form a wash liquor.

[0022] The wash liquor may be formed automatically within the drum of an automatic washing machine, or it may be produced during a manual washing operation.

[0023] The laundry detergent composition can be contained in a water-soluble unit dose product, wherein the water-soluble unit dose product includes a water-soluble film. Without being bound by theory, adding the water-soluble unit dose product to water will cause the water-soluble film to dissolve and release the laundry detergent composition into the water, thereby producing a main wash liquor. When made in the rotating drum of an automatic washing machine, traditionally the fabric to be washed and the water-soluble unit dose product are added to the rotating drum, and the door of the washing machine is closed. The washing machine then automatically adds water to the rotating drum to form a wash liquor.

[0024] Preferably, the wash liquid comprises between 1 L and 64 L, preferably between 2 L and 32 L, more preferably between 3 L and 20 L of water.

[0025] Laundry detergent compositions are described in more detail below.

[0026] The washing liquid contains metal ions, preferably Cu 2+ . The metal ions may be present on the fabric before the fabric is contacted with the wash liquor. The metal ions may be present in the source of malodor on the fabric before the fabric is combined with the wash liquor. The metal ions may be present in the wash liquor when combined with the fabric. If present in the wash liquor, the metal ions may be present in the laundry detergent, water, or a mixture thereof. The water used to prepare the wash liquor may contain between 10 ppb and 2,000 ppb, preferably between 50 ppb and 1,000 ppb of metal ions. Without being bound by theory, tap water contains between 10 ppb and 2,000 ppb, preferably between 50 ppb and 1,000 ppb of Cu 2+ The malodor source may contain metal ions at the point where the malodor source is applied to the fabric. Alternatively, the malodor source may be applied to the fabric (such as may occur during wear where the fabric may come into contact with the wearer's skin) and the metal ions applied later.

[0027] Preferably, the wash liquor comprises from 0.1 ppm to 100 ppm, preferably from 0.15 ppm to 50 ppm of antioxidant.

[0028] b. Washing the fabrics in a wash liquor using an automatic wash operation, a manual wash operation or a combination thereof, preferably an automatic wash operation.

[0029] Those skilled in the art will know how to wash fabrics in an automatic wash operation, a manual wash operation, or a combination thereof.

[0030] Preferably, the temperature of the wash liquor is between 5°C and 90°C, preferably between 10°C and 60°C, more preferably between 12°C and 45°C, most preferably between 15°C and 40°C.

[0031] Preferably, washing of fabrics in the wash liquor takes between 5 and 50 minutes, preferably between 5 and 40 minutes, more preferably between 5 and 30 minutes, even more preferably between 5 and 20 minutes, most preferably between 6 and 18 minutes to complete.

[0032] Preferably, the wash liquor contains between 1 kg and 20 kg, preferably between 3 kg and 15 kg, most preferably between 5 kg and 10 kg of fabric.

[0033] The wash liquor may comprise water of any hardness varying preferably between 0 gpg and 40 gpg. Water of lower hardness is known as soft water, while water of higher hardness is known as hard water.

[0034] c. Separating the fabrics and the wash liquid from each other.

[0035] After the fabric is washed, the fabric and the wash liquor are separated from each other. Such separation may involve removing the fabric from the wash liquor, or draining the wash liquor from the fabric. In automatic washing machine operation, it is preferred to drain the wash liquor from the fabric. For the avoidance of doubt, some of the wash liquor may remain soaked into the fabric after the fabric is separated from the main wash liquor, i.e., the fabric remains wet. For the purposes of the present invention, once the fabric has been separated from the main volume of wash liquor or the main volume of wash liquor has been drained, the fabric and the wash liquor are considered to be separated from each other, although some residual wash liquor may still be soaked into the fabric.

[0036] d. Rinse fabrics

[0037] The method may include the additional step of rinsing the fabric with a liquid that may not contain detergent. This additional step may be used to remove any residual wash liquid from the fabric. The liquid used during the rinsing step may be water. Alternatively, the liquid may be a combination of water and one or more additives, such as a fabric softener.

[0038] e. Dry the fabric.

[0039] The method may include the additional step of drying the fabric. One skilled in the art will appreciate suitable methods for drying the fabric. The fabric may be dried by any suitable means, including but not limited to, online (indoors or outdoors), in an automatic dryer at room temperature, or a combination thereof. One skilled in the art will appreciate when a fabric is considered dry rather than wet.

[0040] Laundry detergent compositions

[0041] The method according to the present invention comprises the step of diluting the laundry detergent composition.

[0042] The laundry detergent composition may be in the form of a powder, liquid, water-soluble unit dose preparation, or a mixture thereof, preferably comprising a water-soluble unit dose of a liquid composition.

[0043] The solid laundry detergent composition may comprise solid particles or may be a single homogeneous solid. Preferably, the solid laundry detergent composition comprises particles. This means that the solid laundry detergent composition comprises individual solid particles, as distinct from a solid being a single homogeneous solid. The particles may be free-flowing or may be compacted, preferably free-flowing.

[0044] The term "liquid laundry detergent composition" means any laundry detergent composition comprising a liquid capable of wetting and treating fabrics, and includes, but is not limited to, liquids, gels, pastes, dispersions, etc. Liquid compositions may include solids or gases in suitably finely divided form, but liquid compositions do not include generally non-fluid forms such as powders, tablets, or granules.

[0045] Water-soluble unit dose preparations are described in more detail below.

[0046] The laundry detergent composition comprises between 0.001% and 5%, more preferably 0.01% to 1%, most preferably 0.025% to 0.5% by weight of the laundry detergent composition of an alkylated phenol or hindered phenol antioxidant.Antioxidants are described in more detail below.

[0047] The laundry detergent composition preferably comprises a non-soap surfactant. More preferably, the non-soap surfactant is selected from a non-soap anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a cationic surfactant, or a mixture thereof. The laundry detergent composition preferably comprises between 10% and 60%, more preferably between 20% and 55%, of the non-soap surfactant by weight of the laundry detergent composition.

[0048] Preferably, the non-soap anionic surfactant comprises linear alkylbenzene sulfonate, alkoxylated alkyl sulfate, alkyl sulfate or mixtures thereof. Preferably, the alkyl sulfate is ethoxylated alkyl sulfate.

[0049] Preferably, the laundry detergent composition comprises between 5% and 50%, preferably between 15% and 45%, more preferably between 25% and 40%, most preferably between 30% and 40% non-soap anionic surfactant by weight of the detergent composition.

[0050] Preferably, the non-soap anionic surfactant comprises linear alkylbenzene sulfonate and alkoxylated alkyl sulfate, wherein the ratio of linear alkylbenzene sulfonate to alkoxylated alkyl sulfate, preferably the weight ratio of linear alkylbenzene sulfonate to ethoxylated alkyl sulfate, is from 1:2 to 20:1, preferably from 1.1:1 to 15:1, more preferably from 1.2:1 to 10:1, even more preferably from 1.3:1 to 5:1, most preferably from 1.4:1 to 3:1.

[0051] Preferably, the laundry detergent composition comprises between 0% and 10%, preferably between 0.01% and 8%, more preferably between 0.1% and 6%, most preferably between 0.15% and 4% of a nonionic surfactant by weight of the laundry detergent composition. The nonionic surfactant is preferably selected from alcohol alkoxylates, oxo alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates or mixtures thereof.

[0052] Preferably, the liquid laundry detergent composition comprises between 1.5% and 20%, more preferably between 2% and 15%, even more preferably between 3% and 10%, most preferably between 4% and 8% of soap, preferably a fatty acid salt, more preferably an amine-neutralized fatty acid salt, by weight of the laundry detergent composition, wherein preferably the amine is an alkanolamine, more preferably selected from monoethanolamine, diethanolamine, triethanolamine or mixtures thereof, more preferably monoethanolamine.

[0053] The laundry detergent composition preferably comprises an ingredient selected from the list comprising cationic polymers, polyester terephthalates, amphiphilic graft copolymers, carboxymethyl cellulose, enzymes, perfumes, encapsulated perfumes, bleaching agents or mixtures thereof. Without being bound by theory, it is believed that further addition of these materials may further contribute to malodor reduction.

[0054] The laundry detergent composition may contain adjunct ingredients selected from non-aqueous solvents, water, hueing dyes, aesthetic dyes, enzymes, cleaning polymers, builders such as fatty acids, bleaching agents, dispersants, dye transfer inhibitor polymers, optical brighteners, opacifiers, defoamers or mixtures thereof.

[0055] The composition can include tinting dyes, sometimes referred to as fabric screening agents, which are well known in the art. Suitable fabric screening agents include dyes, dye-clay conjugates, and pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include dyes selected from the group consisting of direct blue, direct red, direct violet, acid blue, acid red, acid violet, basic blue, basic violet, and basic red. Examples of the dyes include alkoxylated azothiophene, solvent violet 13, acid violet 50, and direct violet 9.

[0056] Preferably, the laundry detergent composition comprises a chelating agent, wherein the chelating agent is preferably selected from phosphonates, aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents or mixtures thereof, more preferably an additional chelating agent selected from DTPA (diethylenetriaminepentaacetic acid), HEDP (hydroxyethanediphosphonic acid), EDDS (ethylenediamine disuccinate (EDDS)), DTPMP (diethylenetriaminepenta (methylenephosphonic acid)), EDTMP (ethylenediaminetetra (methylenephosphonic acid)), (1,2-dihydroxybenzene-3,5-disulfonic acid), HPNO (2-pyridinol-N-oxide), MGDA (methylglycine diacetic acid), GLDA (glutamic acid-N,N-diacetic acid), EDTA (ethylenediaminetetraacetic acid), any suitable derivatives thereof, salts thereof, and mixtures thereof.

[0057] The liquid laundry detergent composition preferably has a pH of between 6 and 10, more preferably between 6.5 and 8.9, most preferably between 7 and 8, wherein the pH of the liquid laundry detergent composition is measured upon 10% dilution in demineralised water at 20°C.

[0058] Water-soluble unit dose products

[0059] The water-soluble unit dose article comprises a water-soluble film and a laundry detergent composition. The laundry detergent composition and the water-soluble film are described in more detail below.

[0060] The water-soluble unit dose product comprises a water-soluble film, which is shaped so that the unit dose product comprises at least one inner compartment surrounded by the water-soluble film, and wherein the laundry detergent composition is present in the compartment. The unit dose product may comprise a first water-soluble film and a second water-soluble film that are sealed to each other to define the inner compartment. The water-soluble unit dose product is configured so that the laundry detergent composition does not leak out of the compartment during storage. However, when the water-soluble unit dose product is added to water, the water-soluble film dissolves and releases the contents in the inner compartment into the wash liquid.

[0061] The compartment should be understood to refer to the enclosed inner space in the unit dose product, which holds the detergent composition. During manufacture, the first water-soluble film can be shaped to include an open compartment in which the detergent composition is added. The second water-soluble film is then covered above the first film in an orientation close to the opening of the compartment. The first film and the second film are then sealed together along the sealing area.

[0062] The unit dose article may include more than one compartment, or even at least two compartments, or even at least three compartments. The compartments may be arranged in a stacked orientation, i.e., positioned one on top of the other. In this orientation, the unit dose article will include three layers of film: top, middle, and bottom. Alternatively, the compartments may be positioned in a side-by-side orientation, i.e., one immediately adjacent to the other. The compartments may even be oriented in a "tire and rim" arrangement, i.e., a first compartment is positioned adjacent to a second compartment, but the first compartment at least partially surrounds the second compartment, but does not completely enclose the second compartment. Alternatively, one compartment may be completely enclosed within another compartment.

[0063] Where the unit dose article comprises at least two compartments, one of the compartments may be smaller than the other. Where the unit dose article comprises at least three compartments, two of the compartments may be smaller than the third, and preferably the smaller compartment is stacked on the larger compartment. The stacked compartments are preferably oriented side by side.

[0064] In a multi-compartment orientation, the laundry detergent composition according to the present invention may be contained in at least one of the compartments. It may, for example, be contained in only one compartment, or may be contained in two compartments, or even in three compartments.

[0065] Each compartment may contain the same or different compositions. The different compositions may all be in the same form, or they may be in different forms.

[0066] The water-soluble unit dose article may comprise at least two internal compartments, wherein the liquid laundry detergent composition is contained in at least one of the compartments, preferably wherein the unit dose article comprises at least three compartments, wherein the detergent composition is contained in at least one of the compartments.

[0067] Figure 1 A water-soluble unit dose article (1) according to the present invention is disclosed. The water-soluble unit dose article (1) comprises a first water-soluble film (2) and a second water-soluble film (3) sealed together at a sealing area (4). A laundry detergent composition (5) is included within the water-soluble unit dose article (1).

[0068] The films of the present invention are soluble or dispersible in water. The water-soluble films preferably have a thickness of 20 to 150 microns, preferably 35 to 125 microns, even more preferably 50 to 110 microns, most preferably about 76 microns.

[0069] Preferably, the membrane has a water solubility of at least 50%, preferably at least 75%, or even at least 95%, as measured by the method set forth herein, using a glass filter having a maximum pore size of 20 microns:

[0070] 5 grams ± 0.1 grams of membrane material are added to a pre-weighed 3L beaker and 2L ± 5ml of distilled water are added. It is vigorously stirred for 30 minutes at 30°C on a magnetic stirrer Labline (model 1250) or equivalent and a 5cm magnetic stirrer (set to 600rpm). Then, the mixture is filtered through a folded qualitative porous glass filter with the above-mentioned specified pore size (maximum 20 microns). The moisture in the collected filtrate is dried by any conventional method, and the weight of the remaining material (the part that is dissolved or dispersed) is measured. Then, the percentage of solubility or dispersion can be calculated.

[0071] Preferred film materials are preferably polymeric materials. As known in the art, film materials can be obtained by, for example, casting, blowing, extruding or blown extrusion of polymeric materials.

[0072] Preferred polymers, copolymers or derivatives thereof suitable for use as pouch materials are selected from polyvinyl alcohol, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and polycarboxylates, polyamino acids or peptides, polyamides, polyacrylamides, maleic acid / acrylic acid copolymers, polysaccharides (including starch and gelatin), natural gums (such as xanthan gum and carrageenan). More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohol, polyvinyl alcohol copolymers and hydroxypropyl methylcellulose (HPMC), and combinations thereof. Preferably, the level of polymer (e.g., PVA polymer) in the pouch material is at least 60%. The polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000, and even more preferably from about 20,000 to 150,000.

[0073] Mixtures of polymers and / or copolymers can also be used as pouch materials, in particular mixtures of polyvinyl alcohol polymers and / or copolymers, in particular mixtures of polyvinyl alcohol homopolymers and / or anionic polyvinyl alcohol copolymers, preferably selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, in particular carboxylated anionic polyvinyl alcohol copolymers. Most preferably, the water-soluble film comprises a blend of polyvinyl alcohol homopolymers and carboxylated anionic polyvinyl alcohol copolymers.

[0074] Preferred membranes exhibit good solubility in cold water (which means unheated distilled water). Preferably, such membranes exhibit good solubility at a temperature of 24° C., even more preferably at a temperature of 10° C. By good solubility, it is meant that the membrane exhibits a water solubility of at least 50%, preferably at least 75%, or even at least 95%, as measured by the method described herein after using a glass filter with a maximum pore size of 20 microns, as described above.

[0075] Preferred membranes are those supplied by Monosol under trade references M8630, M8900, M8779, M8310.

[0076] The film may be opaque, transparent or translucent.The film may include printed areas.

[0077] Printed areas can be achieved using standard techniques such as flexographic printing or inkjet printing.

[0078] The film may contain an aversive agent, such as a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate, or mixtures thereof. Any suitable level of the aversive agent may be used in the film. Suitable levels include, but are not limited to, 1 ppm to 5000 ppm, or even 100 ppm to 2500 ppm, or even 250 rpm to 2000 rpm.

[0079] antioxidants

[0080] The fabric treatment composition comprises an antioxidant. Antioxidants are materials such as those described in Kirk-Othmer (Volume 3, page 424) and Ullmann's Encyclopedia (Volume 3, page 91). The fabric treatment composition comprises an antioxidant level sufficient to provide an antioxidant concentration of at least 25 ppb, preferably at least 100 ppb, more preferably at least 250 ppb, even more preferably at least 500 ppb, and even more preferably at least 1000 ppb in the treatment liquor. The antioxidant level may be from about 0.001% to about 50% by weight of the fabric treatment composition.

[0081] The antioxidant may be selected from the group consisting of alkylated phenols.

[0082] Alkylated phenols may have the general formula:

[0083]

[0084] where R 1 is a C3-C6 branched alkyl group, preferably a tert-butyl group; x is 1 or 2; and R is a C1-C 22 Straight chain alkyl or C3-C 22Branched alkyl groups, each (1) optionally having one or more ester (—CO—) or ether (—O—) bonds therein, and (2) optionally substituted with an organic group comprising an alkyleneoxy or polyalkyleneoxy group selected from EO, PO, BO, and mixtures thereof, more preferably EO alone or an EO / PO mixture; in one aspect, R is preferably methyl or a branched C3-C6 alkyl group, a C1-C6 alkoxy group, preferably a methoxy group.

[0085] The alkylated phenol may be a hindered phenol. As used herein, the term "hindered phenol" is used to refer to a compound comprising a phenol group having (a) at least one C3 or higher branched alkyl group, preferably a C3-C6 branched alkyl group, preferably a tert-butyl group, attached at an ortho position to at least one phenol-OH group, or (b) a substituent independently selected from the group consisting of a C1-C6 alkoxy group, preferably a methoxy group; a C1-C6 alkyl ... 22 Straight chain alkyl or C3-C 22 branched alkyl, preferably methyl or branched C3-C6 alkyl; or mixtures thereof. If the benzene ring contains more than one -OH group, the compound is a hindered phenol, provided that at least one such -OH group is substituted as described immediately above.

[0086] Another class of hindered phenol antioxidants suitable for use in the composition are benzofuran or benzopyran derivatives having the formula:

[0087]

[0088] wherein R1 and R2 are each independently an alkyl group, or R1 and R2 can be taken together to form a C5-C6 cyclic hydrocarbon group; B is absent or CH2; R4 is a C1-C6 alkyl group; R5 is hydrogen or -C(O)R3, wherein R3 is hydrogen or C1-C 19 alkyl; R6 is C1-C6 alkyl; R7 is hydrogen or C1-C6 alkyl; X is –CH2OH or –CH2A, wherein A is a nitrogen-containing unit, phenyl, or substituted phenyl. Preferred nitrogen-containing A units include amino, pyrrole, piperidine, morpholine, piperazine, and mixtures thereof.

[0089] Suitable hindered phenols for use herein include, but are not limited to: 3,3′-bis(1,1-dimethylethyl)-5,5′-dimethoxy-[1,1′-biphenyl]-2,2′-diol; 3-(1,1-dimethylethyl)-1,2-benzenediol; 2-(1,1-dimethylethyl)-4,6-dinitrophenol; 2,2′-butylenebis[6-(1,1-dimethylethyl)-4-methylphenol; 4,4′-[thiobis(methylene)]bis[2,6-bis(1,1-dimethylethyl)phenol; 3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionic acid methyl ester; 2-(1,1-dimethylethyl)-4-(1-methylethyl)phenol; 4,4′-dithiobis[2, 6-bis(1,1-dimethylethyl)phenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl dimethyldithiocarbamate; 2,6-bis(1,1-dimethylethyl)-4-(2-propen-1-yl)phenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid nitrilotri-2,1-ethylenediol; 4,4′-thiobis[2,6-bis(1,1-dimethylethyl)phenol; 3,5-bis(1,1-dimethylethyl)-1,2-benzenediol; 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid hydrazide; 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid ethyl ester; 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid ethyl ester; 4-Methylethyl)-4-hydroxybenzoic acid ethyl ester; 4,4'-[oxybis(methylene)]bis[2,6-bis(1,1-dimethylethyl)phenol; 2-[2-(4-chloro-2-nitrophenyl)diazenyl]-6-(1,1-dimethylethyl)-4-methylphenol; α-[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxy-poly(oxy-1,2-ethanediyl); 2,2'-methylenebis[4,6-bis(1,1-dimethylethyl)]phenol; 2,6-bis[[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenyl]methyl]-4-methylphenol; 2,6- Bis(1,1-dimethylethyl)-4-nonylphenol; 1,1′-bis[2-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]ethyl]thiodipropionate; 2-(1,1-dimethylethyl)-6-methyl-4-[3-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphapin-6-yl]oxy]propyl]phenol; 2-(1,1-dimethylethyl)-1,4-benzenediol 4-acetate; 2,4-bis(1,1-dimethylethyl)-6-(1-phenylethyl)phenol; 3,4′,5-tris(1,1-dimethylethyl)-[1,1′-biphenyl]-4-ol;3,3′,5,5′-tetrakis(1,1-dimethylethyl)-[1,1′-biphenyl]-2,2′-diol; methyl 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenylpropanoate; 4-hydroxy-3,5-dimethylbenzoin; 2-[(2-hydroxy-3,5-dimethylphenyl)methyl]-4,6-dimethylphenol; 2-ethyl-6-methylphenol; 3,4-dihydro-2,2,5,7,8-pentamethylphenol 2H-1-benzopyran-6-ol; 4-hydroxy-3,5-dimethylbenzaldehyde; 3,4-dihydro-6-hydroxy-2,5,7,8-tetramethyl-2H-1-benzopyran-2-carboxylic acid; 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol; 2,2′-methylenebis[6-cyclohexyl-4-methylphenol]; 2,3,5,6-tetramethylphenol; 2,3,4,5,6-pentamethylphenol; and mixtures thereof.

[0090] In one aspect, preferred hindered phenols for use herein include, but are not limited to: 2,6-dimethylphenol; 2,6-diethylphenol; 2,6-bis(1-methylethyl)phenol; 2,4,6-trimethylphenol; 2-(1,1-dimethylethyl)-4-methoxyphenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzoic acid; 3,5-bis(1,1-dimethylethyl)-2-hydroxy-benzoic acid; 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzyl alcohol; 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1- 1,1-dimethylethyl)-phenol; 2-(1,1-dimethylethyl)-4-ethyl-phenol; 2-(1,1-dimethylethyl)-6-methyl-phenol; 2,2′-methylenebis[6-(1,1-dimethylethyl)-4-ethylphenol; 2,6-bis(1,1-dimethylethyl)-4-ethylphenol; 4,4′-thiobis[2-(1,1-dimethylethyl)-6-methylphenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid 1,1′-[(1,2-dioxo-1,2-ethanediyl)bis(imino-2,1-ethanediyl) ] ester; 2,6-bis(1,1-dimethylethyl)-4-nitrosophenol; 2,2′-thiobis[6-(1,1-dimethylethyl)-4-methylphenol; 2,6-bis(1,1-dimethylethyl)-4-(1-methylpropyl)phenol; 2,4-bis(1,1-dimethylethyl)-6-methylphenol; 2,2′-ethylenebis[4,6-bis(1,1-dimethylethyl)]phenol; N,N′-1,3-propanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionamide; 2,6-bis(1,1-dimethylethyl) -1,4-Benzenediol; 4,4'-(1-methylethylidene)bis[2-(1,1-dimethylethyl)phenol; 2-ethylhexyl 2-[[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]thio]acetate; 4-butyl-2,6-bis(1,1-dimethylethyl)phenol; 2-(1,1-dimethylethyl)-4-[1-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-methylethyl]phenyl bis(4-nonylphenyl) phosphite; 4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)bis[2,6-bis(1,1-dimethylethyl)phenol]; 3-(5-chloro-2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenylpropanoate; 4,4′-(1-methylethylidene)bis[2,6-bis(1,1-dimethylethyl)phenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanoate, 1,1′,1″-[(2,4,6-trioxo-1,3,5-triazine-1,3,5(2H,4H,6H)-triyl)tri-2,1-ethanediyl] ester; 2,6-bis(1-methylethyl)phenol; 2,6-diethylphenol; 2,6- Dimethyl-1,4-benzenediol; 3,3′,5,5′-tetramethyl-[1,1′-biphenyl]-4,4′-diol; 2,6-bis(1,1-dimethylethyl)-4-(1-methylpropyl)phenol; 2,2′-methylenebis[4-methyl-6-(1-methylcyclohexyl)phenol; 3,5-bis(1,1-dimethylethyl)-[1,1′-biphenyl]-4-ol; 4-(1,1-dimethylethyl)-2,6-dimethylphenol; 2,3,4,6-tetramethylphenol; 2,4,6-tris(1-methylethyl)phenol; 2,2′-(2-methylpropylidene)bis[4,6-dimethylphenol]; and mixtures thereof.

[0091] On the other hand, highly preferred hindered phenols for use herein include, but are not limited to: 2,6-bis(1-methylpropyl)phenol; 2,6-bis(1,1-dimethylethyl)-4-methyl-phenol (also known as hydroxybutylated toluene, "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-hydroxy-phenylpropionic acid methyl ester; 2-(1,1-dimethylethyl)-4-methylphenol; 2-(1,1-dimethylethyl)-4,6-dimethyl-phenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionic acid 1,1′-[2 ,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl] ester; octadecyl 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanoate; 2,2′-methylenebis[6-(1,1-dimethylethyl)-4-methylphenol; 2-(1,1-dimethylethyl)-phenol; 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-hydroxyphenylpropionamide; 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzoic acid hexadecyl ester; diethyl P-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylphosphonate; 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; 2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]hydrazide of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate; 3-(1,1-dimethylethyl)-4-hydroxyphenylpropionate 1,1′-[1,2-ethanediylbis(oxy-2,1-ethanediyl)]-5-methylphenylpropanoate; 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; 1,1′-(thiobis-2,1-ethanediyl)-3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanoate; 2,4-bis(1,1-dimethylethyl)phenyl 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzoate; 1,1′-(1,6-hexanediyl)-3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanoate;3-(1,1-dimethylethyl)-4-hydroxy-5-methylbenzenepropanoate, 1,1'-[2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2,2-dimethyl-2,1-ethanediyl)]ester; 3-(1,1-dimethylethyl)-β-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-β-methylbenzenepropanoate, 1,1'-(1,2-ethanediyl)ester; 2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylmalonate, 1,3-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)ester; 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanoate, 1-[2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] ]-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]; 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. ;

[0092] In another aspect, highly preferred hindered phenols for use herein may also include 2-(1,1-dimethylethyl)-4-methoxyphenol, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzoic acid, 3,5-bis(1,1-dimethylethyl)-2-hydroxy-benzoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzyl alcohol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylethyl)-phenol, 2-(1,1-dimethylethyl)-4-ethyl-phenol, 2-(1,1-dimethylethyl)-6-methyl-phenol, 3-(1,1-dimethylethyl)-1,2-benzenediol, 2,2′-methylenebis[6-(1,1-dimethylethyl)- 1-Methyl)-6-phenol, 2,6-bis(1,1-dimethylethyl)-4-ethylphenol, 4,4′-thiobis[2-(1,1-dimethylethyl)-6-methylphenol, 2-(1,1-dimethylethyl)-4,6-dinitrophenol, 2,6-bis(1,1-dimethylethyl)-4-nitrosophenol, 2,2′-thiobis[6-(1,1-dimethylethyl)-4-methylphenol, 2,6-bis(1,1-dimethylethyl)-4-(1-methylpropyl)phenol, 2,2′-butylenebis[6-(1,1-dimethylethyl)-4-methylphenol, 2,4-bis(1,1-dimethylethyl)-6-methylphenol, 4,4′-[thiobis(methylene)]bis[2,6-bis(1 ,1-dimethylethyl)phenol, 2,2′-ethylenebis[4,6-bis(1,1-dimethylethyl)]phenol, N,N′-1,3-propylenediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionamide, 3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate, 2-(1,1-dimethylethyl)-4-(1-methylethyl)phenol, 2,6-bis(1,1-dimethylethyl)-1,4-benzenediol, 4,4′-(1-methylethylidene)bis[2-(1,1-dimethylethyl)phenol, 4,4′-disulfidebis[2,6-bis(1,1-dimethylethyl)]phenol, dimethyldithiocarbamic acid[3,5-bis(1,1-dimethyl 2-[[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]thio]acetic acid 2-ethylhexyl ester, 3-(5-chloro-2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenylpropanoic acid methyl ester, 4-butyl-2,6-bis(1,1-dimethylethyl)phenol, 2,6-bis(1,1-dimethylethyl)-4-(2-propen-1-yl)phenol, 2-(1,1-dimethylethyl)-4-[1-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-methylethyl]phenyl bis(4-nonylphenyl) phosphite, 4,4′-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)bis[2,6-bis(1,1-dimethylethyl)phenol], 3-(5-chloro-2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid octyl ester, 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid nitrilotri-2,1-ethylenediester, 4,4'-thiobis[2,6-bis(1,1-dimethylethyl)phenol, 4,4'-(1-methylethylidene)bis[2,6-bis(1,1-dimethylethyl)phenol, 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid 1,1',1"-[(2,4,6-trioxo-1,3,5-triazine-1,3,5(2H,4H,6H)-triyl) tris-2,1-ethylenediyl] ester, 2,6-bis(1-methylethyl)phenol, 2,6-diethylphenol, 2-ethyl-6-methylphenol, 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, 3,4-dihydro-2,2,5,7,8-pentamethyl-2H-1-chromen-6-ol, 2,2'-methylenebis[4-methyl-6-(1-methylcyclohexyl)phenol, 3,5-bis(1,1-dimethylethyl)-[1,1'-biphenyl]-4-ol, 4-(1,1-dimethylethyl)-2,6-dimethylphenol, 2,3,4,6-tetramethylphenol, 2,2'-(2-methylpropylene)bis[4,6-dimethylphenol], and mixtures thereof.

[0093] Preferably, the hindered phenol is selected from the group consisting of: 2,6-bis(1,1-dimethylethyl)-4-methyl-phenol; delta-tocopherol; C1-C2-3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionic acid; 18 Straight chain or branched chain alkyl esters; and mixtures thereof. C1-C 18 Preferred examples of linear or branched alkyl esters include 3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionic acid methyl ester (available under the trade name 35 was commercially available from Raschig USA, Arlington, Texas, United States) and octadecyl 3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionate (available under the trade name TS was commercially available from BASF, Ludwigshafen, Germany).

[0094] In a preferred non-limiting example, the hindered phenol may be 2,6-bis(1,1-dimethylethyl)-4-methyl-phenol.

[0095] Manufacturing method

[0096] Those skilled in the art will know how to prepare water-soluble unit dose articles and laundry detergent compositions according to the present invention using techniques known in the art.

[0097] use

[0098] Another aspect of the present invention is the use of an alkylated phenol or hindered phenol antioxidant for reducing malodor on fabrics, wherein the fabrics comprise at least one malodor source.

[0099] The washing liquid contains metal ions, preferably Cu 2+ The metal ions may be present on the fabric before the fabric is contacted with the wash liquid. The metal ions may be present in the malodor source on the fabric before the fabric is combined with the wash liquid. The metal ions may be present in the wash liquid when combined with the fabric. If present in the wash liquid, the metal ions may be present in the laundry detergent, water, or a mixture thereof. The malodor source may contain the metal ions at the point where the malodor source is applied to the fabric. Alternatively, the malodor source may be applied to the fabric and the metal ions applied later.

[0100] Preferably, at least one malodor source comprises a metal ion, more preferably Cu 2+ .

[0101] Another aspect of the invention is the use of a method according to the invention for reducing malodour on textiles in a wash liquor, and wherein the textiles comprise at least one malodour source, and wherein the wash liquor comprises metal ions, preferably Cu 2+ .

[0102] The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, 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."

[0103] Test Method

[0104] Odor Reduction Test Method

[0105] The compositions were tested for malodor reduction benefits using the following method.

[0106] A. Preparation of 75 grams of malodor marker

[0107] Fatty acids and malodor markers according to Table A were added to a 100 ml glass jar with a Teflon-lined cap and mixed thoroughly using a vortex.

[0108] Table A. Malodor Marker Compositions

[0109]

[0110]

[0111] B. Preparation of Body Stain Malodor Composition

[0112] Specific amounts of each material according to Table B were provided in 200 mL glass jars with Teflon-lined caps. Artificial body scale (ABS) is commercially available through Accurate Product Development; 2028 Bohlke Blvd, Fairfield, OH 45014.

[0113] Table B. Body Stain Malodor Composition

[0114]

[0115] C. Preparation of odor test fabric

[0116] Sixteen malodor test fabrics per wash load were prepared by applying 300 μl of the body soil malodor composition described in Table B to degummed 2×5 inch white poly-cotton 50 / 50 (PCW50 / 50) samples. 48 grams of the liquid detergent to be tested (see, e.g., Table 1 in Example 1 below) were added to a Duet 9200 washing appliance set to the normal cycle; a 77°F wash cycle followed by a 60°F rinse cycle. Cincinnati, OH, USA Municipal tap water was used, which contained ambient levels of copper due to, e.g., copper plumbing. The malodor test fabrics were washed in 7 gpg wash water with a 3.9 kg, 50×50 cm load of clean cotton and poly-cotton cloth, and then dried in a Maytag double stack tumble dryer set to low for 20 minutes. The dried fabrics were placed in a Mylar bag and sealed for 24 hours.

[0117] D. Odor analysis and detection on fabrics

[0118] The malodor reduction using the ABS / squalene malodor sensor was quantitatively determined by gas chromatography-mass spectrometry using an Agilent gas chromatograph 7890B equipped with a mass selective detector (5977B), a Chemstation quantitative pack, and a Gerstel multipurpose sampler equipped with a solid phase microextraction (SPME) probe. Calibration standards for 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 material purchased from Sigma Aldrich). The fabric was cut into uniform 2-inch by 2.5-inch pieces and placed in 10 mL headspace crimp-top vials. Prior to analysis, the vials were equilibrated for greater than 12 hours. The following settings were used in the autosampler: 80°C incubation temperature, 90 min incubation time, VT32-10 sample tray type, 22 mm vial penetration, 20 min extraction time, 54 mm injection penetration, and 300 s desorption time. The following settings were used for the pre-split / splitless inlet helium: split mode, 250°C temperature, 12 psi pressure, 79.5 mL / min total flow, 3 mL / min septum purge flow, 50:1 split ratio, and 22.5 min GC run time. The following settings were used in the oven: 40°C initial temperature, 12°C / min heating program, 250°C temperature, and 5 min hold time. Based on the partition coefficient (K at 80°C) of each component, the total nMol / L of 6-methyl-5-hepten-2-one (K = 3353), trans-2-heptenal (K = 3434), and 3-methyl-2-butenal (K = 1119) were calculated.

[0119] These values (in nmol / L) for the three measurements were added together to provide the total ABS / squalene marker (nmol / L) for a given test group.

[0120] E. Calculation of % of odor reduction oxidation products

[0121] The % Malodor Reduction Oxidation Products is provided as a percentage that compares the reduction in the amount of selected malodor markers provided by the test composition compared to a (no-antioxidant) reference composition. This value is determined as follows:

[0122] % reduction of oxidation products = (marker ref -Markers test )×100 / marker ref

[0123] markers ref and markers test The value of is defined as follows:

[0124] markers ref = Total ABS / squalene marker (nmol / L) of fabric washed with a formulation containing no antioxidant (e.g., a reference or control formulation)

[0125] markers test = Total ABS / squalene markers (nmol / L) of fabric washed with formulations containing the tested antioxidants

[0126] Since the measured oxidation products are generally considered to be malodorous, it is believed that the greater the % reduction in oxidation products provided by the composition, the less malodorous the treated fabric may have. Therefore, larger % malodor reduction oxidation product values are generally preferred. The compositions and methods of the present disclosure can provide a % malodor reduction oxidation product value 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%.

[0127] Reduction in malodor can also be reported as a marker ref and markers test The difference between and is thus shown as the absolute difference (eg ΔABS / squalene oxidation).

[0128] Test Method for Determining the Logarithm of the Octanol / Water Partition Coefficient (log D) at pH 7

[0129] For each antioxidant, the logarithm of the octanol / water partition coefficient at pH 7.00 (log D) was determined. Unitless log D values at pH 7 for known antioxidants were obtained from Chemical Abstracts Service (CAS, Columbus, Ohio, USA) where available. CAS provided data using Advanced Chemistry Development (ACD / Labs) Software V11.02 ( If the value was not available from CAS, it was determined using ACD software (Version 14.02 (Linux), available from Advanced Chemistry Development Inc., ACD / Labs, Toronto, Canada) using the default log PConsenses and pKa classical algorithms for log D calculations.

[0130] The antioxidants of the present invention have a log D at pH 7.00 that is greater than or equal to one or more of the claimed values (CVs). If the log D of the antioxidant compound of interest is not listed in the information available from Chemical Abstracts Service (CAS, Columbus, Ohio, USA), it can be calculated directly using ACD software.

[0131] If the calculated log D value at pH 7 (obtained from CAS (if available) or calculated using software) is less than CV-0.50, or is not listed and the log D at pH 7 is determined to be less than CV-0.50 via calculation using ACD software, then no experimental value needs to be measured. If the calculated log D value at pH 7 is listed as equal to or greater than CV-0.50 and less than or equal to CV+0.50, or is not listed and the log D at pH 7 is determined to be equal to or greater than CV-0.50 and less than or equal to CV+0.50 via calculation using ACD software, then experimental determination of the value must be performed to arrive at a value for the purposes of the present invention. In the present invention, the determination of the octanol-water partition coefficient is performed according to OECD Test No. 117: Partition Coefficient (n-Octanol / Water), HPLC Method. This method is available from the OECD iLibrary (https: / / www.oecd-ilibrary.org / ), an online library of the Organization for Economic Cooperation and Development (OECD).

[0132] Reversed-phase HPLC is performed on an analytical column packed with a solid phase containing long hydrocarbon chains chemically bonded to silica. Chemical substances are retained in the column in proportion to their hydrocarbon-water partition coefficient, with hydrophilic chemicals eluting first and lipophilic chemicals eluting last. The HPLC method covers a log Pow range of 0 to 6, but it can be extended to cover a log Pow range between 6 and 10 in special cases. The HPLC operating mode is isocratic. The test substance is injected into the column in the smallest detectable amount. The retention time is determined in duplicate. The partition coefficient of the test substance is obtained by interpolating the calculated capacity factor on the calibration chart. Extrapolation is necessary for very low and very high partition coefficients.

[0133] The pH of the eluent is critical for ionizable species. For the purposes of this invention, when performing the OECD 117 test, the eluent needs to be buffered to pH 7.00 ± 0.05. The value obtained depends on the log D at pH 7 of the material of interest.

[0134] Example

[0135] The examples provided below are intended to be illustrative in nature and not intended to be limiting.

[0136] Example 1. Exemplary Formulation (Heavy Duty Liquid Laundry Detergent)

[0137] The following heavy-duty liquid laundry detergent compositions can be prepared by conventional means known to those of ordinary skill in the art by combining the ingredients listed in Table 1. Composition 1A is a conventional premium laundry detergent that does not contain the antioxidants of the present disclosure. Compositions 1B to 1H are prepared from 1A by adding 0.035 wt % of the indicated antioxidants.

[0138] Table 1. Wt% of active ingredients in compositions 1A to 1H

[0139]

[0140]

[0141] 1. Linear alkylbenzene sulfonate with an average aliphatic carbon chain length of C11-C12, supplied by Stepan (Northfield, Illinois, USA)

[0142] 2. AE9 is a C12-14 alcohol ethoxylate with an average degree of ethoxylation of 9, supplied by Huntsman (Salt Lake City, Utah, USA)

[0143] 3. Diethylenetetraaminepentaacetic acid (DTPA), supplied by Dow Chemical (Midland, Michigan, USA); hydroxyethanediphosphonic acid (HEDP) supplied by Solutia, St Louis, Missouri, USA, or tetrasodium glutamate diacetate (GLDA) supplied by AkzoNobel, Amsterdam, The Netherlands, or diethylenetriamine (DETA) supplied by Huntsman, The Woodlands, Texas, USA may also be used.

[0144] 4. Polyethyleneimine (MW=600) with 20 ethoxylated groups per -NH group.

[0145] 5. The amphiphilic alkoxylated grease cleaning polymer is polyethyleneimine (MW=600) with 24 ethoxylated groups per -NH and 16 propoxylated groups per -NH.

[0146] 6. Proteases can be supplied by Genencor International (Palo Alto, California, USA) (e.g., Purafect ) or supplied by Novozymes (Bagsvaerd, Denmark) (e.g., ).

[0147] 7. All are products of Novozymes (Bagsvaerd, Denmark).

[0148] 8. Suitable fluorescent brighteners are e.g. AMS, CBS-X

[0149] 9. Methyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, CAS 6386-38-5

[0150] 10. 1,1′-[2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl]3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanoate, CAS 6683-19-8

[0151] 11. N,N′-1,6-Hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionamide, CAS 23128-74-7

[0152] 12.1,3,5-Tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, CAS 27676-62-6

[0153] 13. α-Tocopherol (3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H-1-benzopyran-6-ol), CAS 10191-41-0

[0154] 14. Chromanol (3,4-dihydro-2,2,5,7,8-pentamethyl-2H-1-benzopyran-6-ol), CAS 950-99-2

[0155] 15.3,4-Dihydro-6-hydroxy-2,5,7,8-tetramethyl-2H-1-benzopyran-2-carboxylic acid, CAS 53188-07-1

[0156] Example 2. Malodor Control by Using Antioxidants

[0157] To demonstrate the malodor controlling effect of the antioxidants of the present disclosure, various liquid detergent compositions were prepared according to Example 1 in Table 1 above. The compositions were tested for % reduction in oxidation products according to the test method provided above. The results are shown in Table 2.

[0158] Table 2. Effect of hindered phenols at 0.035 wt% on the formation of malodor markers .

[0159]

[0160]

[0161] The results show that although many of these structures provide a significant reduction in the total oxidation markers detected, not all antioxidants do so. The antioxidant in 1H, which has an ionizable carboxylic acid group, fails to show a beneficial effect. Compositions 1F and 1G have antioxidants with very similar structures relative to the phenolic portion, but do not have groups that are easily ionized or other strong solubilizing groups at neutral pH. The antioxidant used in composition 1H has a calculated log D value of -0.93 at pH 7 (calculated using Advanced Chemistry Development (ACD / Labs) Software V11.02), which means that it is almost 10 times more likely to be in water than in octanol when water is at pH 7 and the volumes of water and octanol are the same. Other hindered phenol antioxidants used (including those in compositions 1F and 1G) have log D values ranging from 3.79 to 18.83 at pH 7. Given that body soils are largely hydrophobic, it is perhaps understandable that a more highly water-soluble material such as 3,4-dihydro-6-hydroxy-2,5,7,8-tetramethyl-2H-1-benzopyran-2-carboxylic acid used in Formulation 9H did not provide a beneficial effect - it had little driving force to partition into the hydrophobic soil, which it must if it is to affect the soil's post-wash auto-oxidation events.

[0162] Example 3. Cu 2+ Impact on odor

[0163] This example demonstrates that the presence of copper in a wash liquor significantly affects the amount of auto-oxidation after subsequent washes, resulting in detectable malodor. Four parallel washes of a standard body soil sample were performed using 1000 ppm of commercially available Tide liquid detergent, with three wash solutions spiked with 400, 800, or 1200 ppb copper. The fourth wash liquor had no copper added and served as a control.

[0164] Analysis of washed and dried samples to determine the levels of malodor markers (3-methyl-2-butenal, trans-2-methyl-heptenal, and 6-methyl-5-hepten-2-one) showed that the addition of copper to the wash liquor resulted in increased levels of malodor markers produced, as shown in Table 3 below.

[0165] Table 3. Effect of copper ions on odor generation in washing liquid .

[0166] deal with <![CDATA[Add Cu 2+ (ppb)]]> ABS / squalene marker (nmol / L) A 0 62 B 200 120 C 400 162 D 800 163

[0167] Interestingly, adding more copper beyond 400 ppb did not further increase the levels of the markers detected, indicating that 400 ppb copper was likely sufficient to maximize the subsequent auto-oxidation of the soil present. For any given level of soil remaining on the fabric, it is reasonable to assume that there is a corresponding maximum amount of malodor markers that can be produced by that soil.

[0168] The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, 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."

[0169] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art to any of the presently disclosed or claimed inventions, or an admission that it, by itself or in combination with any one or more of the references, proposes, suggests, or discloses any such invention. Further, 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.

[0170] Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the invention. It is therefore intended that all such changes and modifications within the scope of the invention be encompassed in the appended claims.

Claims

1. A method for reducing malodor on fabrics, the method comprising the following steps: a. combining a fabric with a wash liquor, wherein the fabric comprises at least one malodor source, and wherein the wash liquor comprises a metal ion Cu 2+ , and wherein the wash liquor is prepared by diluting the laundry detergent composition in water by a factor between 100-fold and 3000-fold; b. washing the fabric in the wash liquor using an automatic washing operation, a manual washing operation, or a combination thereof; c. separating the fabric and the wash liquid from each other; d. drying the fabric; wherein the laundry detergent composition comprises from 0.025% to 1.5% by weight of the laundry detergent composition of a hindered phenol antioxidant selected from the group consisting of: C1-C12-3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionic acid; 18 linear or branched alkyl esters; 1,1'-[2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl] 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanoate; N,N'-1,6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanamide; 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; and chromanol (3,4-dihydro-2,2,5,7,8-pentamethyl-2H-1-chromen-6-ol); and wherein at least one of the antioxidants has a log D value at pH 7 equal to or greater than 1.

50.

2. A method according to claim 1, wherein the metal ions are introduced into the wash liquor by being present on the fabrics prior to contact with the wash liquor, by being present in the water used to prepare the wash liquor, or by a mixture thereof.

3. The method according to claim 1, a. wherein the fabric is washed in the wash liquor at a temperature between 5 ℃ and 60 ℃; b. wherein the washing operation in step b takes between 5 minutes and 60 minutes; c. or a mixture thereof.

4. The method of any one of claims 1-3, wherein the laundry detergent composition comprises a non-soap surfactant.

5. The method of claim 4, wherein the non-soap surfactant is selected from the group consisting of a non-soap anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a cationic surfactant, or a mixture thereof.

6. The method of claim 4, wherein the laundry detergent composition comprises between 10% and 60%, by weight of the laundry detergent composition, of the non-soap surfactant.

7. The method of claim 5, wherein the non-soap anionic surfactant comprises linear alkylbenzene sulfonate, alkoxylated alkyl sulfate, or mixtures thereof.

8. The method of claim 7, wherein the weight ratio of linear alkylbenzene sulfonate to ethoxylated alkyl sulfate is from 1:2 to 20:

1.

9. The method of claim 5, wherein the laundry detergent composition comprises between 5% and 50%, by weight of the detergent composition, of the non-soap anionic surfactant.

10. The method of claim 5, wherein the laundry detergent composition comprises between 0% and 10%, by weight of the laundry detergent composition, of a nonionic surfactant.

11. The method according to claim 5, wherein the nonionic surfactant is selected from alcohol alkoxylates, oxo alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates or mixtures thereof.

12. The method of any one of claims 1-3, wherein the laundry detergent composition comprises between 1.5% and 20% soap, by weight of the laundry detergent composition.

13. The method of claim 12, wherein the soap is a fatty acid salt.

14. The method of claim 12, wherein the soap is an amine-neutralized fatty acid salt.

15. The method of claim 14, wherein the amine is an alkanolamine.

16. The method of claim 14, wherein the amine is selected from monoethanolamine, diethanolamine, triethanolamine, or a mixture thereof.

17. The method according to any one of claims 1 to 3, wherein the laundry detergent composition comprises an ingredient selected from the list comprising: a cationic polymer, a polyester terephthalate, an amphiphilic graft copolymer, a carboxymethyl cellulose, an enzyme, a perfume, a bleach or mixtures thereof.

18. The method of claim 17, wherein the flavorant is an encapsulated flavorant.

19. The method of any one of claims 1-3, wherein the laundry detergent composition comprises a chelating agent.

20. The method of claim 19, wherein the chelating agent is selected from phosphonates, aminocarboxylates, polyfunctionally substituted aromatic chelating agents, or mixtures thereof.

21. The method of claim 20, wherein the phosphonate is an aminophosphonate.

22. The method of claim 19, wherein the chelating agent is selected from additional chelating agents.

23. The method of claim 22, wherein the additional chelating agent is selected from the group consisting of DTPA, HEDP, EDDS, DTPMP, EDTMP, Tiron ® , HPNO, MGDA, GLDA, EDTA, any suitable derivatives thereof, salts thereof, and mixtures thereof.

24. The method of any one of claims 1-3, wherein the laundry detergent composition comprises a hueing dye.

25. The method of any one of claims 1-3, wherein at least one of the antioxidants has a log D value equal to or greater than 2.50 at pH 7.

26. Use of the method according to any one of claims 1 to 3 for reducing malodour on textiles in a wash liquor, and wherein the textiles comprise at least one malodour source, and wherein the wash liquor comprises the metal ion Cu in a concentration equal to or greater than 50 ppb. 2+ .

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