Cleaning Composition

Abstract

The present disclosure relates generally to cleaning compositions, and more particularly to cleaning compositions comprising a mannanase enzyme and a xyloglucanase enzyme at a concentration of 0.0001% to 2% of the pure enzyme by weight of the total composition.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates generally to cleaning compositions, and more particularly to cleaning compositions comprising a combination of enzymes and polymers suitable for removing stains from soiled materials. [Background technology]

[0002] Modern laundry detergent and / or fabric care compositions contain a variety of detergent ingredients with one or more objectives to leave fabrics that are not only clean, but also retain their appearance and integrity. As such, detergent components such as perfumes, stain removers, fabric brighteners, fabric softeners, chelating agents, bleaching agents and catalysts, dye fixatives, and enzymes are incorporated into laundry detergent and / or fabric care compositions. One such specific example is the use of enzymes, particularly proteases, lipases, amylases, and / or cellulases.

[0003] Proteases are enzymes commonly used in cleaning applications. Proteases are known for their ability to hydrolyze other proteins. This property has been exploited by incorporating naturally occurring or engineered protease enzymes into laundry detergent compositions.

[0004] The inclusion of lipolytic enzymes in detergent compositions to improve cleaning performance is known, for example to aid in the removal of triglyceride-containing soils and stains from fabrics.

[0005] Amylase enzymes have long been recognized as detergent compositions for removing starchy food residues or starchy films from dishes or hard surfaces, and for cleaning starchy soils and other soils commonly found in laundry applications.

[0006] Stain removal is an important aspect of detergents, and sebum stains are considered to be predictive of body dirty stains in cleaning utility products. Even with the inclusion of proteases and amylases, there is still room for improvement in removing sebum stains. Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, there remains a need for laundry detergents and / or fabric care enzymes that have improved performance in a typical cleaning / fabric care cycle when cleaning sebum stains. [Means for solving the problem]

[0008] The present disclosure seeks to solve one or more of these needs by providing a composition comprising a detergent component, a mannanase enzyme at a concentration of 0.0001% to 2% by weight of the total composition of pure enzyme, and at least one or more cellulase enzymes, wherein the cellulase is selected from an endoglucanase (endolase) or a xyloglucanase enzyme.

[0009] The present disclosure further describes a detergent composition comprising a detergent ingredient, a mannanase enzyme at a concentration of 0.0001% to 2% of the pure enzyme by weight of the total composition, and a graft copolymer.The present disclosure further describes a detergent composition comprising a detergent ingredient, a mannanase enzyme at a concentration of 0.0001% to 2% of the pure enzyme by weight of the total composition, a cellulase, and a graft copolymer. DETAILED DESCRIPTION OF THE INVENTION

[0010] The features and advantages of the present invention will become apparent from the following description, including examples intended to give a broad representation of the invention. Various modifications will become apparent to those skilled in the art from this description and practice of the invention. The scope is not intended to be limited to the particular forms disclosed, but rather the invention covers all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.

[0011] As used herein, articles such as "the," "a," and "an," when used in a claim or the specification, are understood to mean one or more of what is claimed or described.

[0012] As used herein, the terms "include," "includes," and "including" are intended to be non-limiting.

[0013] The terms "substantially free" or "substantially free," as used herein, refer to either the complete absence of a component or its minimal presence merely as an impurity or unintended by-product of another component. A composition that is "substantially free" of a component means that the composition contains less than about 0.5%, 0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition, of that component.

[0014] As used herein, the phrases "detergent composition" and "cleaning composition" are used interchangeably and include compositions and formulations designed to clean soiled materials. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric strengthening compositions, fabric deodorizing compositions, laundry prewashes, laundry pretreatments, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, cleaning additives, post-rinse fabric treatments, ironing aids, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions may be used as laundry pretreatments, laundry post-treatments, or added during the rinse or wash cycle of a laundry operation.

[0015] The term "linear" refers to a straight chain, unbranched hydrocarbon.

[0016] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification includes every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0017] All cited patents and other documents are, in relevant part, incorporated by reference as if fully restated herein. The citation of any patent or other document is not an admission that the cited patent or other document is prior art to the present invention.

[0018] All concentrations and ratios herein are by weight of the detergent composition unless otherwise specified.

[0019] composition The composition of the present disclosure may be a detergent composition, more specifically, a laundry detergent composition. The composition may have a form selected from the group consisting of liquid, powder, single-phase or multi-phase unit dose, pouch, tablet, gel, paste, bar, and flake. The composition may have a form selected from the group consisting of liquid laundry detergent, gel detergent, single-phase or multi-phase unit dose detergent, single-phase or multi-phase or multi-compartment water-soluble pouch detergent, laundry pretreatment product, fabric softener composition, and mixtures thereof.

[0020] The term "liquid" includes aqueous compositions, non-aqueous compositions, gels, pastes, dispersions, and the like. As used herein, the phrase "laundry detergent composition" refers to a composition that can be used in laundry washing and / or rinsing operations. The laundry detergent composition may also be a laundry pretreatment composition. The composition may be a liquid laundry detergent composition present in a water-soluble unit dose article.

[0021] The compositions of the present disclosure may be detergent compositions and may include a combination of enzymes designed to remove sebum stains.

[0022] surfactants The compositions disclosed herein may comprise a surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, ampholytic surfactants, and mixtures thereof.

[0023] Anionic surfactants The compositions of the present disclosure may comprise at least about 10% by weight, or at least about 20% by weight, or at least about 30% by weight, or at least about 50% by weight, or at least about 60% by weight, or at least about 70% by weight of anionic surfactant. The compositions of the present disclosure may comprise less than 100% by weight, or less than 90% by weight, or less than about 85% by weight, or less than about 75% by weight, or less than about 70% by weight of anionic surfactant. The detergent compositions of the present disclosure may comprise from about 10% to about 50%, or from about 20% to about 70%, or from about 30% to about 75%, or from about 30% to about 65%, or from about 35% to about 65%, or from about 40% to about 60% anionic surfactant.

[0024] Anionic surfactants may exist in acid form, and the acid form may be neutralized to form surfactant salts. Typical neutralizing agents include hydroxides, such as metal counterion bases, such as NaOH or KOH. Further suitable neutralizing agents for neutralizing these acid forms of anionic surfactants include ammonia, amines, or alkanolamines. Non-limiting examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art. Suitable alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. Amine neutralization may be complete or partial; for example, a portion of the anionic surfactant mixture may be neutralized with sodium or potassium, and a portion of the anionic surfactant mixture may be neutralized with amines or alkanolamines.

[0025] Non-limiting examples of suitable anionic surfactants include any conventional anionic surfactant. This may include, for example, sulfate detergent surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid detergent surfactants, such as alkylbenzene sulfonates. Suitable anionic surfactants may be derived from renewable resources, waste, petroleum, or a mixture thereof. Suitable anionic surfactants may be linear, partially branched, branched, or a mixture thereof.

[0026] Alkoxylated alkyl sulfate materials include ethoxylated alkyl sulfate surfactants, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates. Examples of ethoxylated alkyl sulfates include water-soluble salts, particularly alkali metal, ammonium, and alkylolammonium salts, of organosulfur reaction products having alkyl groups containing from about 8 to about 30 carbon atoms in their molecular structure and sulfonic acids and salts thereof. (The term "alkyl" includes the alkyl portion of an acyl group. In some examples, the alkyl group contains from about 15 carbon atoms to about 30 carbon atoms. In other examples, the alkyl ether sulfate surfactant may be a mixture of alkyl ether sulfates having an average (arithmetic mean) carbon chain length in the range of from about 12 to 30 carbon atoms, in some examples from about 12 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide, in some examples from 1.8 moles of ethylene oxide. In a further example, the alkyl ether sulfate surfactant may have a carbon chain length of from about 10 carbon atoms to about 18 carbon atoms, and a degree of ethoxylation of from about 1 to about 6 moles of ethylene oxide. In yet a further example, the alkyl ether sulfate surfactant may include a peaked ethoxylation distribution.

[0027] Non-alkoxylated alkyl sulfates may also be added to the detergent compositions of the present disclosure and used as an anionic surfactant component. Examples of non-alkoxylated, e.g., non-ethoxylated, alkyl sulfate surfactants include higher C8-C 20 and those produced by the sulfation of fatty alcohols. In some examples, primary alkyl sulfate surfactants have the general formula: ROSO3 - M + (wherein R is typically a linear C8-C 20 In some examples, R is a hydrocarbyl group, which may be linear or branched, and M is a water-solubilizing cation. 10~C 18 In another example, R is C 12 / C 14 alkyl and M is sodium, such as that derived from a natural alcohol.

[0028] Other useful anionic surfactants may include alkali metal salts of alkylbenzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms in a linear (straight chain) or branched chain configuration. In some examples, the alkyl group is linear. Such linear alkylbenzene sulfonates are known as "LAS." In other examples, the linear alkylbenzene sulfonate may have an average of about 11 to 14 carbon atoms in the alkyl group. In a specific example, the linear alkylbenzene sulfonate may have an average of about 11.8 carbon atoms in the alkyl group, which may be abbreviated as C11.8LAS.

[0029] Suitable alkylbenzene sulfonates (LAS) can be obtained by sulfonating commercially available linear alkylbenzenes (LABs). Suitable LABs include low 2-phenyl LABs, such as those supplied by Sasol under the trade name Isochem® or Petrelab® by Petresa; other suitable LABs include high 2-phenyl LABs, such as those supplied by Sasol under the trade name Hyblene®. Suitable anionic detersive surfactants are alkylbenzene sulfonates obtained by the DETAL catalyzed process, although other synthetic routes, such as HF, may also be suitable. In one embodiment, magnesium salts of LAS are used.

[0030] Another example of a suitable alkylbenzene sulfonate is modified LAS (MLAS), which is a positional isomer containing a branch, such as a methyl branch, where the aromatic ring is attached to the 2- or 3-position of the alkyl chain.

[0031] The anionic surfactant may include a 2-alkyl branched primary alkyl sulfate that is 100% branched at the C2 position (C1 is the carbon atom covalently bonded to the alkoxylated sulfate moiety). 2-Alkyl branched alkyl sulfates and 2-alkyl branched alkyl alkoxy sulfates are generally derived from 2-alkyl branched alcohols (as hydrophobes). 2-Alkyl branched alcohols derived from the oxo process, such as 2-alkyl-1-alkanols or 2-alkyl primary alcohols, are commercially available from Sasol, e.g., LIAL®, ISALCHEM® (prepared from LIAL® alcohols by a fractional distillation process). C14 / C15 branched primary alkyl sulfates are also commercially available, e.g., LIAL® 145 sulfate.

[0032] The anionic surfactant may include a mid-chain branched anionic surfactant, for example, a mid-chain branched anionic detersive surfactant such as a mid-chain branched alkyl sulfate and / or a mid-chain branched alkyl benzene sulfonate.

[0033] Further suitable anionic surfactants include methyl ester sulfonates, paraffin sulfonates, α-olefin sulfonates, and internal olefin sulfonates.

[0034] The compositions disclosed herein may comprise an anionic surfactant selected from the group consisting of linear or branched alkylbenzene sulfonates, linear or branched alkoxylated alkyl sulfates, linear or branched alkyl sulfates, methyl ester sulfonates, paraffin sulfonates, α-olefin sulfonates, internal olefin sulfonates, and mixtures thereof. The compositions disclosed herein may comprise an anionic surfactant selected from the group consisting of linear or branched alkylbenzene sulfonates, linear or branched alkoxylated alkyl sulfates, linear or branched alkyl sulfates, and mixtures thereof. The compositions disclosed herein may also comprise a 2-alkyl branched primary alkyl sulfate.

[0035] Nonionic surfactants The compositions disclosed herein may contain a nonionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols. Nonionic surfactants have the formula R(OC2H4) n OH ethoxylated alcohols and ethoxylated alkylphenols, where R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkylphenyl radicals in which the alkyl group contains from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.

[0036] Other non-limiting examples of nonionic surfactants useful herein include C8-C 18 Alkyl ethoxylates (such as NEODOL® nonionic surfactants from Shell), where the alkoxylate units can be ethyleneoxy units, propyleneoxy units, or mixtures thereof, C6-C 12 Alkylphenol alkoxylate, C 12 ~C 18 C6-C with alcohol and ethylene oxide / propylene oxide block polymer 12 Alkylphenol condensates, such as Pluronic® from BASF, C 14 ~C 22 Medium-chain branched alcohols, BA, C 14 ~C 22 Medium Chain Branched Alkyl Alkoxylate, BAE x (wherein x is 1 to 30), alkyl polysaccharides, specifically alkyl polyglycosides, polyhydroxy fatty acid amides, and ether-terminated poly(oxyalkylated) alcohol surfactants are examples.

[0037] Suitable nonionic detersive surfactants also include alkyl polyglucosides and alkyl alkoxylated alcohols. Suitable nonionic surfactants further include those sold by BASF under the trade name Lutensol®.

[0038] Cationic surfactants The composition disclosed herein can comprise cationic surfactant.Non-limiting examples of cationic surfactant include quaternary ammonium surfactant, which can have 26 or less carbon atoms, and include alkoxylate quaternary ammonium (AQA) surfactant; dimethylhydroxyethyl quaternary ammonium; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactant; cationic ester surfactant; and amino surfactant, for example, amidopropyldimethylamine (APA).

[0039] Suitable cationic detersive surfactants also include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and mixtures thereof.

[0040] Suitable cationic detersive surfactants are quaternary ammonium compounds having the general formula: (R)(R1)(R2)(R3)N + X - wherein R is a linear or branched, substituted or unsubstituted C 6~18 R1 and R2 are independently selected from methyl or ethyl moieties, R3 is a hydroxyl, hydroxymethyl or hydroxyethyl moiety, and X is an anion that provides charge neutrality; suitable anions include halides such as chloride, sulfates, and sulfonates. Suitable cationic detersive surfactants include mono-C 6~18 Alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride. A highly suitable cationic detersive surfactant is mono-C 8~10 Alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride, mono-C 10~12 Alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride, and mono-C 10Alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride.

[0041] Zwitterionic surfactants The compositions disclosed herein may contain zwitterionic surfactants. Examples of zwitterionic surfactants include secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives, or derivatives of quaternary ammonium compounds, quaternary phosphonium compounds, or tertiary sulfonium compounds. Suitable examples of zwitterionic surfactants include alkyl dimethyl betaine and coco dimethylamidopropyl betaine, C8-C9 18 (For example, C 12 ~C 18 ) Amine oxides and alkyl groups of C8 to C 18 betaines, including sulfo and hydroxy betaines such as N-alkyl-N,N-dimethylamino-1-propanesulfonate, which may be:

[0042] amphoteric surfactants The composition disclosed herein may contain amphoteric surfactant.Examples of amphoteric surfactant include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group can be linear or branched, and one of the aliphatic substituents contains at least about 8 carbon atoms, or about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-soluble group, such as carboxy, sulfonate, or sulfate.Suitable amphoteric surfactants also include sarcosinate, glycinate, taurinate, and mixtures thereof.

[0043] Enzyme system The cleaning compositions of the present disclosure include an enzyme system. The enzyme system may be present in the cleaning composition at a concentration of about 0.0001% to about 5% by weight, or about 0.001% to about 2% by weight of the cleaning composition. The enzyme system may include a mannanase enzyme at a concentration of about 0.0001% to about 2% by weight of the cleaning composition, e.g., about 0.001% to about 1.5% by weight, about 0.009% to about 1.2% by weight, or about 0.01% to about 1% by weight of the cleaning composition, and one or more cellulase enzymes at a concentration of about 0.0001% to about 2% by weight of the cleaning composition, e.g., about 0.001% to about 1.5% by weight, about 0.009% to about 1.2% by weight, or about 0.01% to about 1% by weight of the cleaning composition.

[0044] An enzyme system comprises multiple enzymes, which may be provided singly or in combination, such as in a premix containing multiple enzymes.

[0045] The enzyme system includes a mannanase enzyme. The system may further include one or more cellulase enzymes. Surprisingly, it has been discovered that combining a mannanase with one or more cellulase enzymes results in a surprisingly improved ability to remove sebum stains from fabrics. The enzyme system may include a mannanase enzyme at a concentration of 0.0001% to 2% by weight of the total composition, e.g., about 0.001% to about 1.5%, about 0.009% to about 1.2%, or about 0.01% to about 1% of the pure enzyme. The enzyme system may comprise one or more cellulosic enzymes selected from the group consisting of xyloglucanase enzymes and any variants thereof, and endoglucanase (endolase) enzymes and any variants thereof, each at a concentration of 0.0001% to 2% by weight of the total composition, e.g., about 0.001% to about 1.5% by weight, about 0.009% to about 1.2% by weight, or about 0.01% to about 1% by weight of pure enzyme.

[0046] The enzyme system may further comprise a polymer. In particular, the enzyme system may further comprise a graft polymer, as described below.

[0047] cellulase Consumer products can contain cellulases of bacterial or fungal origin, including chemically modified or genetically engineered mutants. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, and Acremonium, such as fungal cellulases produced by Humicola insolens, Myceliophthora thermophila, and Fusarium oxysporum, as disclosed in U.S. Patent Nos. 4,435,307, 5,648,263, 5,691,178, 5,776,757, and 5,691,178. Suitable cellulases include alkaline or neutral cellulases with color care benefits. Commercially available cellulases include CELLUZYME®, CAREZYME®, and CAREZYME PREMIUM (Novozymes A / S), CLAZINASE®, and PURADAX HA® (Genencor International Inc.), KAC-500® (Kao Corporation).

[0048] Preferred cellulases include the following: a) A variant exhibiting at least 60% identity to SEQ ID NO: 2 in WO20171084560. Preferred substitutions include one or more positions corresponding to positions 292, 274, 266, 265, 255, 246, 237, 224, and 221 of the mature polypeptide of SEQ ID NO: 2, wherein the variant has cellulase activity. b) A variant exhibiting at least 70% identity to SEQ ID NO: 5 of WO2017106676. Preferred substitutions include one or more positions corresponding to positions 4, 20, 23, 29, 32, 36, 44, 51, 77, 80, 87, 90, 97, 98, 99, 102, 112, 116, 135, 136, 142, 153, 154, 157, 161, 163, 192, 194, 204, 208, 210, 212, 216, 217, 221, 222, 225, 227, and 232.

[0049] The bacterial cleaning cellulase can be a glycosyl hydrolase having enzymatic activity on amorphous cellulose substrates, wherein the glycosyl hydrolase is selected from GH family 5, 7, 12, 16, 44, or 74. Suitable glycosyl hydrolases also include GH family 44 glycosyl hydrolases (wild type) from Paenibacillus polyxyma, such as XYG1006, as described in U.S. Pat. No. 7,361,736, or variants thereof. GH family 12 glycosyl hydrolases (wild-type) from Bacillus licheniformis, such as SEQ ID NO: 1 as described in U.S. Pat. No. 6,268,197, or variants thereof; GH family 5 glycosyl hydrolases (wild-type) from Bacillus agaradhaerens, or variants thereof; GH family 5 glycosyl hydrolases (wild-type) from Paenibacillus, such as XYG1034 and XYG1022 as described in U.S. Pat. No. 6,630,340, or variants thereof; GH family 74 glycosyl hydrolases (wild-type) from Jonesia sp, such as XYG1020 as described in WO 2002 / 077242, or variants thereof; and Trichoderma reesei, such as the enzyme described in more detail in U.S. Pat. No. 7,172,891, SEQ ID NO: 2. Suitable bacterial cleaning cellulases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A / S, Bagsvaerd, Denmark).

[0050] In one aspect, the composition can include a fungal cleaning cellulase belonging to glycosyl hydrolase family 45 having a molecular weight of 17 kDa to 30 kDa, such as endoglucanases sold under the trade names Biotouch® NCD, DCC, DCL, and FLX1 (AB Enzymes, Darmstadt, Germany). Further preferred cellulases include those described in WO2016066896.

[0051] Mannanase As used herein, the term "mannanase" or "galactomannanase" refers to a mannanase enzyme, defined in accordance with what is known in the art as mannan endo-1,4-beta-mannosidase, also known as beta-mannanase and endo-1,4-mannanase, that catalyzes the hydrolysis of 1,4-beta-D-mannosidic linkages in mannans, galactomannans, glucomannans, and galactoglucomannans. Mannanases are classified as EC 3.2.1.78 according to enzyme nomenclature.

[0052] Suitable mannanases may be selected from the group consisting of: a) A mannanase having mannanase activity and a polypeptide having at least 85% sequence identity to residues 27-331 of SEQ ID NO: 3. SEQ ID NO: 3 corresponds to the full-length amino acid sequence of Man7 mannanase endogenous to Bacillus hemicellulosilyticus, including the signal sequence. b) The mannanase has mannanase activity and a polypeptide having at least 60% identity to SEQ ID NO: 4. In one embodiment of the invention, the mannanase has mannanase activity and a polypeptide having at least 80% identity to SEQ ID NO: 4. SEQ ID NO: 4 corresponds to the full-length amino acid sequence of the Man4 mannanase endogenous to Paenibacillus sp. c) Mannanases of glycoside hydrolase family 26 that catalyze the hydrolysis of 1,4-3-D-mannosidic bonds in mannans, galactomannans, and glucomannans. Suitable examples are described in WO2015040159.

[0053] Further preferred mannanases include those sold under trade names such as Mannaway® (all Novozymes A / S, Bagsvaerd, Denmark), Purabrite®, Effectenz®, Preferenz® (Genencor International Inc, Palo Alto, California), and Biotouch® (AB Enzymes, Darmstadt, Germany).

[0054] Proteases The compositions of the present invention can include proteases in addition to the proteases of the present invention. Mixtures of two or more proteases, especially when used in conjunction with anti-redeposition agents and / or sulfonated polymers, can contribute to enhanced cleaning over a wider temperature, cycle duration, and / or substrate range and can provide superior shine benefits.

[0055] Suitable proteases for use in combination with the variant proteases of the present invention include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, plant, or microbial origin. In one aspect, such suitable proteases may be of microbial origin.

[0056] Preferred concentrations of protease in the products of the present invention include about 0.05 to about 10 mg, more preferably about 0.5 to about 7 mg, and especially about 1 to about 6 mg of active protease per gram of composition.

[0057] amylase Preferably, the compositions of the present invention may contain amylase. Suitable α-amylases include those of bacterial or fungal origin, including chemically or genetically modified mutants. Preferred alkaline α-amylases are derived from Bacillus species, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus species, such as Bacillus species NCBI12289, NCBI12512, NCBI12513, DSM9375 (U.S. Pat. No. 7,153,818), DSM12368, DSMZ No. 12649, KSM AP1378 (WO 97 / 00324), KSM K36, or KSM K38 (EP 1,022,334).

[0058] Preferably, the product of the invention contains at least 0.01 mg, preferably about 0.05 to about 10 mg, more preferably about 0.1 to about 6 mg, especially about 0.2 to about 5 mg of active amylase per gram of composition.

[0059] Preferably, the protease and / or amylase of the compositions of the present invention is in the form of a granule, the granule comprising more than 29% sodium sulfate by weight of the granule, and / or the sodium sulfate and the active enzyme (protease and / or amylase) are in a weight ratio of 3:1 to 100:1, or preferably 4:1 to 30:1, or more preferably 5:1 to 20:1.

[0060] Lipase The enzyme system preferably further comprises a lipase. The presence of oils and / or fats can further increase the recovery of stains containing mannans and other polysaccharides. Therefore, the presence of lipase in the enzyme package can further improve the removal of such stains. Suitable lipases include those of bacterial, fungal, or synthetic origin, and their variants. Chemically modified or engineered variants are also suitable. Examples of suitable lipases include lipases from Humicola (synonym Thermomyces), such as H. lanuginosa (T. lanuginosus).

[0061] Pectate lyase Other preferred enzymes include pectate lyases sold under the trade names Pectawash®, Pectaway®, and Xpect®.

[0062] Nuclease enzymes The composition can include a nuclease enzyme, which is an enzyme capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids.

[0063] The enzyme system may include extracellular polymer degrading enzymes, including endo-β-1,6-galactanase enzymes.

[0064] Other enzymes The enzyme system can include other enzymes. Suitable enzymes provide cleaning performance and / or fabric care benefits. Examples of other suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, amylases, other cellulases, pectate lyases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, nucleases, reductases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, known amylases, or combinations thereof. Preferred enzyme systems further include a cocktail of conventional detergent enzymes, such as proteases, lipases, cutinases, and / or cellulases, in addition to amylases. Detersive enzymes are described in more detail in US Pat. No. 6,579,839.

[0065] Enzyme Stabilization System The compositions may optionally comprise from about 0.001% to about 10%, or from about 0.005% to about 8%, or from about 0.01% to about 6%, by weight of the composition, of an enzyme stabilization system. The enzyme stabilization system may be any stabilization system compatible with detersive enzymes. Such a system may be inherently provided by other formulation actives or may be added separately by the formulator or manufacturer of detergent-compatible enzymes. Such stabilization systems may include, for example, calcium ions, boric acid, propylene glycol, diethylene glycol, 2-methyl-1,3-propanediol, glycerol, sorbitol, calcium formate, short-chain carboxylic acids, boronic acids, chlorine bleach scavengers, and mixtures thereof, and are designed to address different stabilization concerns depending on the type and physical form of the detergent composition. For aqueous detergent compositions containing proteases, reversible protease inhibitors such as boron compounds, including borate, 4-formylphenylboronic acid, phenylboronic acid, and derivatives thereof, or compounds such as calcium formate, sodium formate, and 1,2-propanediol may be added to further improve stability.

[0066] Graft Copolymer The compositions and methods of the present disclosure relate to graft polymers. Broadly speaking, the graft polymers can be constructed and / or obtained by grafting (a) a polyalkylene oxide with (b) N-vinylpyrrolidone and (c) a vinyl ester, or by grafting (a) a polyalkylene oxide with (b) a vinyl ester. Graft polymers are described in more detail below.

[0067] Compositions according to the present disclosure may comprise from about 0.1% to about 50%, or from about 40%, or from about 25%, or from about 0.1% to about 15%, or from about 0.1% to about 10%, or from about 0.2% to about 5%, or from about 0.5% to about 7% by weight of the graft polymer. The graft polymer may be present in an aqueous treatment solution, such as the wash solution or rinse solution of an automatic washing machine, in an amount of from about 5 ppm, or from about 10 ppm, or from about 25 ppm, or from about 50 ppm, or from about 1500 ppm, or from about 1000 ppm, or from about 500 ppm, or from about 250 ppm.

[0068] The graft polymer can be constructed and / or obtained by grafting (a) a polyalkylene oxide having a number average molecular weight of about 1,000 to about 20,000, or about 15,000, or about 12,000, or about 10,000 daltons and based on ethylene oxide, propylene oxide, or butylene oxide, preferably ethylene oxide, with (b) N-vinylpyrrolidone and (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or the methyl or ethyl ester of acrylic or methacrylic acid, preferably vinyl acetate or a derivative thereof, wherein the weight ratio of (a):(b) is about 1:0.1 to about 1:1, the amount by weight of (a) being greater than the amount of (c), and the order of addition of the monomers (b) and (c) in the graft polymerization is not critical.

[0069] The graft polymer can be constructed and / or obtained by grafting (a) an alkylene oxide based on ethylene oxide having a number average molecular weight of about 1,000 to 20,000, or about 15,000, or about 12,000, or about 10,000 daltons, with (b) N-vinylpyrrolidone, and (c) vinyl acetate or a derivative thereof, wherein the weight ratio of (a):(b) is in the range of about 1:0.1 to about 1:2, or about 1:1; the weight ratio of (b):(c) is about 1:0.1 to about 1:5, or about 1:4; and the weight ratio of (a):(c) is about 1:0.1 to about 1:5, or about 1:3; and the order of addition of the monomers (b) and (c) in the graft polymerization is not critical.

[0070] The graft polymer can be obtained by grafting (a) an alkylene oxide having a number average molecular weight of about 1,000 to 20,000, or to about 15,000, or to about 12,000, or to about 10,000 Daltons and based on ethylene oxide with (b) N-vinylpyrrolidone, and (c) vinyl acetate or a derivative thereof, wherein the order of addition of the monomers (b) and (c) in the graft polymerization is not critical, the number of grafting sites is less than 1 per 50 ethylene oxide groups, and the composition is a fabric care composition.

[0071] The graft base used may be a polyalkylene oxide as specified in (a) above. The polyalkylene oxide of component (a) may have a number average molecular weight of about 300, or about 1000, or about 2000, or about 3,000, or about 20,000, or about 15,000, or about 12,000, or about 10,000, or about 8,000, or about 6,000 Daltons (Da). Without being bound by theory, it is believed that when the molecular weight of component (a) (e.g., polyethylene glycol) is relatively low, dye transfer prevention performance may be reduced. Additionally or alternatively, if the molecular weight is too high, the polymer may not remain suspended in solution and / or may adhere to the treated fabric.

[0072] The polyalkylene oxide can be based on ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, preferably ethylene oxide. The polyalkylene oxide can be based on an ethylene oxide homopolymer or an ethylene oxide copolymer having an ethylene oxide content of about 40 to about 99 mole %. Suitable comonomers for such copolymers include propylene oxide, n-butylene oxide, and / or isobutylene oxide. Suitable copolymers include copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and / or copolymers of ethylene oxide, propylene oxide, and at least one butylene oxide. The copolymers can have an ethylene oxide content of about 40 to about 99 mole %, a propylene oxide content of about 1 to about 60 mole %, and a butylene oxide content of about 1 to about 30 mole %. The graft base can be linear (straight chain) or branched, for example a branched homopolymer and / or a branched copolymer.

[0073] Branched copolymers can be prepared by adding ethylene oxide, with or without propylene oxide and / or butylene oxide, to a polyhydric low molecular weight alcohol, such as trimethylolpropane, a pentose, or a hexose. The alkylene oxide units can be randomly distributed in the polymer or present internally as blocks.

[0074] The polyalkylene oxide of component (a) may be the corresponding polyalkylene glycol in free form (i.e., with OH end groups) or may be capped with one or both end groups. Suitable end groups may be, for example, C1-C25 alkyl groups, phenyl groups, or C1-C14 alkylphenyl groups. The end groups may be C1-alkyl (e.g., methyl) groups. Suitable materials for the graft base include polyethylene glycols PEG300, PEG1000, PEG2000, PEG4000, PEG6000, PEG8000, and / or PEG10000, and / or monomethoxypolyethylene glycols MPEG2000, MPEG4000, MPEG6000, MPEG8000, and MEG10000, which are commercially available under the trade name Pluriol® from BASF.

[0075] Polyalkylene oxides can be grafted with N-vinylpyrrolidone as the monomer of component (b). Without wishing to be bound by theory, it is believed that the presence of N-vinylpyrrolidone ("VP") monomer in the grafted polymers of the present disclosure provides water solubility and better film-forming properties compared to similar polymers that do not contain the VP monomer. The vinylpyrrolidone repeat unit possesses amphiphilic properties with polar amide groups capable of forming dipoles, and nonpolar portions with methylene groups in the backbone and ring, making it hydrophobic. Too much vinylpyrrolidone content can lead to physical instability due to negative interactions with other ingredients in detergents, such as polishing agents, and high vinylpyrrolidone content also increases material costs.

[0076] The polyalkylene oxide can be grafted with a vinyl ester as the monomer of component (c). The vinyl ester can be derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms, or 1 to 3 carbon atoms, or 1 to 2 carbon atoms, or 1 carbon atom. The vinyl ester can be derived from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, or a mixture thereof. Suitable vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl isovalerate, vinyl caproate, or a mixture thereof. Preferred monomers of component (c) include vinyl acetate, vinyl propionate, methyl acrylate, a mixture of vinyl acetate and methyl acrylate, or a mixture thereof, preferably vinyl acetate. The monomers of the graft polymer, e.g., components (a), (b), and / or (c), can be present in a specific ratio, such as a weight ratio and / or a molar ratio.

[0077] For example, the weight ratio of (a):(b) can be from about 1:0.1 to about 1:1, or from about 1:0.2 to about 1:0.7. The weight ratio of (a):(b) can be from about 1:0.1 to about 1:2, or up to about 1:1. If the VP ratio is too high, the polymer may negatively interact with other detergent ingredients, such as brighteners, and / or may not work well with some hydrolyzed reactive dyes.

[0078] The weight ratio of (a):(c) can be greater than 1:1, from about 1:0.1 to about 1:0.8, or from about 1:0.2 to about 1:0.6. The weight ratio of (a):(c) can be from about 1:0.1 to about 1:5, or to about 1:3. The amount by weight of (a) can be greater than the amount of (c). Without being bound by theory, it is believed that relatively high concentrations of component (c) (e.g., vinyl acetate), particularly in relation to component (a), can result in reduced dye transfer prevention performance and / or relatively high hydrophobicity, which can lead to formulation and / or stability challenges.

[0079] The weight ratio of (b):(c) can be from about 1:0.1 to about 1:5, or to about 1:4. Without being bound by theory, too high a VP to VAc ratio can result in poor feel of the treated fabric. Additionally, negative interactions with ingredients such as brighteners can occur.

[0080] The graft polymer of the present disclosure can be characterized by a relatively low degree of branching (i.e., degree of grafting). In the graft polymer of the present disclosure, the average number of graft sites can be 1 or less, or 0.8 or less, or 0.6 or less, or 0.5 or less, or 0.4 or less per 50 alkylene oxide groups, e.g., ethylene oxide groups. The graft polymer can contain, on average, at least 0.05, or at least 0.1 graft sites per 50 alkylene oxide groups, e.g., ethylene oxide groups, based on the resulting reaction mixture. The degree of branching can be, for example, 13 The number of graft sites and the number of graft sites can be determined by the integrals of the signals of the -CH2- groups of the polyalkylene oxide using C NMR spectroscopy. The number of graft sites can be adjusted by manipulating the temperature and / or feed rate of the monomers. For example, the polymerization may be carried out in such a way that an excess of component (a) and the formed graft polymer are always present in the reactor. For example, the quantitative molar ratio of component (a) and the polymer to the ungrafted monomer (and initiator, if present) is generally about 10:1 or more, or about 15:1 or more, or about 20:1 or more.

[0081] The graft polymers of the present disclosure can be characterized by a relatively narrow molar mass distribution. For example, the graft polymers can have a polydispersity M of about 3 or less, or about 2.5 or less, or about 2.3 or less. w / M n The polydispersity of the graft polymer may be from about 1.5 to about 2.2. The polydispersity may be measured by gel permeation chromatography using narrow distribution polymethyl methacrylate as the standard.

[0082] The graft polymer can be prepared by grafting a suitable polyalkylene oxide (component (a)) with a monomer (component (b)) in the presence of a free radical initiator and / or by the action of high-energy radiation (which may include the action of high-energy electrons). This can be done, for example, by dissolving the polyalkylene oxide in at least one monomer (b), adding a polymerization initiator, and polymerizing the mixture completely. Alternatively, the graft polymerization can be carried out semi-continuously by first introducing a portion (e.g., 10%) of a mixture of the polyalkylene oxide to be polymerized, at least one monomer (b) and / or (c), and the initiator, heating the mixture to the polymerization temperature, and, after the initiation of polymerization, adding the remainder of the mixture to be polymerized at a rate appropriate for the polymerization rate. Alternatively, the graft polymer can be obtained by introducing the polyalkylene oxide of group (a) into a reactor, heating it to a polymerization temperature, and adding at least one monomer of group (b) and / or (c) and a polymerization initiator all at once, little by little, or continuously, preferably continuously, and polymerizing them.

[0083] In preparing the graft polymer, the order in which monomers (b) and (c) are grafted onto component (a) is not important and / or can be freely selected. For example, N-vinylpyrrolidone can be grafted onto component (a) first, followed by monomer (c) or a mixture of monomers from group (c). It is also possible to graft a monomer from group (c) onto graft base (a) first, followed by N-vinylpyrrolidone. It is also possible to graft a mixture of monomers (b) and (c) onto graft base (a) in one step. The graft polymer can be prepared by preparing graft base (a), then grafting N-vinylpyrrolidone and then vinyl acetate onto the graft base.

[0084] Any suitable polymerization initiator can be used, and examples of the polymerization initiator include organic peroxides such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl permalate, cumene hydroperoxide, diisopropyl peroxodicarbamate, bis(o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, mixtures thereof, redox initiators, and / or azo starters. The selection of the initiator may be related to the selection of the polymerization temperature.

[0085] The graft polymerization can be carried out at about 50° C. to about 200° C., or about 70° C. to about 140° C. The graft polymerization can typically be carried out under atmospheric pressure, but can also be carried out under reduced or superatmospheric pressure.

[0086] The graft polymerization can be carried out in a solvent. Suitable solvents include monohydric alcohols such as ethanol, propanol, and / or butanol; polyhydric alcohols such as ethylene glycol and / or propylene glycol; alkylene glycol ethers such as ethylene glycol monomethyl and ethyl ether and / or propylene glycol monomethyl and ethyl ether; polyalkylene glycols such as di- or tri-ethylene glycol and / or di- or tri-propylene glycol; polyalkylene glycol monoethers such as poly(C2-C3-alkylene)glycol mono(C1-C16-alkyl)ether having 3 to 20 alkylene glycol units; carboxylic acid esters such as ethyl acetate and ethyl propionate; aliphatic ketones such as acetone and / or cyclohexanone; cyclic ethers such as tetrahydrofuran and / or dioxane; or mixtures thereof.

[0087] Graft polymerization may also be carried out using water as a solvent. In such cases, the first step may be the introduction of a solution that is somewhat soluble in water, depending on the amount of monomer added (component (b)). To transfer water-insoluble products that may form during polymerization into solution, organic solvents, such as monohydric alcohols having 1 to 3 carbon atoms, acetone, and / or dimethylformamide, can be added. In the graft polymerization process in water, the water-insoluble graft polymer can also be converted into a fine dispersion by adding a conventional emulsifier or protective colloid, such as polyvinyl alcohol. The emulsifier used may be an ionic or nonionic surfactant with an HLB value of about 3 to about 13. The HLB value is determined based on the method described in W.C. Griffin's paper in J. Soc. Cosmet. Chem. 5 (1954), 249.

[0088] The amount of surfactant used in the graft polymerization process can be about 0.1 to about 5% based on the weight of the graft polymer. When water is used as a solvent, a solution or dispersion of the graft polymer may be obtained. When a solution of the graft polymer is prepared in an organic solvent or a mixture of an organic solvent and water, the amount of the organic solvent or solvent mixture per 100 parts by weight of the graft polymer can be about 5 to about 200 parts by weight, preferably about 10 to about 100 parts by weight.

[0089] The graft polymers may have a K value of from about 5 to about 200, preferably from about 5 to about 50, measured according to H. Fikentscher in a 2% strength by weight solution in dimethylformamide at 25°C.

[0090] After graft polymerization, the graft polymer may optionally be subjected to partial hydrolysis. The graft polymer may contain up to 60 mol%, or up to 50 mol%, or up to 40 mol%, or up to 25 mol%, or up to 20 mol%, or up to 15 mol%, or up to 10 mol% of the graft-on monomer of component (c) that has been hydrolyzed. For example, hydrolysis of a graft polymer prepared using vinyl acetate or vinyl propionate as component (c) results in a graft polymer containing vinyl alcohol units. Hydrolysis can be carried out, for example, by adding a base such as aqueous sodium hydroxide or potassium hydroxide, or by adding an acid, and optionally heating the mixture. Without being bound by theory, it is believed that increasing the concentration of hydrolyzed component (c) increases the relative hydrophilicity of the graft polymer.

[0091] A suitable amphiphilic graft copolymer is Sokalan® HP22, supplied by BASF. Suitable polymers include random graft copolymers, preferably polyvinyl acetate-grafted polyethylene oxide copolymers having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is typically about 6000, the weight ratio of polyethylene oxide to polyvinyl acetate is about 40-60, and there is no more than one grafting point per 50 ethylene oxide units.

[0092] builder The composition may include a builder. The composition typically includes at least about 1% by weight of builder, based on the total weight of the composition. Liquid detergent compositions may include up to about 10% by weight of builder, and in some examples, up to 8% by weight of builder, based on the total weight of the composition.

[0093] Suitable builders include aluminosilicates (e.g., zeolite builders such as zeolite A, zeolite P, and zeolite MAP), silicates, phosphates, such as polyphosphates (e.g., sodium tripolyphosphate), especially its sodium salt; carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sesquicarbonates; organic mono-, di-, tri-, and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium, or alkanolammonium salts, as well as oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic types, and phytic acid. Additional suitable builders may be selected from citric acid, lactic acid, fatty acids, polycarboxylate builders, such as copolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and copolymers of acrylic acid and / or maleic acid, and other suitable ethylenic monomers with various types of additional functional groups. Alternatively, the composition may be substantially free of builders.

[0094] structurant / thickener Suitable structurants / thickeners include dibenzylidene polyol acetal derivatives. The fluid detergent composition can include from about 0.01% to about 1%, or from about 0.05% to about 0.8%, or from about 0.1% to about 0.6%, or even from about 0.3% to about 0.5% by weight of a dibenzylidene polyol acetal derivative (DBPA). The DBPA derivative can include a dibenzylidene sorbitol acetal derivative (DBS).

[0095] Suitable structurants / thickeners also include bacterial cellulose. The fluid detergent composition may contain from about 0.005% to about 1% by weight of bacterial cellulose network. The term "bacterial cellulose" encompasses any type of cellulose produced by fermentation of bacteria of the genus Acetobacter, such as CELLULON® by CPKelco US, and includes materials commonly referred to as microfibrillated cellulose, reticulated bacterial cellulose, and the like.

[0096] Suitable structurants / thickeners also include coated bacterial cellulose. The bacterial cellulose may be at least partially coated with a polymeric thickener. The at least partially coated bacterial cellulose may comprise about 0.1% to about 5%, or even about 0.5% to about 3%, by weight of bacterial cellulose and about 10% to about 90% by weight of the polymeric thickener. Suitable bacterial celluloses include those described above, and suitable polymeric thickeners include carboxymethylcellulose, cationic hydroxymethylcellulose, and mixtures thereof.

[0097] Suitable structurants / thickeners also include cellulose fibers. The composition may contain about 0.01% to about 5% cellulose fibers by weight of the composition. Cellulose fibers can be extracted from vegetables, fruits, or wood. Commercially available examples include Avicel® from FMC, Citri-Fi from Fiberstar, or Betafib from Cosun.

[0098] Suitable structurants / thickeners also include non-polymeric crystalline hydroxyl-functional materials. The composition may comprise from about 0.01% to about 1% by weight of the composition of a non-polymeric crystalline hydroxyl-functional structurant. The non-polymeric crystalline hydroxyl-functional structurant may generally comprise a crystallizable glyceride that can be pre-emulsified to aid dispersion in the final fluid detergent composition. The crystallizable glyceride may include hydrogenated castor oil, or "HCO," or a derivative thereof, provided that it can be crystallized in the liquid detergent composition.

[0099] Suitable structurants / thickeners also include polymeric structurants. The composition may contain from about 0.01% to about 5% by weight of a naturally derived and / or synthetic polymeric structurant. Examples of naturally derived polymeric structurants for use in the present invention include hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Suitable polysaccharide derivatives include pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Examples of synthetic polymeric structurants for use in the present invention include polycarboxylates, polyacrylates, hydrophobically modified ethoxylated urethanes, hydrophobically modified nonionic polyols, and mixtures thereof.

[0100] Suitable structurants / thickeners also include diamide gelling agents. The external structuring system may include a diamide gelling agent having a molecular weight of about 150 g / mol to about 1,500 g / mol, or even about 500 g / mol to about 900 g / mol. Such diamide gelling agents may contain at least two nitrogen atoms, at least two of which form amide functional substituents. The amide groups may be different or the same. Non-limiting examples of diamide gelling agents are N,N'-(2S,2'S)-1,1'-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide, dibenzyl (2S,2'S)-1,1'-(propane-1,3-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)dicarbamate, dibenzyl (2S,2'S)-1,1'-(dodecane-1,12-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)dicarbamate.

[0101] Polymeric dispersants The cleaning composition may include one or more polymeric dispersants. Examples are carboxymethylcellulose, poly(vinyl-pyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic acid / acrylic acid copolymers, and lauryl methacrylate / acrylic acid copolymers.

[0102] The cleaning composition has the following general structure: bis((C2H5O)(C2H4O) n )(CH3)-N + -C x H 2x -N + -(CH3)-bis((C2H5O)(C2H4O) n ), wherein n=20-30 and x=3-8, or sulfated or sulfonated variants thereof.

[0103] The cleaning composition may include an amphiphilic alkoxylated grease-cleaning polymer, which has balanced hydrophilic and hydrophobic properties to remove grease particles from fabrics and surfaces. The amphiphilic alkoxylated grease-cleaning polymer may include a core structure and multiple alkoxylate groups attached to the core structure. These may include, for example, alkoxylated polyalkyleneimines having an inner polyethylene oxide block and an outer polypropylene oxide block. Such compounds may include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and sulfated versions thereof. Polypropoxylated derivatives may also be included. A wide variety of amines and polyalkyleneimines can be alkoxylated to various degrees. A useful example is a 600 g / mole polyethyleneimine core ethoxylated to 20 EO groups per NH, available from BASF. The detergent compositions described herein may comprise from about 0.1% to about 10%, in some examples from about 0.1% to about 8%, and in other examples from about 0.1% to about 6%, by weight of the detergent composition, of an alkoxylated polyamine.

[0104] Carboxylate polymer—The detergent composition may also contain one or more carboxylate polymers, which may optionally be sulfonated. Suitable carboxylate polymers include maleate / acrylate random copolymers or poly(meth)acrylate homopolymers. In one embodiment, the carboxylate polymer is a poly(meth)acrylate homopolymer having a molecular weight of 4,000 Da to 9,000 Da or 6,000 Da to 9,000 Da.

[0105] Alkoxylated polycarboxylates may also be used in the detergent compositions herein to remove grease. Such materials are described in International Publication No. WO 91 / 08281 and International Application No. PCT 90 / 01815. Chemically, these materials comprise poly(meth)acrylates with one ethoxy side chain for every 7-8 (meth)acrylate units. The side chains have the formula -(CH2CHO) m (CH2)n CH3, where m is 2-3 and n is 6-12. The side chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary but may be in the range of about 2000 to about 50,000. The detergent compositions described herein may comprise from about 0.1% to about 10%, in some examples from about 0.25% to about 5%, and in other examples from about 0.3% to about 2%, by weight of the detergent composition, of an alkoxylated polycarboxylate.

[0106] Stain Removal Polymer Suitable copolymers may comprise a structure defined by a combination of structural units (I), (II), (III), (IV), for example, a combination of one or more of (I) and (IV), a combination of one or more of (II) and (IV), a combination of one or more of (III) and (IV), a combination of one or more of (I), (II) and (IV), a combination of one or more of (II), (III) and (IV), a combination of one or more of (I) and (II), or a combination of any two or more of (I), (II), (III), or (IV), a combination of one or more of (I), (II), (III), and (IV), a combination of one or more of (I) and (II), or a combination of any two or more of (I), (II), (III), or (IV): (I)-[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d (II)-[(OCHR 3 -X-CHR 4 ) b -O-OC-Ar-CO-] e (III)-[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e (IV)-[(OCHR 5 -CHR 6 ) c-OR 7 ] f During the ceremony, a, b, and c are 1 to 200; d, e, and f are 1 to 50; Ar is 1,4-substituted phenylene; sAr is a 1,3-substituted phenylene substituted at the 5-position with SO3M; M is Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri-, or tetra-alkylammonium (the alkyl groups are C1-C 18 Alkyl or C2-C 10 hydroxyalkyl), or mixtures thereof; X is a difunctional group containing at least one carbon atom and at least one hydroxyl unit or at least one amine unit; R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently H or C1 to C 18 n- or iso-alkyl; R 7 is a straight or branched chain C1-C 18 Alkyl, or linear or branched C2-C 30 Alkenyl or cycloalkyl groups having 5 to 9 carbon atoms, or C8 to C 30 Aryl group or C6-C 30 It is an arylalkyl group.

[0107] The polyester terephthalate according to the present invention generally has a number average molecular weight of 700 to 50,000 g / mol, preferably 800 to 25,000 g / mol, more preferably 1,000 to 15,000 g / mol, and most preferably 1,200 to 12,000 g / mol.

[0108] Examples of suitable polyester stain release polymers include TexCare® polymers supplied by Clariant, such as TexCare® SRA-100, SRA-300, SRN-100, SRN-170, SRN-240, SRN-260, SRN-300, and SRN-325. Other suitable stain release polymers are Marloquest® polymers supplied by Sasol, such as Marloquest® SL, HSCB, L235M, B, and G82. Other suitable polyester stain release polymers are the REPLE-O-TEX® line of polymers supplied by Rhodia, such as REPEL-O-TEX® SF, SF-2, and SRP6. Cellulosic Polymers

[0109] The cleaning compositions of the present invention may also include one or more cellulosic polymers, including those selected from alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, and alkyl carboxyalkyl celluloses. In one embodiment, the cellulosic polymer is selected from the group consisting of carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose, methylcarboxymethyl cellulose, and mixtures thereof. In one embodiment, the carboxymethyl cellulose has a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.

[0110] amine Additional amines may be used in the compositions described herein to further remove grease and particles from soiled materials. The compositions described herein may contain from about 0.1% to about 10%, or from about 0.1% to about 4%, or from about 0.1% to about 2% of the additional amine by weight of the composition. Non-limiting examples of additional amines include, but are not limited to, polyetheramines, polyamines, oligoamines, triamines, diamines, pentamines, tetraamines, or combinations thereof. Specific examples of suitable additional amines include tetraethylenepentamine, triethylenetetraamine, diethylenetriamine, or mixtures thereof.

[0111] bleach The detergent compositions of the present invention may contain one or more bleaching agents. Suitable bleaching agents other than bleach catalysts include photobleaches, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, and mixtures thereof. Generally, when a bleaching agent is used, the detergent compositions of the present invention may contain from about 0.1% to about 50%, or even from about 0.1% to about 25%, by weight of the detergent composition, of the bleaching agent.

[0112] bleaching catalyst The detergent compositions of the present invention may also contain one or more bleach catalysts capable of accepting an oxygen atom from a peroxyacid and / or its salt and transferring the oxygen atom to an oxidizable substrate. Suitable bleach catalysts include, but are not limited to, iminium cations and polyions, iminium zwitterions, modified amines, modified amine oxides, N-sulfonylimines, N-phosphonylimines, N-acylimines, thiadiazole dioxides, perfluoroimines, cyclic sugar ketones, and mixtures thereof.

[0113] Brightener Optical brighteners or other brightening or whitening agents can be incorporated into the detergent compositions described herein at levels of from about 0.01% to about 1.2% by weight of the composition. Commercially available optical brighteners suitable for the present invention can be divided into subgroups, including, but not limited to, derivatives of stilbenes, pyrazolines, coumarins, benzoxazoles, carboxylic acids, methine cyanines, dibenzothiophene-5,5-dioxides, azoles, 5- and 6-membered heterocycles, and various other materials. In some examples, the optical brightener is disodium 4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate (whitening agent 15, commercially available under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation), disodium 4,4′-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate (commercially available under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation), disodium 4,4′-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate (commercially available under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation). More preferably, the optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate.

[0114] The whitening agent may be added in particulate form or as a premix with a suitable solvent, e.g., a non-ionic surfactant, propanediol.

[0115] Fabric color toning agent The composition may include a fabric hueing agent (sometimes referred to as a tinting agent, bluing agent, or whitening agent). Typically, the hueing agent imparts a blue or purple hue to the fabric. The hueing agents can be used either alone or in combination to create a specific hue and / or tint different types of fabric. This can be achieved, for example, by mixing a red and a green-blue dye to produce a blue or purple hue. The hueing agent may be selected from any known chemical class of dyes, including, but not limited to, acridines, anthraquinones (including polycyclic quinones), azines, azos including premetallized azos (e.g., monoazos, diazos, trisazos, tetrakisazos, polyazos), benzodifurans and benzodifuranones, carotenoids, coumarins, cyanines, diazahemicyanines, diphenylmethanes, formasans, hemicyanines, indigoids, methanes, naphthalimides, naphthoquinones, nitro and nitroso, oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof.

[0116] Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes also include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes classified under the Color Index (CI) classification of direct dyes, basic dyes, reactive or hydrolyzed reactive dyes, solvent dyes, or disperse dyes, which are classified as, for example, blue, purple, red, green, or black, and which produce the desired shade either alone or in combination. Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing covalently attached (sometimes referred to as bonded) chromogens (dye-polymer conjugates), such as polymers having chromogens copolymerized into the polymer backbone, and mixtures thereof. Suitable polymeric dyes also include those selected from the group consisting of fabric substantive colorants sold under the name Liquitint® (Milliken, Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers containing a moiety selected from the group consisting of hydroxyl moieties, primary amine moieties, secondary amine moieties, thiol moieties, and mixtures thereof. Suitable polymeric dyes also include those selected from the group consisting of Liquitint® Violet CT, carboxymethyl cellulose (CMC) covalently bonded to a reactive blue, reactive violet, or reactive red dye, such as CMC conjugated with CI Reactive Blue 19 sold by Megazyme (Wicklow, Ireland) under the trade name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenyl-methane polymeric colorants, alkoxylated thiophene polymeric colorants, and mixtures thereof.

[0117] The aforementioned fabric toning agents may be used in combination (any mixture of fabric toning agents may be used).

[0118] Mounting agent The composition may include an encapsulating agent. The encapsulating agent may include a core and a shell having an inner surface and an outer surface, the shell encapsulating the core.

[0119] The encapsulating agent may include a core and a shell, wherein the core comprises a material selected from fragrances, whitening agents, dyes, insect repellents, silicones, waxes, fragrances, vitamins, fabric softeners, skin care agents such as paraffin, enzymes, antibacterial agents, bleaching agents, sensates, or mixtures thereof, and the shell comprises a material selected from polyethylene, polyamides, polyvinyl alcohol, optionally containing other comonomers, polystyrene, polyisoprene, polycarbonates, polyesters, polyacrylates, polyolefins, polysaccharides such as alginates and / or chitosan, gelatin, shellac, epoxy resins, vinyl polymers, water-insoluble inorganic materials, silicones, amino resins, or mixtures thereof. When the shell comprises an amino resin, the amino resin may comprise a polyurea, polyurethane, and / or polyurea urethane. The polyurea may comprise polyoxymethylene urea and / or melamine formaldehyde.

[0120] The encapsulant may include a core, and the core may include a fragrance. The encapsulant may include a shell, and the shell may include melamine formaldehyde and / or crosslinked melamine formaldehyde. The encapsulant may include a core including a fragrance and a shell including melamine formaldehyde and / or crosslinked melamine formaldehyde.

[0121] Suitable encapsulants may comprise a core material and a shell, the shell at least partially surrounding the core material. The core of the encapsulant comprises a perfume raw material and / or optionally another material, such as a material selected from vegetable oils, esters of vegetable oils, esters, linear or branched hydrocarbons, partially hydrogenated terphenyls, dialkyl phthalates, alkyl biphenyls, alkylated naphthalenes, petroleum refinements, aromatic solvents, silicone oils, or mixtures thereof.

[0122] The encapsulant wall may comprise a suitable resin, such as a reaction product of an aldehyde and an amine. Suitable aldehydes include formaldehyde. Suitable amines include melamine, urea, benzoguanamine, glycoluril, or a mixture thereof. Suitable melamines include methylolmelamine, methylated methylolmelamine, iminomelamine, and a mixture thereof. Suitable ureas include dimethylolurea, methylated dimethylolurea, urea-resorcinol, or a mixture thereof.

[0123] Suitable formaldehyde scavengers may be used together with the encapsulating agent, for example in a capsule slurry, and / or may be added to the composition before, during, or after the encapsulating agent is added to such composition.

[0124] Suitable capsules can be purchased from Encapsys Inc. (Appleton, Wisconsin USA).

[0125] fragrance Perfumes and fragrance ingredients may be used in the detergent compositions described herein. Non-limiting examples of perfumes and fragrance ingredients include, but are not limited to, aldehydes, ketones, esters, and the like. Other examples include various natural extracts and natural essences, which can include complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam extract, sandalwood oil, pine oil, cedar, and the like. The final perfume can include a highly complex mixture of such ingredients. The finished perfume can be included at a concentration ranging from about 0.01% to about 2% by weight of the detergent composition.

[0126] Dye transfer inhibitor The fabric detergent composition may also include one or more materials effective in inhibiting the transfer of dyes from one fabric to another during the washing process. Generally, such dye transfer inhibitors can include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. When used, these agents may be used at a concentration of from about 0.0001% to about 10% by weight of the composition, in some instances from about 0.01% to about 5% by weight of the composition, and in other instances from about 0.05% to about 2% by weight of the composition.

[0127] chelating agents The detergent compositions described herein may also contain one or more metal ion chelating agents. Suitable molecules include copper, iron, and / or manganese chelating agents and mixtures thereof. Such chelating agents can be selected from the group consisting of phosphonates, aminocarboxylates, aminophosphonates, succinates, polyfunctionally substituted aromatic chelating agents, 2-pyridinol-N-oxide compounds, hydroxamic acids, carboxymethyl inulin, and mixtures thereof. The chelating agents can be present in acid form or salt form, including alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof. Other chelating agents suitable for use herein are commercially available DEQUEST series, as well as chelating agents from Monsanto, Akzo-Nobel, DuPont, Dow, and the Trilon® series from BASF and Nalco.

[0128] The chelating agent may be present in the detergent compositions disclosed herein from about 0.005% to about 15%, from about 0.01% to about 5%, from about 0.1% to about 3.0%, or from about 0.2% to about 0.7%, or from about 0.3% to about 0.6% by weight of the detergent compositions disclosed herein.

[0129] Foam suppressor The detergent compositions described herein can incorporate compounds to reduce or suppress foam formation. Foam suppression can be particularly important in so-called "high concentration wash processes" and in front-loading washing machines. The detergent compositions herein may contain from 0.1% to about 10%, by weight of the composition, of a suds suppressor.

[0130] Examples of foam suppressors include monocarboxylic fatty acids and soluble salts thereof, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C 18 ~C 40 Included are ketones (eg, stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point below about 100° C., silicone suds suppressors, and secondary alcohols.

[0131] Further suitable antifoaming agents are those derived from phenylpropylmethyl-substituted polysiloxanes.

[0132] The detergent composition may comprise a suds suppressor selected from an organo-modified silicone polymer having aryl or alkylaryl substituents in combination with a primary filler that is a silicone resin and modified silica. The detergent composition may comprise from about 0.001% to about 4.0%, by weight of the composition, of such suds suppressor.

[0133] The detergent composition may comprise a suds suppressor selected from: a) a mixture of about 80 to about 92% ethylmethyl, methyl(2-phenylpropyl)siloxane, about 5 to about 14% MQ resin in octyl stearate, and about 3 to about 7% modified silica; b) a mixture of about 78 to about 92% ethylmethyl, methyl(2-phenylpropyl)siloxane; about 3 to about 10% MQ resin in octyl stearate; and about 4 to about 12% modified silica; or c) mixtures thereof, the percentages being by weight of the antifoam agent.

[0134] Conditioning Agent The compositions of the present invention may contain a high-melting-point fatty compound. High-melting-point fatty compounds useful herein have a melting point of 25°C or higher and are selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof. Such compounds with low melting points are not intended to be included in this section. The high-melting-point fatty compound is present in the composition at a concentration of about 0.1% to about 40% by weight of the composition, preferably about 1% to about 30% by weight, more preferably about 1.5% to about 16% by weight, and even more preferably about 1.5% to about 8% by weight.

[0135] The compositions of the present invention may also include a nonionic polymer as a conditioning agent.

[0136] Conditioning agents suitable for use in the compositions include those generally characterized as silicones (e.g., silicone oils, cationic silicones, silicone gums, high refractive index silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty acid esters), or combinations thereof, or conditioning agents that otherwise form liquid particles dispersed in the aqueous surfactant matrix herein. The concentration of silicone conditioning agents typically ranges from about 0.01 to about 10%.

[0137] The compositions of the present invention may also include from about 0.05% to about 3% of at least one organic conditioning oil, either as the sole conditioning agent or in combination with other conditioning agents, such as silicones (described herein). Suitable conditioning oils include hydrocarbon oils, polyolefins, and fatty acid esters.

[0138] Fabric-reinforced polymers. Suitable fabric-reinforced polymers are typically cationically charged and / or have a high molecular weight. Suitable concentrations of this component range from 0.01% to 50%, preferably 0.1% to 15%, more preferably 0.2% to 5.0%, and most preferably 0.5% to 3.0% by weight of the composition. The fabric-reinforced polymer may be a homopolymer or may be formed from two or more types of monomers. The monomer weight of the polymer generally ranges from 5,000 to 10,000,000, typically at least 10,000, and preferably 100,000 to 2,000,000. Preferred fabric reinforcing polymers have a cationic charge density of at least about 0.2 meq / g, preferably at least 0.25 meq / g, more preferably at least 0.3 meq / g, but also preferably less than 5 meq / g, more preferably less than 3 meq / g, and most preferably less than 2 meq / g, at the pH of the intended use of the composition (which pH generally ranges from pH 3 to pH 9, preferably from pH 4 to pH 8). The fabric reinforcing polymer may be of natural or synthetic origin.

[0139] pearlescent agent The laundry detergent compositions of the present invention may also contain pearlescent agents. Non-limiting examples of pearlescent agents include mica, titanium dioxide-coated mica, bismuth oxychloride, fish scales, and alkylene glycol monoesters and diesters. The pearlescent agent may be ethylene glycol distearate (EGDS).

[0140] antioxidants The compositions of the present disclosure may also contain an antioxidant. Without being bound by theory, it is believed that antioxidants, particularly in combination with the oligoamines of the present disclosure, can help improve the malodor control and / or cleaning performance of the compositions. Antioxidants can also help reduce yellowing that may be associated with amines, allowing for the formulation of relatively high levels of amines. Antioxidants are materials such as those described in Kirk-Othmer (Vol. 3, p. 424) and Ullmann's Encyclopedia (Vol. 3, p. 91).

[0141] The compositions of the present disclosure may also include an antioxidant, preferably a hindered phenol antioxidant, in an amount of from about 0.001% to about 2%, preferably from about 0.01% to about 0.5%, by weight of the composition.

[0142] Suitable antioxidants include those having the following general formula:

[0143] [ka] [Wherein R is C1 to C 22 Straight chain alkyl or C3-C 22 and (2) optionally substituted with an organic group comprising an alkyleneoxy or polyalkyleneoxy group selected from EO (ethoxy), PO (propoxy), BO (butoxy), and mixtures thereof, more preferably EO alone or an EO / PO mixture; R is preferably methyl, branched C3-C6 alkyl, or C1-C6 alkoxy, preferably methoxy; R is C3-C6 branched alkyl, preferably tert-butyl; and x is 1 or 2.

[0144] A preferred class of alkylated phenols having this formula can include hindered phenol compounds. As used herein, the term "hindered phenol" refers to (a) at least one C3 or higher branched alkyl, preferably a C3-C6 branched alkyl, preferably tert-butyl, attached in the ortho position relative to at least one phenolic -OH group, or (b) a C1-C6 alkoxy, preferably methoxy, ... 22 Straight chain alkyl or C3-C 22 The term "hindered phenol" is used to refer to a compound containing a phenol group bearing either a branched alkyl, preferably methyl, or a branched C3-C6 alkyl, or a substituent independently selected from the group consisting of a mixture thereof. If the phenyl ring contains multiple -OH groups, the compound is a hindered phenol as long as at least one such -OH group is substituted as described immediately above. If any R group in the above structure contains three or more consecutive monomers, the antioxidant is defined herein as a "polymeric hindered phenol antioxidant." Compositions according to the present disclosure may contain a hindered phenol antioxidant. A preferred hindered phenol antioxidant is 3,5-di-tert-butyl-4-hydroxytoluene (BHT).

[0145] A further class of hindered phenol antioxidants that may be suitable for use in the compositions is represented by the following formula:

[0146] [ka] wherein R1 and R2 are each independently alkyl, or R1 and R2 can join together to form a C5-C6 cyclic hydrocarbyl moiety; B is absent or CH2; R4 is a C1-C6 alkyl; R5 is hydrogen or —C(O)R3; and R3 is hydrogen or a C1-C6 alkyl group. 19R is alkyl, R is C1-C6 alkyl, R is hydrogen or C1-C6 alkyl, X is -CH2OH or -CH2A, and A is a nitrogen-containing unit, phenyl, or substituted phenyl. Preferred nitrogen-containing A units include amino, pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.

[0147] Suitable hindered phenol antioxidants may include 2,6-bis(1,1-dimethylethyl)-4-methyl-phenol, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid, methyl ester, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, octadecyl ester, or mixtures thereof.

[0148] Commercially available antioxidants that may be suitable include BHT, RALOX 35™, and / or TINOGARD TS™.

[0149] Additional antioxidants may be used. Examples of antioxidants suitable for use in the composition 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 may 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.

[0150] It may be preferable to use non-yellowing antioxidants, such as non-yellowing hindered phenol antioxidants.If it leads to perceptible negative attributes in consumer experience (for example, yellow by-products adhere to fabrics), the antioxidants that form such yellow by-products can be avoided.Those skilled in the art can make informed decisions about the selection of antioxidants to use.

[0151] Odor reducer Suitable oligoamines for reducing malodour in fabrics include diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), dipropylenetriamine (DPTA), 5-methyldipropylenetriamine (5-MeDPTA), triethylenetetraamine (TETA), 4-methyltriethylenetetraamine (4-MeTETA), 4,7-dimethyltriethylenetetraamine (4,7-Me2TETA), 1,1,4,7,7-pentamethyldiethylenetriamine (M5-DETA), tripropylenetetraamine (TPTA), tetraethylenepentamine (TEPA), tetrapropylenepentamine (TPPA), pentaethylenehexamine (PEHA), pentapropylenehexamine (PPHA), hexaethyleneheptamine (HEHA), hexapropyleneheptamine (HPHA), N,N'-bis(3-aminopropyl)ethylenediamine, or mixtures thereof.

[0152] The oligoamine is preferably diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), 1,1,4,7,7-pentamethyldiethylenetriamine (M5-DETA), dipropylenetriamine (DPTA), 5-methyldipropylenetriamine (5-MeDPTA), triethylenetetramine (TETA), tripropylenetetraamine (TPTA), tetraethylenepentamine (TEPA), tetrapropylenepentamine (TPTA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof, more preferably diethylenetriamine. The diethylenetriamine may be selected from diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), 1,1,4,7,7-pentamethyldiethylenetriamine (M5-DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof, even more preferably diethylenetriamine (DETA), 4-methyldiethylenetriamine (4-MeDETA), N,N'-bis(3-aminopropyl)ethylenediamine, and mixtures thereof, most preferably diethylenetriamine (DETA). DETA may be preferred due to its low molecular weight and / or relatively low manufacturing costs.

[0153] buffer system The detergent compositions described herein may be formulated so that during use in aqueous cleaning operations, the wash water has a pH of from about 7.0 to about 12, and in some examples, from about 7.0 to about 11. Techniques for controlling pH at recommended use levels include the use of buffers, alkalis, or acids, and are known to those skilled in the art. These techniques include, but are not limited to, the use of sodium carbonate, citric acid or sodium citrate, lactic acid or lactate salts, monoethanolamine or other amines, boric acid or borate salts, and other pH-adjusting compounds known in the art.

[0154] The detergent compositions herein may comprise a dynamic wash pH profile, in which the wax-coated citric acid particles may be used in conjunction with other pH control agents to (i) achieve a wash liquor pH greater than 10 after about 3 minutes of contact with water, (ii) achieve a wash liquor pH less than 9.5 after about 10 minutes of contact with water, (iii) achieve a wash liquor pH less than 9.0 after about 20 minutes of contact with water, and (iv) optionally achieve an equilibrium wash liquor pH in the range of about 7.0 to about 8.5.

[0155] Water-soluble film The compositions of the present disclosure may be encapsulated in a water-soluble film, for example, a film comprising polyvinyl alcohol (PVOH).

[0156] Other supplement ingredients A wide variety of other ingredients may be used in the detergent compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, and solid or other liquid fillers, erythrosine, colloidal silica, waxes, probiotics, surfactin, aminocellulose polymers, zinc ricinoleate, perfume microcapsules, rhamnolipids, sophorolipids, glycopeptides, methyl ester sulfonates, methyl ester ethoxylates, sulfonated estolides, degradable surfactants, biopolymers, silicones, modified silicones, aminosilicones, deposition aids, locust bean gum, cationic hydroxyethyl cellulose polymers, cationic guar, hydrotropes (especially cumene sulfonates, toluene sulfonates, xylene sulfonates, and naphthyl salts), antioxidants, BHT, PVA particle-encapsulated dyes. or fragrances, pearlizing agents, effervescent agents, color change systems, silicone polyurethanes, opacifiers, tablet disintegrants, biomass fillers, quick-drying silicones, glycol distearate, hydroxyethyl cellulose polymers, hydrophobically modified cellulose polymers or hydroxyethyl cellulose polymers, starch flavor encapsulating agents, emulsified oils, bisphenol antioxidants, microfibrillar cellulose structuring agents, properfumes, styrene / acrylate polymers, triazines, soaps, superoxide dismutase, benzophenone protease inhibitors, functionalized TiO2, dibutyl phosphate, silica flavor capsules, and other adjunct ingredients, silicates (e.g., sodium silicate, potassium silicate), choline oxidase, pectate lyase, mica, titanium dioxide coated mica, bismuth oxychloride, and other active agents.

[0157] The compositions described herein may also contain vitamins and amino acids, such as water-soluble vitamins and their derivatives, water-soluble amino acids and their salts and / or derivatives, water-insoluble amino acid viscosity modifiers, dyes, non-volatile solvents or diluents (water-soluble and water-insoluble), pearlizing aids, foam boosters, additional surfactants or non-ionic co-surfactants, pediculicides, pH adjusters, fragrances, preservatives, chelating agents, proteins, skin active agents, sunscreens, UV absorbers, vitamins, niacinamide, caffeine, and minoxidil.

[0158] The compositions of the present invention may also contain pigment materials such as nitroso, monoazo, disazo, carotenoid, triphenylmethane, triarylmethane, xanthene, quinoline, oxazine, azine, anthraquinone, indigoid, thioindigoid, quinacridone, phthalocyanine, plant and natural colors, including water-soluble components such as those with CI names. The detergent compositions of the present invention may also contain antimicrobial agents.

[0159] water The compositions disclosed herein may contain about 1 to about 80% water by weight of the composition. When the composition is a heavy-duty liquid detergent composition, the composition typically contains about 40% to about 80% water. When the composition is a compact liquid detergent, the composition typically contains about 20% to about 60%, or about 30% to about 50% water. When the composition is in unit dose form, for example, encapsulated in a water-soluble film, the composition typically contains less than 20%, or less than 15%, or less than 12%, or less than 10%, or less than 8%, or less than 5% water.

[0160] How to use The present invention includes a method for cleaning soiled materials.The compact fluid detergent composition suitable for sale to consumers is suitable for use in laundry pre-treatment applications, laundry cleaning applications, and home care applications.

[0161] Such methods include, but are not limited to, contacting the detergent composition, either in neat form or diluted in a wash liquor, with at least a portion of the soiled material, and then optionally rinsing the soiled material. The soiled material may be subjected to a washing step before the optional rinsing step.

[0162] For use in laundry pretreatment applications, the method can include contacting soiled fabrics with the detergent compositions described herein. Following pretreatment, the soiled fabrics can be laundered in a washing machine or otherwise rinsed.

[0163] A machine washing method can include treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispersed therein an effective amount of a machine laundry detergent composition according to the present invention. An "effective amount" of detergent composition means about 20 g to about 300 g of product dissolved or dispersed in a wash solution volume of about 5 L to about 65 L. Water temperatures can range from about 5°C to about 100°C. The ratio of water to soiled material (e.g., fabric) can be about 1:1 to about 30:1. The compositions can be used at concentrations of about 500 ppm to about 15,000 ppm in solution. In the context of fabric washing compositions, the use concentration can also vary depending on the type and severity of 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-loading, front-loading, top-loading, vertical-axis Japanese automatic washing machine).

[0164] The detergent compositions herein can be used to launder fabrics at reduced wash temperatures. These fabric laundering methods include the steps of: adding the laundry detergent composition to water to form a wash liquor; and adding fabrics to be laundered to the wash liquor, the temperature of the wash liquor being 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 laundry detergent composition with water.

[0165] Another method involves contacting a nonwoven substrate impregnated with the detergent composition with the soiled material. As used herein, "nonwoven substrate" can include any conventional nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics. Non-limiting examples of suitable commercially available nonwoven substrates include those sold under the tradenames SONTARA® by DuPont and POLYWEB® by James River Corp.

[0166] Also included are hand wash / soak methods and combination hand wash using semi-automatic washing machines.

[0167] Packaging the composition Compact fluid detergent compositions suitable for consumer use can be packaged in any suitable container, including those constructed from paper, cardboard, plastic materials, and any suitable laminate. Compact fluid detergent compositions can also be enclosed in a water-soluble film and packaged as unitized dose detergent compositions, for example, as single-compartment pouches or multi-compartment pouches having stacked and / or side-by-side compartments. [Example]

[0168] In the following examples, the individual ingredients within the cleaning compositions are expressed as a percentage by weight of the cleaning composition.

[0169] Example 1. Liquid or gel detergent Table 1 shows exemplary liquid or gel detergent fabric care compositions that can be prepared by mixing the listed ingredients in the proportions shown below. The graft copolymer, mannanase and cellulase enzymes, xyloglucanase and endolase are added as described in the specific examples below.

[0170] [Table 1] 1Available from Shell Chemicals (Houston, TX). 2 Available from Huntsman Chemicals (Salt Lake City, UT). 3 Available from Sasol Chemicals, Johannesburg, South Africa. 4 Available from The Procter & Gamble Company, Cincinnati, OH. 5 Available from Sigma Aldrich chemicals (Milwaukee, WI). 6 Available from DuPont-Genencor (Palo Alto, CA). 7 Available from Novozymes (Copenhagen, Denmark). 8 Polyethyleneimine core with a molecular weight of 600 g / mol and 20 ethoxylate groups per —NH available from BASF (Ludwigshafen, Germany). 9 Polyethyleneimine core with 24 ethoxylate groups per —NH and 16 propoxylate groups per —NH, molecular weight 600 g / mol. Available from BASF (Ludwigshafenm, Germany). 10 Available from BASF (Ludwigshafenm, Germany) and described in U.S. Pat. No. 8,143,209. 11 Available from BASF, Ludwigshafenm, Germany, as described in WO 01 / 05874 or as described herein. 12 Available from Elementis Specialties (Highstown, NJ) under the trade name Thixin®.

[0171] Example 2. Soluble single or multi-compartment unit dose liquid detergent The following compositions were prepared by mixing the individual components in the proportions indicated below and then enclosing them in a water-soluble poly(vinyl alcohol) film manufactured by Monosol to form water-soluble unit-dose laundry pouches. Each unit-dose laundry pouch contained 29.9 g of detergent composition. The graft copolymer, mannanase and cellulase enzymes, xyloglucanase, and endolase were added as described in the specific examples below.

[0172] [Table 2] 1 Available from Shell Chemicals (Houston, TX). 2 Available from Huntsman Chemicals (Salt Lake City, UT). 3 Available from Sasol Chemicals, Johannesburg, South Africa. 4 Available from The Procter & Gamble Company, Cincinnati, OH. 5 Available from Sigma Aldrich chemicals (Milwaukee, WI). 6 Available from DuPont-Genencor (Palo Alto, CA). 7 Available from Novozymes (Copenhagen, Denmark). 8 Available from Ciba Specialty Chemicals (High Point, NC). 9 Available from Milliken Chemical (Spartanburg, SC). 10Polyethyleneimine core with a molecular weight of 600 g / mol and 20 ethoxylate groups per —NH available from BASF (Ludwigshafen, Germany). 11 Polyethyleneimine core with 24 ethoxylate groups per —NH and 16 propoxylate groups per —NH, molecular weight 600 g / mol. Available from BASF (Ludwigshafenm, Germany). 12 Available from BASF, Ludwigshafenm, Germany, WO 01 / 05874, or as described herein. 13 Available from Elementis Specialties (Highstown, NJ) under the trade name Thixin®.

[0173] Example 3. Improving sebum removal of detergents with mannanase and cellulase enzymes. Stain removal is an important aspect of detergents, and sebum stains are believed to predict body soiling in utility cleaning applications. The compositions of the present invention, including a combination of mannanase and at least one cellulase enzyme, have excellent sebum stain removal with PSC132-identified sebum. As can be seen from Table 3, the addition of cellulase enzymes, xyloglucanase (XYG) (3B), or a combination of XYG and endolase (3C) to Comparative Example 3A results in sebum stain removal within a standard deviation, thus providing comparable removal. While sebum stain removal is improved with mannanase (3E), the combination of mannanase and xyloglucanase (3F) and the combination of mannanase, xyloglucanase, and endolase (3H) provide even greater sebum stain removal, with an improvement of 10-12 units. These improvements are surprising because XYG or the combination of XYG and Endolase do not show any improvement in sebum removal over the comparative detergents (3B and 3C compared to 3A). Without being bound by theory, it is believed that the mannanase and cellulase enzymes exert a synergistic effect in removing sebum stains, and that the enzymes complement each other in an unexpected way to cleanse sebum to a level not achievable by either enzyme individually.

[0174] [Table 3] a) Xyloglucanase (XYG) available under the trade name Whitezyme from Novozymes (Copenhagen, Denmark); b) Endolase available under the trade name Celluclean 5000l from Novozymes (Copenhagen, Denmark); c) Stain removal data lower standard deviation LSD = 3; high standard deviation HSD = 5; d) Stain removal data lower standard deviation LSD = 2; high standard deviation HSD = 3; e) Stain removal data lower standard deviation LSD = 2; high standard deviation HSD = 4

[0175] Example 4. Graft Copolymer Examples The following table, Table 4, provides illustrative, non-limiting examples of graft copolymers according to the present disclosure. See Examples 4A-4C.

[0176] [Table 4] PEG = poly(ethylene glycol); VP = vinylpyrrolidone; VAc = vinyl acetate

[0177] Synthetic graft copolymer 4A is described in WO 01 / 05874 and is available from BASF (Ludwigshafenm, Germany). Synthesis of graft copolymer 4B A polymerization vessel equipped with a stirrer and reflux condenser is initially charged under a nitrogen atmosphere with 720 g of PEG (4000 g / mol) and 60 g of ethyl acetate. The mixture is homogenized at 70 °C. Next, 432 g of vinyl acetate (2 h), 288 g of vinylpyrrolidone (5 h), 576 g of ethyl acetate (5 h), and 30.2 g of tert-butyl perpivalate (196.6 g of ethyl acetate (5.5 h) are metered in. After complete addition of the feed, the solution is stirred at 70 °C for 1 h. Then, 3.8 g of tert-butyl perpivalate in 25.0 g of ethyl acetate (1.5 h) is metered in, followed by stirring for 0.5 h. The volatiles are removed by vacuum stripping. Then, 676.8 g of deionized water is added, and steam distillation is carried out at 100 °C for 1 h. The resulting graft polymer is characterized by a K value of 20.8. The solids content of the final solution is 48.8%.

[0178] Polymer 4B is hydrolyzed to give 4C.

[0179] Example 5. ASTM Dust Sebum Removal Increased with 3.4% Graft Copolymer 4A and XYG and Mannanase Table 5 shows that the addition of 3.4% graft copolymer 4A with mannanase and XYG improves ASTM dust sebum removal (Example 5E). Example 5B with mannanase or Example 5C with mannanase and XYG have the same sebum removal as Comparative Detergent Example 5A. The addition of 3.4% graft copolymer 4A (Example 5D) has similar sebum removal to Comparative Detergent Example 5A. Surprisingly, the combination of 3.4% graft copolymer 4A, mannanase, and XYG in Detergent 1A (Example 5E) improves sebum stain removal by 9 units. Without being bound by theory, it is believed that the combination of mannanase and xyloglucanase may unexpectedly impact sebum stains by complementing each other in an unexpected way to cleanse sebum at a level not achievable by each individual enzyme. Furthermore, without wishing to be bound by theory, it is believed that the addition of the graft copolymer aids in removing sebum in an unexpected way, resulting in a significant increase in the removal of sebum stains.

[0180] [Table 5] a) Graft copolymer added to detergent composition 1A at 3.4%; b) Stain removal data Lower standard deviation LSD=5; High standard deviation HSD=8;

[0181] Example 6. ASTM Dust Sebum Removal Increased with 3.4% Graft Copolymer 4B and XYG and Mannanase Table 6 shows that the addition of graft copolymer 4B with mannanase and XYG (Example 6D) improved ASTM dust sebum removal by 10 units compared to detergent Example 6A without mannanase and cellulase enzymes and Example 6B with mannanase and XYG. As shown in Table 6 below, the addition of graft copolymer 4B without mannanase and XYG (Example 6C) improved sebum removal by 5 units, and the improvement increased to 10 units for Example 6D with graft copolymer 4B, mannanase, and XYG enzymes.

[0182] [Table 6] a) Graft copolymer added at 6.8% to detergent composition 1A; b) Stain removal data Lower standard deviation LSD=3; High standard deviation HSD=4;

[0183] Example 7. Improvement of sebum removal with graft copolymer 4C Table 7 shows that the addition of graft copolymer 4C, mannanase, and XYG improves sebum removal for PCS132. Example 7B shows that the addition of 0.6% graft copolymer 4C, mannanase, and XYG improves sebum removal by 11 units compared to Example 7A, a detergent containing only 0.6% graft copolymer 4A without additional mannanase and cellulase enzymes. Sebum removal efficacy is further increased with 4.5% graft copolymer 4C, mannanase, and XYG, resulting in 14 units of sebum removal efficacy compared to Comparative Example 7A, which contains 0.6% graft copolymer 4A.

[0184] [Table 7] a) Xyloglucanase (XYG) available under the trade name Whitezyme from Novozymes (Copenhagen, Denmark). b) Stain removal data Lower standard deviation LSD=4 High standard deviation HSD=6.

[0185] Test Method Sebum stain removal method CW120 cotton technical stain swatches containing PCS132 identified sebum and PCS94 ASTM dust sebum (available from Accurate Product Development, Fairfield, OH) are treated with the detergent composition of the present invention using the cotton short cycle wash setting of a Miele W174 WE FL washing machine. The washing machine has a fill capacity of 13.1 L and uses water at 40°C for the wash and 15°C for the rinse cycle. The wash and rinse cycles are performed using 15 grains per gallon of water. After filling with water at the beginning of the wash cycle, 58 g of the detergent composition is added to the washing machine drum. Two CW120 stain swatches and 2.9 kg of desized fabric ballast are then placed in the drum. The desized ballast consisted of approximately 50% by weight 100% cotton T-shirts (Gildan T-shirts, TCS Apparel), 25% by weight 50% polyester / 50% cotton pillowcases (Standard Textile Company), and 25% by weight 86% cotton / 14% polyester towels (Standard Textile Company). A total of eight CW120 swatches were averaged from two internal replicates across four different wash cycles. The treated fabrics were dried in a Kenmore series dryer on the cotton / hot setting.

[0186] Using standard colorimetric measurements, the L for each stain before and after cleaning was * , a * , and b * The value was obtained. * , a * , b * From the values, the stain level was calculated by comparing the initial stain level before washing with the stain level after washing, with an initial background corresponding to the unsoiled fabric area.

[0187] Stain removal from the swatches was measured as follows:

[0188]

number

[0189] The SRI value is the average SRI value from eight replicates. The stain level of the fabric before washing (ΔE initial ) is high, stains are removed during the washing process, and stain levels after washing (ΔE washed ) is lowered. The better the stain is removed, the lower the ΔE washed The value of ΔE initial and ΔE washed The difference between (ΔE initial -ΔE washed ) is greater. Therefore, the better the cleaning performance, the higher the Stain Removal Index value.

[0190] Working Example: A. A detergent composition comprising detergent ingredients, a mannanase enzyme at a concentration of 0.0001% to 2% pure enzyme by weight of the total composition, and at least one cellulase enzyme. B. The detergent composition of paragraph A, wherein at least 1v of the cellulase enzyme is selected from the group consisting of an endolase enzyme or a xyloglucanase enzyme. C. The detergent composition of paragraph A or B, wherein the Endolase enzyme is present at a concentration of 0.0001% to 2% of pure enzyme by weight of the composition. D. The detergent composition of any one of paragraphs A-C, wherein the xyloglucanase enzyme is present at a concentration of 0.0001% to 2% of pure enzyme by weight of the composition. E. The detergent composition of any one of paragraphs A-D, further comprising a surfactant chosen from anionic surfactants, nonionic surfactants, cationic surfactants, and / or mixtures thereof. F. The detergent composition of any one of paragraphs A through E, further comprising a bleaching agent. G. The detergent composition of any one of paragraphs A-F, further comprising a builder, preferably zeolite, layered sodium silicate, sodium tripolyphosphate, and / or mixtures thereof. H. The detergent composition of any one of paragraphs A through G, wherein the composition further comprises a suspension graft copolymer. I. The detergent composition of paragraph H, wherein the suspension graft copolymer is selected from the group consisting of poly(vinyl acetate)-g-poly(ethylene glycol), poly(vinylpyrrolidone)-poly(vinyl acetate)-g-poly(ethylene glycol), and combinations thereof. J. The detergent composition of paragraph I, wherein the graft copolymer has a hydrolysis rate of vinyl acetate units of 0 to 60%. K. The detergent composition of any one of paragraphs A-J, wherein the composition further comprises a dye transfer inhibitor. L. The detergent composition of paragraph K, wherein the dye transfer inhibitor is selected from the group consisting of polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. M. The detergent composition of any one of paragraphs A-L, wherein the composition further comprises a structuring agent. N. The detergent composition of any one of paragraphs HM, wherein the suspension graft copolymer is present at a concentration of from about 0.1% to about 15% by weight of the composition. O. A method of treating fabrics, comprising contacting the fabrics with the detergent composition described in any one of paragraphs A-N.

[0191] 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 "approximately 40 mm."

[0192] All documents cited herein, including any cross-referenced documents or related patents or applications, are incorporated herein by reference in their entirety unless expressly excluded or otherwise limited. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or that it alone, or in combination with any other reference(s), teaches, suggests, or discloses any such invention. 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.

[0193] 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 detergent composition comprising: detergent ingredients; a mannanase enzyme at a concentration of 0.0001% to 2% pure enzyme by weight of the total composition; at least one cellulase enzyme at a concentration of 0.0001% to 2% pure enzyme by weight of the total composition; and a suspension graft copolymer at a concentration of 0.1% to 15% by weight of the total composition; the at least one cellulase enzyme is selected from the group consisting of an endolase enzyme or a xyloglucanase enzyme; the suspension graft copolymer is selected from the group consisting of poly(vinyl acetate)-g-poly(ethylene glycol), poly(vinylpyrrolidone)-poly(vinyl acetate)-g-poly(ethylene glycol), and combinations thereof; A detergent composition wherein said suspension graft copolymer has a hydrolysis rate of said vinyl acetate units of 20 to 60 mole percent.

2. 10. The detergent composition of claim 1, comprising a surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, and / or mixtures thereof.

3. 3. The detergent composition of claim 1, further comprising a bleaching agent.

4. The detergent composition according to any one of claims 1 to 3, further comprising a builder.

5. A detergent composition described in any one of claims 1 to 4, wherein the builder is selected from the group consisting of zeolite, layered sodium silicate, sodium tripolyphosphate, and mixtures thereof.

6. A detergent composition according to any preceding claim, wherein the composition further comprises a dye transfer inhibitor.

7. 7. The detergent composition of claim 6, wherein the dye transfer inhibitor is selected from the group consisting of polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof.

8. A detergent composition according to any preceding claim, wherein the composition further comprises a structuring agent.

9. A method of treating fabrics, comprising contacting said fabrics with a detergent composition according to any one of claims 1 to 8.

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