Detergent compositions containing branched surfactants

Abstract

The present invention relates generally to detergent compositions, and more particularly to detergent compositions containing branched surfactants.

Description

[Technical Field]

[0001] The present invention relates generally to detergent compositions, and more particularly to detergent compositions containing branched surfactants. [Background technology]

[0002] Due to the increasing popularity of easy-care fabrics made from synthetic fibers, as well as ever-increasing energy costs and growing ecological concerns among detergent users, the once-popular warm and hot water washing has given way to cold water (below 30°C) fabric washing. Many commercial laundry detergents are advertised as being suitable for washing fabrics at 15°C or even 9°C. To obtain satisfactory washing results at such low temperatures, results comparable to those obtained with hot water washing, there is a great demand for low temperature detergents.

[0003] Branched surfactants are known to be particularly effective under cold water wash conditions. For example, surfactants with branches toward the center of the hydrophobe's carbon chain, known as mid-chain branched surfactants, are known for their cold water wash effectiveness. 2-Alkyl branched or "β-branched" primary alkyl sulfates (also known as 2-alkyl primary alcohol sulfates) are also known. 2-Alkyl branched primary alkyl alkoxy sulfates have a branch 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 the hydrophobe). 2-Alkyl branched alcohols, such as 2-alkyl-1-alkanols or 2-alkyl primary alcohols, are derived from the Oxo process and are commercially available from Sasol under the trademark ISALCHEM®. 2-Alkyl branched alcohols (and the 2-alkyl branched alkyl sulfates derived from them) are positional isomers, varying in the position of the hydroxymethyl group (consisting of a methylene bridge (-CH2- unit) attached to a hydroxy (-OH) group) on the carbon chain. Thus, 2-alkyl branched alcohols generally consist of a mixture of positional isomers. Commercially available 2-alkyl branched alcohols also contain some proportion of linear alcohols. For example, Sasol's ISALCHEM® Alcohols are prepared from Sasol's oxo-alcohols (LIAL® Alcohols) by a fractionation process that yields over 90% 2-alkyl branched material, with the remainder being linear. 2-Alkyl branched alcohols are also available with a variety of chain lengths. 2-Alkyl primary alcohol sulfates with alkyl chain distributions of 12 to 20 carbons are known. ISALCHEM® 145 (C 14 ~C 15 -alcohol) and ISALCHEM® 167 (C 16 ~C 17ISALCHEM® alcohols (single and blends) ranging from C9 to C17 are commercially available, including ISALCHEM® 123-alcohol. An alcohol ethoxylate based on ISALCHEM® 123 is available under the trade name COSMACOL® AE-3. Summary of the Invention [Problem to be solved by the invention]

[0004] There is a continuing need for branched surfactants that can improve cleaning performance at low wash temperatures, e.g., 30°C or even lower, at a reasonable cost and without interfering with laundry detergent manufacturing and quality, including negative effects on stability and viscosity. Surprisingly, it has been found that detergent compositions containing 2-alkyl primary alcohol alkoxy sulfates having a predominantly C15 alkyl chain length distribution, including specific proportions of specific positional isomers, enhance stain removal (especially in cold water) and improve product stability. [Means for solving the problem]

[0005] The present invention provides a detergent composition comprising from about 0.1% to about 99% by weight of the composition of a first surfactant, wherein the first surfactant is a surfactant isomer of Formula I: A mixture of and a surfactant of formula II Or It becomes essential,

[0006] [ka] About 50% to about 100% by weight of the first surfactant is the isomer having m+n=11, and about 25% of the mixture weight %~about 50 weight % of the surfactant isomer of Formula I having n=0, and about 0.001% to about 25% by weight of the first surfactant is a surfactant of Formula II, where X is a hydrophilic moiety. The detergent composition may further include one or more auxiliary cleaning additives.

[0007] The present invention further relates to a method of pre-treating or treating soiled fabrics comprising contacting the soiled fabrics with the cleaning compositions of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] Features and advantages of the present invention will become apparent from the following description, including examples intended to give a broad expression of the invention. Various modifications will become apparent to those skilled in the art from this specification 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.

[0009] As used herein, the articles including "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.

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

[0011] As used herein, the term "gallon" refers to "US gallon."

[0012] As used herein, the terms "substantially free of" or "substantially free from" refer to either a complete absence or minimal amount of a component simply as an impurity or unintended by-product of another component. A composition "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.

[0013] As used herein, the term "soiled material" is used non-specifically and may refer to any type of flexible material made of a network of natural or man-made fibers, including, but not limited to, natural, man-made, and synthetic fibers such as cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations. Soiled material may further refer to any type of hard surface, including, but not limited to, natural, man-made, and synthetic surfaces, such as, but not limited to, tile, granite, plaster, glass, composites, vinyl, hardwood, metal, cooking surfaces, plastics, and the like, as well as blends and combinations.

[0014] 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 is included within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0015] 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.

[0016] All concentrations and ratios herein are by weight of the detergent composition unless otherwise specified.

[0017] Detergent Composition As used herein, the phrase "detergent composition" or "cleaning composition" includes 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, dishwashing compositions, 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 can be used as laundry pretreatments, laundry post-treatments, or can be added during the rinse or wash cycle of a laundry operation. The detergent compositions may have a form selected from liquids, powders, single-phase or multi-phase unit doses, pouches, tablets, gels, pastes, bars, or flakes.

[0018] surfactants The detergent compositions of the present invention may comprise one or more surfactants.

[0019] In particular, the detergent compositions of the present invention contain 2-alkyl primary alkyl alcohol sulfates and 2-alkyl primary alkyl alcohol ethoxy sulfates with a specific alkyl chain length distribution that improves stain removal (especially in cold water). 2-Alkyl branched alcohols (as well as 2-alkyl branched alkyl sulfates and 2-alkyl branched alkyl ethoxy sulfates, and other surfactants derived therefrom) are positional isomers that differ in the position of the hydroxymethyl group (consisting of a methylene bridge (—CH2— unit) bonded to a hydroxy (—OH) group) on the carbon chain. Therefore, 2-alkyl branched alkyl alcohols generally consist of a mixture of positional isomers. Furthermore, it is well known that fatty alcohols and surfactants, such as 2-alkyl branched alcohols, are characterized by chain length distribution. In other words, fatty alcohols and surfactants generally consist of a blend of molecules with different alkyl chain lengths (although it is possible to obtain pieces with a single chain length). In particular, the 2-alkyl primary alcohols described herein, which may have a specific alkyl chain length distribution and / or specific proportions of specific positional isomers, cannot be obtained by simply blending commercially available materials. Specifically, a distribution of about 50% to about 100% by weight of surfactants with m+n=11 cannot be achieved by blending commercially available materials.

[0020] The detergent composition comprises from about 0.1% to about 99% by weight of the composition of a first surfactant, the first surfactant being a surfactant isomer of Formula I: A mixture of and a surfactant of formula II Or It becomes essential,

[0021] [ka] About 50% to about 100% by weight of the first surfactant is the isomer having m+n=11, and about 25% of the mixture weight %~about 50 weight% surfactant isomer of Formula I has n=0, and about 0.001% to about 25% by weight of the first surfactant is a surfactant of Formula II, where X is a hydrophilic moiety.

[0022] X can be neutralized with, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, calcium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diamines, polyamines, primary amines, secondary amines, tertiary amines, amine-containing surfactants, or combinations thereof.

[0023] X is a sulfate, alkoxylated alkyl sulfate, sulfonate, amine oxide, polyalkoxylate, polyhydroxy moiety, phosphate ester, glycerol sulfonate, polygluconate, polyphosphate ester, phosphonate, sulfosuccinate, sulfosuccaminates, polyalkoxylated carboxylate, glucamide, taurinate, sarcosinate, glycinate, isethionate, dialkanolamide, monoalkanolamide, monoalkanolamide sulfate, diglycolamide, diglycolamide sulfate, glycerol ester, glucan, The hydroxybenzoates may be selected from glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, alkylated quaternary ammonium compounds (quats), alkylated / polyhydroxyalkylated quaternary ammonium compounds, alkylated / polyhydroxylated oxypropyl quaternary ammonium compounds, imidazolines, 2-yl-succinates, sulfonated alkyl esters, sulfonated fatty acids, and mixtures thereof.

[0024] The first surfactant comprises about 15% of the mixture. weight %~about 40 weight %, e.g., about 20 weight%~about 40 weight %, about 25 weight % ~ approx. 35 weight %, or about 30 weight %~about 40 weight The first surfactant may comprise a surfactant isomer of Formula I with n=1, such as about 60% of the mixture. weight %~about 90 weight %, e.g., about 65 weight %~about 85 weight %, about 70 weight %~about 90 weight %, or about 80 weight %~about 90 weight % of surfactant isomers of Formula I having n<3, such as about 90%. weight %~about 100 weight %, e.g., about 95 weight %~100 weight %, etc. surfactants An isomer may have a first surfactant with m+n=11.

[0025] The first surfactant is Agent about 15% to about 40% by weight of a compound of Formula I, wherein n=1; surfactants Isomers and the first surfactant Agent about 5% to about 20% by weight of a compound of formula I, wherein n=2; surfactants The first surfactant may have the formula I, where n is 6 or greater, surfactants The first surfactant may be present in a mixture of up to about 40% by weight of the isomer. weight % of surfactant isomers of Formula I where n>2. The first surfactant may comprise up to about 25% of the mixture. weight % of surfactant isomers of Formula I with n>2. The first surfactant may have up to about 20% by weight of surfactant isomers of Formula II surfactants may have:

[0026] The detergent composition may further comprise auxiliary cleaning additives, which may be builders, organic polymeric compounds, enzymes, enzyme stabilizers, one or more solvent bleaching systems, brighteners, colorants, chelating agents, suds suppressors, conditioning agents, moisturizers, fragrances, fillers or carriers, alkalinity systems, pH control systems, and buffers, and mixtures thereof.

[0027] The detergent composition may further comprise from about 0.1% to about 99% by weight of the composition of a second surfactant, the second surfactant being a surfactant isomer of formula III: A mixture of and a surfactant of formula IV Or It becomes essential,

[0028] [ka] No. 2 About 50% by weight to about 100% by weight of the surfactants have m+n=9 surfactants isomers, 2About 0.001% to about 25% by weight of the surfactant is a surfactant of Formula IV, where X is a hydrophilic moiety. X can be neutralized with, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, calcium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diamines, polyamines, primary amines, secondary amines, tertiary amines, amine-containing surfactants, or combinations thereof. X is sulfate, alkoxylated alkyl sulfate, sulfonate, amine oxide, polyalkoxylate, polyhydroxy moiety, phosphate ester, glycerol sulfonate, polygluconate, polyphosphate ester, phosphonate, sulfosuccinate, sulfosuccinate, polyalkoxylated carboxylate, glucamide, taurinate, sarcosinate, glycinate, isethionate, dialkanolamide, monoalkanolamide, monoalkanolamide sulfate, diglycolamide, diglycolamide sulfate, glycerol ester, glycerol ester The sulfonated alkyl esters may be selected from steric sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, alkylated quaternary ammonium compounds, alkylated / polyhydroxyalkylated quaternary ammonium compounds, alkylated / polyhydroxylated oxypropyl quaternary ammonium compounds, imidazolines, 2-yl-succinates, sulfonated alkyl esters, sulfonated fatty acids, and mixtures thereof.

[0029] The said mixture About 25% to about 50% of the mixture, for example, 30% to 45%, 35% to 45%, or 40% to 50%, etc. a second surfactant isomer of formula III may have n=0. The said mixture About 15% to about 40% of the mixture, for example, 20% to 40%, 25% to 35%, or 30% to 40%, etc. a second surfactant isomer of formula III may have n=1. The said mixtureAbout 50% to about 90% of the mixture, for example, 55% to 90%, 60% to 80%, or 70% to 90%, etc. a second surfactant isomer of formula III may have n<3. About 90% to about 100%, such as 95% to 100%, of the second surfactants have m+n=9. surfactants It may contain isomers.

[0030] The second surfactant is Agent about 25% to about 50% by weight of a compound of formula III, wherein n=0; surfactants Isomers and second surfactants Agent about 15% to about 40% by weight of a compound of formula III, wherein n=1; surfactants Isomers and second surfactants Agent about 5% to about 20% by weight of a compound of formula III, wherein n=2 surfactants and isomers. weight Up to about 35% of the mixture may have n>2. weight % of the surfactant isomers of formula III may have n>2. The agent , up to about 20% by weight of formula IV surfactants may include:

[0031] The detergent composition comprises about 30 weight% ~about 99 weight % of the first surfactant and about 0.5 weight %~about 40 weight % of a second surfactant, preferably 0.5 weight% ~20 weight % of a second surfactant, more preferably 0.5 weight% ~12.5 weight % of a second surfactant. weight % ~ approx. 99 weight % of the first surfactant and up to about 25 weight % of a second surfactant.

[0032] The detergent composition may comprise the second surfactant to the first surfactant in a ratio of from 0.5:10 to 4:10, such as 1:10, 2:10, or 3:10.

[0033] The detergent composition may further comprise a third surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, or mixtures thereof, or the detergent composition comprises an anionic surfactant selected from alkyl benzene sulfonates, alkoxylated alkyl sulfates, alkyl sulfates, and mixtures thereof.

[0034] The detergent composition may be in a form selected from the group consisting of granular detergents, detergent bars, liquid laundry detergents, gel detergents, single-phase or multi-phase unit dose detergents, single-phase or multi-phase or multi-compartment water-soluble pouch detergents, liquid hand dishwashing compositions, laundry pre-treatment products, multi-compartment non-dissolving packages, detergents contained on or in porous substrates or nonwoven sheets, automatic dishwashing detergents, hard surface cleaners, fabric softener compositions, and mixtures thereof.

[0035] The detergent composition may be incorporated into the textile. The detergent composition may be incorporated into the fibers of the textile, into particles within the textile, or a combination thereof.

[0036] The detergent composition may have from about 0.1% to about 100% of the carbon content of the first surfactant, second surfactant, or combination thereof derived from renewable resources.

[0037] The detergent composition may be used in a method of pre-treating or treating soiled fabrics comprising contacting the soiled fabrics with the detergent composition.

[0038] The detergent composition may include an additional surfactant (e.g., a third surfactant, a fourth surfactant) selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. The additional surfactant may be a detersive surfactant, which one skilled in the art will understand to include any surfactant or mixture of surfactants that provides cleaning, stain removal, or laundering benefits to soiled materials.

[0039] The detergent composition may contain from about 0.01% to about 5% by weight of the alcohol composition. The detergent composition may contain from about 0.5% to about 3.0% by weight of the alcohol composition. At such concentrations, the alcohol composition may provide a suds suppressing effect to the detergent composition.

[0040] The detergent composition may contain from about 0.01% to about 0.5% of the alcohol composition by weight of the detergent composition. At such concentrations, the alcohol composition may be an impurity.

[0041] Suitable alkyl sulfate anionic surfactants can be made using the following process. A two-stage process can be used to produce branched aldehyde products from linear alpha-olefin feedstocks, from which the alkyl sulfate anionic surfactants described herein can be derived. The two-stage process uses a rhodium organophosphorus catalyst in both the first and second process steps. The first step is an isomerization reaction step, and the second step is a hydroformylation reaction step. The branched aldehydes can undergo a further hydrogenation step to produce branched alcohols.

[0042] The isomerization and hydroformylation reactions disclosed herein may be catalyzed by a rhodium organophosphorus catalyst, which may be at least one of: (1) an organometallic complex of rhodium and one organophosphorus ligand; or (2) an organometallic complex of rhodium and two or more organophosphorus ligands.

[0043] The organophosphorus ligand can be a phosphine. A non-limiting example of a phosphine ligand is triphenylphosphine. The organophosphorus ligand can be a phosphite. A non-limiting example of a phosphite ligand is tris(2,4-di-t-butylphenyl)phosphite. Mixtures of different organophosphorus ligands, such as a mixture of phosphines and phosphites, can also be used. A non-limiting example of a mixture of organophosphorus ligands is a mixture of triphenylphosphine and tris(2,4-di-t-butylphenyl)phosphite. The reaction system can contain an inert high-boiling solvent, such as a polyalphaolefin. The first catalyst can be formed when the molar ratio of phosphorus to rhodium is in the range of 1:1 to 1000:1, or 5:1 to 50:1, or 15:1 to 25:1. The rhodium concentration may range from 1 ppm to 1000 ppm, or from 10 ppm to 200 ppm, or from 25 ppm to 75 ppm. The molar ratio of CO to H2 may range from 10:1 to 1:10, or from 2:1 to 1:2, or from 1.3:1 to 1:1.3.

[0044] During the isomerization reaction, the first step can be isomerizing linear alpha olefins in the presence of carbon monoxide (CO) and hydrogen (H) at a first pressure. The isomerization can be catalyzed by a rhodium organophosphorus catalyst, which can be at least one of: (1) an organometallic complex of rhodium with one type of organophosphorus ligand; or (2) an organometallic complex of rhodium with two or more types of organophosphorus ligand. The isomerization reaction can produce isomerized olefins, including the same or different types of linear internal olefins.

[0045] The isomerization step can be carried out at a temperature ranging from 30° C. to 500° C., or from 50° C. to 150° C., or from 70° C. to 100° C. The isomerization step can be carried out at a gauge pressure ranging from 0.1 bar (0.01 MPa above atmospheric pressure) to 10 bar (1 MPa above atmospheric pressure), or from 0.5 bar (0.05 MPa above atmospheric pressure) to 5 bar (0.5 MPa above atmospheric pressure), or from 1 bar (0.1 MPa above atmospheric pressure) to 2 bar (0.2 MPa above atmospheric pressure).

[0046] The isomerization step may produce a reaction product comprising 20% ​​by weight or more isomerized olefins, or 40% by weight or more isomerized olefins, or 60% by weight or more isomerized olefins, or 90% by weight or more isomerized olefins.

[0047] In the hydroformylation reaction step, the isomerized olefin is hydroformylated in the presence of CO and H2 at a second pressure higher than the first pressure to produce a branched aldehyde. The hydroformylation reaction can be catalyzed by a rhodium organophosphorus catalyst, which can be at least one of (1) an organometallic complex of rhodium with one organophosphorus ligand, or (2) an organometallic complex of rhodium with two or more organophosphorus ligands. The resulting branched aldehyde is a 2-alkyl branched aldehyde. When the linear alpha olefin is 1-dodecene, the resulting branched aldehyde is a branched C13 aldehyde. When the linear alpha olefin is 1-tetradecene, the resulting branched aldehyde is a branched C15 aldehyde.

[0048] The hydroformylation step can be carried out at a temperature ranging from 30° C. to 500° C., or from 50° C. to 150° C., or from 70° C. to 100° C. The hydroformylation step can be carried out at a gauge pressure ranging from 5 bar (0.5 MPa above atmospheric pressure) to 400 bar (40 MPa above atmospheric pressure), or from 10 bar (1.0 MPa above atmospheric pressure) to 100 bar (10 MPa above atmospheric pressure), or from 15 bar (1.5 MPa above atmospheric pressure) to 20 bar (2 MPa above atmospheric pressure).

[0049] The hydroformylation process may produce a reaction product containing 25% or more branched aldehydes by weight, or 40% or more branched aldehydes by weight, or 60% or more branched aldehydes by weight, or 90% or more branched aldehydes by weight.

[0050] The product of the hydroformylation reaction can be distilled. The process can include separating the branched aldehyde product from the hydroformylation as an overhead from the first catalyst stream via a distillation process. The distillation step can be carried out at a temperature ranging from 100°C to 200°C, or from 125°C to 175°C. The distillation step can be carried out under vacuum at a pressure of less than 500 mbar absolute (0.05 MPa), or less than 100 mbar absolute (0.01 MPa), or less than 30 mbar absolute (0.003 MPa).

[0051] The process may also include hydrogenating the branched aldehyde product in the presence of a hydrogenation catalyst to produce a branched alcohol product composition. The hydrogenation catalyst may be a base metal catalyst, a nickel-supported catalyst, a cobalt-supported catalyst, a Raney® (W.R. Grace & Co., 7500 Grace Drive, Columbia, MD 21044) nickel catalyst, or a precious metal catalyst. The hydrogenation step may be carried out at a temperature ranging from 30°C to 500°C, or from 50°C to 200°C, or from 100°C to 150°C. The hydrogenation step may be carried out at a gauge pressure ranging from 5 bar (0.5 MPa above atmospheric pressure) to 400 bar (40 MPa above atmospheric pressure), or from 10 bar (1 MPa above atmospheric pressure) to 100 bar (10 MPa above atmospheric pressure), or from 30 bar (3 MPa above atmospheric pressure) to 50 bar (5 MPa above atmospheric pressure).

[0052] The hydrogenation step may produce a reaction product comprising 25% or more branched alcohols by weight, or 40% or more branched alcohols by weight, or 60% or more branched alcohols by weight, or 90% or more branched alcohols by weight.

[0053] Alkyl sulfates are typically prepared by the reaction of fatty alcohols with sulfur trioxide (SO3) or its derivatives, or by the reaction of unsaturated compounds with sulfuric acid. The use of sulfur trioxide has been particularly successful in the production of alkyl sulfate anionic surfactants for use in detergent compositions.

[0054] Suitable derivatives of sulfur trioxide include sulfur trioxide complexes such as chlorosulfonic acid, sulfuric acid, or sulfamic acid. Sulfur trioxide is preferred because it tends to produce a purer product. The sulfation reaction is typically carried out in a continuous process using a cascade of falling film or tube bundle reactors, with sulfur trioxide being added in equimolar or slight excess amounts, typically at temperatures ranging from 20°C to 60°C. The reaction temperature is determined, at least in part, by the freezing point of the aliphatic alcohol being reacted. The reaction typically produces the acid form of the alkyl sulfate anionic surfactant, which is typically neutralized in a subsequent step using an alkali such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, calcium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diamines, polyamines, primary amines, secondary amines, tertiary amines, amine-containing surfactants, and mixtures thereof.

[0055] It is also well known that the process of sulfating fatty alcohols to obtain alkyl sulfate anionic surfactants also produces various impurities. The exact nature of these impurities depends on the conditions of sulfation and neutralization. However, generally, the impurities in the sulfation process include one or more inorganic salts, unreacted fatty alcohol, and olefins ("The Effect of Reaction By-Products on the Viscosities of Sodium Lauryl Sulfate Solutions," Journal of the American Oil Chemists' Society, Vol. 55, No. 12, pp. 909-913 (1978), C.F. Pustnik and S.E. McGuire). The concentration of non-alkyl sulfate impurities in the alkyl sulfate anionic surfactant of the present invention can be less than 6% by weight, preferably less than 4% by weight, and most preferably less than 2% by weight, based on the weight of the alkyl sulfate anionic surfactant.

[0056] In the case of alkyl alkoxy sulfates, fatty alcohols are first alkoxylated prior to sulfation. Alkoxylation is a process in which lower molecular weight epoxides (oxiranes), such as ethylene oxide, propylene oxide, and butylene oxide, are reacted with fatty alcohols. These epoxides can be reacted with fatty alcohols using various base or acid catalysts. In base-catalyzed alkoxylation, the alcoholate anion initially formed by reaction with the catalyst (alkali metal, alkali metal oxide, carbonate, hydroxide, or alkoxide) nucleophilically attacks the epoxide.

[0057] Traditional alkaline catalysts for alkoxylation include potassium hydroxide and sodium hydroxide, which produce a somewhat broad distribution of alkoxylates. Other catalysts for alkoxylation have been developed that produce narrower alkoxylate oligomer distributions. Suitable examples of narrow-range alkoxylation catalysts include many alkaline earth (Mg, Ca, Ba, Sr, etc.) derived catalysts, Lewis acid catalysts such as zirconium dodecane oxide sulfate, and certain boron halide catalysts. A specific average alkoxylation degree can be achieved by selecting the starting amounts of fatty acid alcohol and ethylene oxide, or by blending together various amounts of alkoxylated surfactants with different average alkoxylation degrees.

[0058] impurities The process for making the 2-alkyl primary alcohol derived surfactants of the present invention can produce various impurities and / or contaminants at different steps of the process.

[0059] The starting C15 aldehydes and C13 aldehydes, as well as the C14 olefin and C12 olefin sources used in hydroformylation to produce the subsequent alcohols and corresponding surfactants used in the present invention, can have low levels of impurities that lead to impurities in the starting C15 alcohols and C13 alcohols, and therefore to impurities in the C15 alkyl sulfates and C13 alkyl sulfates. Without being bound by theory, such impurities present in the C14 olefin and C12 olefin feedstocks can include vinylidene olefins, branched olefins, paraffins, aromatic components, and low levels of olefins with chain lengths other than the intended 14 or 12 carbons. Branched and vinylidene olefins are typically 5% or less in the C14 and C12 alpha-olefin sources. The resulting impurities in the C15 alcohols and C13 alcohols may include low levels, typically less than 5% by weight of the mixture, preferably less than 1%, of linear and branched alcohols ranging from C10 to C17 alcohols, particularly C11 and C15 alcohols in C13 alcohols, and particularly C13 and C17 alcohols in C15 alcohols; low levels of branching at positions other than the 2-alkyl position resulting from branched and vinylidene olefins, typically less than about 5% by weight of the alcohol mixture, preferably less than 2% by weight; paraffins and olefins, typically less than 1% by weight of the alcohol mixture, preferably less than about 0.5%; and low levels of aldehydes, typically having a carbonyl number less than 500 mg / kg, preferably less than about 200 mg / kg. These impurities in the alcohol can result in low levels of paraffins, linear and branched alkyl sulfates having total carbon numbers other than C15 or C13, and alkyl sulfates having branches at positions other than the 2-alkyl position, where the branches can vary in length but are typically linear alkyl chains having 1 to 6 carbons. The hydroformylation process can also produce impurities such as linear and branched paraffins, residual olefins from incomplete hydroformylation, and esters, formates, and heavy ends (dimers, trimers).Impurities that are not reduced to alcohol in the hydrogenation step can be removed during final purification of the alcohol by distillation.

[0060] It is also well known that the process of sulfating fatty alcohols to obtain alkyl sulfate surfactants also produces various impurities. The exact nature of these impurities depends on the conditions of sulfation and neutralization. However, generally, the impurities in the sulfation process include one or more inorganic salts, unreacted fatty alcohol, and olefins ("The Effect of Reaction By-Products on the Viscosities of Sodium Lauryl Sulfate Solutions," Journal of the American Oil Chemists' Society, Vol. 55, No. 12, pp. 909-913 (1978), C.F. Pustnik and S.E. McGuire).

[0061] Alkoxylated impurities may include dialkyl ethers, polyalkylene glycol dialkyl ethers, olefins, and polyalkylene glycols. Impurities may also include catalysts or components of catalysts used in various processes.

[0062] Synthesis Example The following examples are representative and non-limiting.

[0063] Alcohol Composition—Using the above process (Rh hydroformylation, hydrogenation), the alcohol composition described in Examples 1 and 2 was obtained and analyzed by gas chromatography with flame ionization detection (GC / FID). Samples were prepared as 1% (w / v) dichloromethane solutions and injected onto a capillary GC column, DB-1 (15 m high x 0.25 mm internal diameter, 0.1 μm film thickness), using an oven temperature program of 80°C (initial temperature, hold for 1 minute), 220°C (heating at 10°C / min), 350°C (heating at 30°C / min), and 350°C (hold for 1 minute) for a total run time of 19 minutes. Additional GC parameters include column flow rate: 1.4 mL / min (H), injection temperature: 300°C, sample volume: 1 μL, split ratio: 1 / 400, FID temperature: 350°C, H flow rate: 40 mL / min, air flow: 400 mL / min, and makeup gas flow rate: 25 mL / min.

[0064] Example 1: Preparation of branched C13 alcohol products A C12 linear alpha olefin feedstock (1-dodecene) was obtained from Chevron Phillips Chemical Company LP (P.O. Box 4910, The Woodlands, Texas 77387-4910) and is identified by the trade name AlphaPlus® 1-dodecene (Chevron Phillips Chemical Company LP, US, phone (800) 231-3260). The homogeneous rhodium organophosphorus catalyst used in this example was prepared in a high-pressure stainless steel stirred autoclave. To an autoclave was added 0.027 wt. % Rh(CO)2ACAC ((acetylacetonato)dicarbonylrhodium(I)), 1.36 wt. % tris(2,4-di-t-butylphenyl)phosphite ligand, and 98.62 wt. % Synfluid® PAO 4 cSt (Chevron Phillips Chemical Company LP, P.O. Box 4910, The Woodlands, TX 77387-4910, phone number (800) 231-3260) inert solvent. The mixture was heated at 80°C for 4 hours under a CO / H2 atmosphere and 2 bar (g) pressure to produce an active rhodium catalyst solution (109 ppm rhodium, P:Rh molar ratio = 20). 1-Dodecene linear alpha olefin was added to the rhodium catalyst solution in the autoclave to produce a starting reaction mixture with a rhodium concentration of 35 ppm. The alpha-olefin feedstock was then isomerized in the presence of a CO / H atmosphere and a pressure of 1 bar (g) at 80°C for 10 hours. The isomerized olefins were then hydroformylated in the presence of a CO / H atmosphere and a pressure of 20 bar (g) at 70°C for 8 hours. The molar ratio of CO to H in both the isomerization and hydroformylation steps was equal to 1:1.15. The resulting hydroformylation reaction product was flash distilled at 140-150°C and 25 mbar to recover the rhodium catalyst solution as a bottom product and the branched C13 aldehyde overhead product, which had the following compositions:

[0065] [Table 1] The weight percent of branching in the branched C13 aldehyde product was 86.2%.

[0066] The branched C13 aldehyde product was hydrogenated in a high-pressure Inconel 625 stirred autoclave at 150°C and 20 bar (g) hydrogen pressure. The hydrogenation catalyst used was Raney® Nickel 3111 (WR Grace & Co., 7500 Grace Drive, Columbia, MD 21044, USA, Tel. 1-410-531-4000) catalyst used at 0.25 wt% loading. The aldehyde was hydrogenated for 10 hours, and the resulting reaction mixture was filtered to produce a branched C13 alcohol product containing:

[0067] [Table 2] The weight percent of 2-alkyl branches in the branched C13 alcohol product was 85.6%.

[0068] Example 2: Preparation of branched C15 alcohol products The recovered rhodium catalyst stream from Example 1 was charged to a high-pressure, stainless steel, stirred autoclave, and a C14 linear alpha olefin feedstock (1-tetradecene) from Chevron Phillips Chemical Company LP (AlphaPlus® 1-Tetradecene, Chevron Phillips Chemical Company LP, P.O. Box 4910, The Woodlands, TX 77387-4910, telephone number (800) 231-3260) was added. The resulting mixture had a rhodium concentration of approximately 30 ppm. The 1-tetradecene linear alpha olefin was then isomerized in the presence of a CO / H atmosphere and 1 bar(g) pressure at 80°C for 12 hours. The isomerized olefin was then hydroformylated in the presence of a CO / H atmosphere and 20 bar(g) pressure at 70°C for 8 hours. The resulting reaction product was flash distilled at 150-160°C and 25 mbar to recover the rhodium catalyst solution as a bottom product and the branched C15 aldehyde overhead product. The recovered rhodium catalyst solution was then used again to complete a second batch of 1-tetradecene isomerization (4 hours) and hydroformylation (6 hours). The C15 aldehyde products from the two batches were combined to yield a branched C15 aldehyde product containing:

[0069] [Table 3] The weight percent of branching in the branched C15 aldehyde product was 87.8%.

[0070] The branched C15 aldehyde product was hydrogenated in a high-pressure Inconel 625 stirred autoclave at 150°C and 20 bar (g) hydrogen pressure. The hydrogenation catalyst used was Raney® Nickel 3111 (WR Grace & Co., 7500 Grace Drive, Columbia, MD 21044, USA, Tel. 1-410-531-4000) catalyst used at 0.25 wt% loading. The aldehyde was hydrogenated for 10 hours, and the resulting reaction mixture was filtered to produce a branched C15 alcohol product containing:

[0071] [Table 4] The weight percent of 2-alkyl branches in the branched C15 alcohol product was 83.6%.

[0072] Example 3. Synthesis of narrowly branched pentadecanol (C15) sulfate using a falling film sulfation reactor (inventive example 3) The alcohol from Example 2 was sulfated in a falling film using a Chemithon single 15 mm x 2 m tubular reactor with SO3 produced from a sulfur-fired gas plant operating at 5.5 lb / hr of sulfur and producing 3.76% SO3 by volume. The alcohol feed rate was 17.4 kg / hr and the feed temperature was 83°F. Conversion of the alcohol to an alcohol sulfate acid mixture was achieved with 97% completeness. Neutralization with 50% sodium hydroxide was completed at ambient process temperature, resulting in a 0.54% excess of sodium hydroxide. 30 gallons of sodium were used to neutralize the C15 narrow-branched alcohol sulfate paste. Analysis by standard cationic SO3 titration determined the final average product activity to be 74.5%. The average unsulfated level was 2.65% w / w.

[0073] Example 4. Synthesis of narrowly branched tridecanol (C13) sulfate using a falling film sulfation reactor (inventive example 4) The alcohol from Example 1 was sulfated in a falling film using a Chemithon single 15 mm x 2 m tubular reactor with SO3 produced from a sulfur-fired gas plant operating at 5.5 lb / hr of sulfur and producing 3.76% SO3 by volume. The alcohol feed rate was 15.2 kg / hr and the feed temperature was 81°F. Conversion of the alcohol to an alcohol sulfate acid mixture was achieved with 96.5% completeness. Neutralization with 50% sodium hydroxide was complete to 0.65% excess sodium hydroxide at ambient process temperature. 33 gallons of sodium were used to neutralize the C13 narrow-branched alcohol sulfate paste. Analysis by standard cationic SO3 titration determined the final average product activity to be 73.4%. The average unsulfated level was 2.10% w / w.

[0074] Alkyl sulfate

[0075] [Table 5] * Based on weight of starting alcohol ** Based on the weight of 2-alkyl branched C15 alcohol

[0076] [Table 6] * Based on weight of starting alcohol ** Based on the weight of 2-alkyl branched C13 alcohol

[0077] Additional surfactants In addition to the first surfactant, the detergent composition may contain additional surfactants, such as a second surfactant and a third surfactant. The detergent composition may contain from about 1% to about 75% by weight of the composition of the additional surfactant, such as a second surfactant and a third surfactant. The detergent composition may contain from about 2% to about 35% by weight of the composition of the additional surfactant, such as a second surfactant and a third surfactant. The detergent composition may contain from about 5% to about 10% by weight of the composition of the additional surfactant, such as a second surfactant and a third surfactant. The additional surfactant may be selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof.

[0078] Laundry care ingredients The detergent or laundry care composition may, in some aspects, include other suitable adjuvants, which may be incorporated in whole or in part. The adjuvants may be selected according to the intended function of the selected care composition. The first composition may include an additive. In some aspects, in the case of a multi-compartment unit dose article, the additive may be part of a non-first (e.g., second, third, fourth, etc.) composition enclosed in a separate compartment from the first composition. The non-first composition may be any suitable composition. The non-first composition may be in the form of a solid, liquid, dispersion, gel, paste, or mixture thereof. When the unit dose includes multiple compartments, the leuco colorant may be added to or present in one, two, or even all compartments. In one embodiment, the leuco colorant may be added to a larger compartment to provide a lower concentration, thereby minimizing any issues related to potential contact staining. On the other hand, concentrating the antioxidant with the leuco colorant in a compartment with a smaller volume may provide a higher local concentration of the antioxidant, thereby providing enhanced stability. Thus, as will be appreciated by those skilled in the art, the formulator can select the location and amount of leuco colorant according to the desired properties of the unit dose.

[0079] adjuvants The laundry care composition may comprise a surfactant system having a first surfactant, a second surfactant, or a combination of the first surfactant and the second surfactant plus an additional surfactant. The entire combination of surfactants, including the first surfactant, the second surfactant, and any other surfactants, constitutes a surfactant system. The laundry care composition may comprise from about 1% to about 80%, or from 1% to about 60%, preferably from about 5% to about 50%, and more preferably from about 8% to about 40%, by weight of the laundry care composition.

[0080] Surfactants: Suitable surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, and amphoteric surfactants, as well as mixtures thereof. Suitable surfactants may be linear or branched, substituted or unsubstituted, and derived from petrochemicals or biological materials. A preferred surfactant system includes both anionic and nonionic surfactants, preferably in a weight ratio of 90:1 to 1:90. In some cases, a weight ratio of anionic surfactant to nonionic surfactant of at least 1:1 is preferred. However, in other cases, a ratio of less than 10:1 may be preferred. When present, the total surfactant concentration is preferably 0.1% to 60%, 1% to 50%, or even 5% to 40% by weight of the compositions of the present invention.

[0081] Anionic surfactants: Anionic surfactants include, but are not limited to, surface-active compounds containing an organic hydrophobic group containing approximately 8 to 22 carbon atoms or approximately 8 to 18 carbon atoms in its molecular structure and at least one water-solubilizing group, preferably selected from sulfonate, sulfate, and carboxylate, for forming a water-soluble compound. Typically, the hydrophobic group contains a C8 to C22 alkyl or acyl group. Such surfactants are used in the form of water-soluble salts, and the salt-forming cation is typically selected from sodium, potassium, ammonium, magnesium, and mono-, with sodium cations being commonly selected.

[0082] The anionic surfactants and auxiliary anionic co-surfactants of the present invention may exist in acid form, which can be neutralized to form surfactant salts suitable for use in the detergent compositions. Typical neutralizing agents include metal counterion bases such as hydroxides, e.g., NaOH or KOH. More preferred agents for neutralizing the acid forms of the anionic surfactants and auxiliary anionic surfactants or co-surfactants of the present invention include ammonia, amines, oligoamines, or alkanolamines. Alkanolamines are preferred. Suitable non-limiting examples include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art. For example, highly preferred 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 may be neutralized with sodium or potassium, and a portion of the anionic surfactant may be neutralized with an amine or alkanolamine.

[0083] Suitable sulfonate surfactants include methyl ester sulfonates, alpha olefin sulfonates, alkyl benzene sulfonates, especially alkyl benzene sulfonates, preferably C 10~13Alkylbenzene sulfonates, more preferably C12 alkylbenzene sulfonates, are included.Suitable alkylbenzene sulfonates (LAS) can be obtained, preferably 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 by Petresa under the trade name Petrelab®, and other suitable LABs include high 2-phenyl LABs such as those supplied by Sasol under the trade name Hyblene®. Preferred anionic surfactants are alkylbenzene sulfonates obtained by the DETAL catalytic process, DETAL-PLUS catalytic process, although other synthetic routes may be suitable, such as HF and other alkylation catalysts such as zeolites ZSM-4, ZSM-12, ZSM-20, ZSM-35, ZSM-48, ZSM-50, MCM-22, TMA offretite, TEA mordenite, clinoptilolite, mordenite, REY, and zeolite beta. In one embodiment, the magnesium salt of LAS is used.

[0084] Preferably, the composition may contain from about 0.5% to about 30%, by weight of the laundry detergent composition, of a HLAS surfactant selected from alkyl benzene sulfonic acids, alkali metal or amine salts of C10-16 alkyl benzene sulfonic acids, the HLAS surfactant containing more than 50% C12, preferably more than 60% C12, preferably more than 70% C12, more preferably more than 75% C12.

[0085] Suitable sulfate surfactants include alkyl sulfates, preferably C 8~18 Alkyl sulfate, or mainly C 12 Alkyl sulfates are included.

[0086] Preferred sulfate surfactants are alkyl alkoxylated sulfates, preferably C 8~18Alkyl alkoxylated sulfates, preferably C 8~18 C alkyl ethoxylated sulfates, preferably the alkyl alkoxylated sulfates have an average degree of alkoxylation of 0.5 to 20, preferably 0.5 to 10, preferably the alkyl alkoxylated sulfates have an average degree of ethoxylation of 0.5 to 10, preferably 0.5 to 5, more preferably 0.5 to 3, or about 1.5 to 3, or about 1.8 to 2.5. 8~18 The alkyl ethoxylated sulfates may have a broad or peaked alkoxy distribution. The alkyl moieties of the AES may contain, on average, 13.7 to about 16, or 13.9 to 14.6 carbon atoms. At least about 50%, or at least about 60%, of the AES molecules may contain alkyl moieties having 14 or more carbon atoms, preferably 14 to 18, or 14 to 17, or 14 to 16, or 14 to 15 carbon atoms.

[0087] The alkyl sulfates, alkyl alkoxylated sulfates, and alkyl benzene sulfonates may be linear or branched (including dialkyl-substituted or mid-chain branched), substituted or unsubstituted, and derived from petrochemical or biomaterial sources. Preferably, the branched group is alkyl. Typically, the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, cyclic alkyl groups, and mixtures thereof. Single or multiple alkyl branches may be present on the hydrocarbyl backbone of the starting alcohol used to prepare the sulfated anionic surfactants used in the detergents of the present invention. Most preferably, the branched sulfated anionic surfactant is selected from alkyl sulfates, alkyl ethoxy sulfates, and mixtures thereof.

[0088] Alkyl sulfates and alkyl alkoxy sulfates are commercially available with a variety of chain lengths, degrees of ethoxylation, and branching, including Neodol alcohols from Shell, Lial, Isalchem, Safol, Alfol®, Nacol®, Nafol®, Isofol®, and Marlipal® from Sasol, and those based on natural alcohols from The Procter & Gamble Chemicals.

[0089] Other suitable anionic surfactants include C10-C26 linear or branched, preferably C10-C20 linear, and most preferably C16-C18 linear alkyl alcohols and alkyl ether carboxylates, including 2-20, preferably 7-13, more preferably 8-12, and most preferably 9.5-10.5 ethoxylates. Acid or salt forms, such as sodium or ammonium salts, may be used, and the alkyl chain may contain one cis or trans double bond. Alkyl ether carboxylic acids are available from Kao (Akypo®), Huntsman (Empicol®), and Clariant (Emulsogen®).

[0090] Other suitable anionic surfactants include classes of glycolipids, such as sophorolipids and rhamnolipids, as well as amino acid-based surfactants, such as acylglycinates, acylsarcosinates, acylglutaminates, and acyltaurinates. Rhamnolipids can have one rhamnose sugar ring or two rhamnose sugar rings.

[0091] nonionic surfactants; Suitable nonionic surfactants include C8-C 18 Alkyl ethoxylates (e.g., NEODOL® nonionic surfactants sold by Shell); C6-C 12Alkylphenol alkoxylates (preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units or mixtures thereof); ethylene oxide / propylene oxide block polymers, C 12 ~C 18 Alcohols and C6-C 12 The surfactants are selected from the group consisting of alkylphenol condensates (e.g., Pluronic® sold by BASF); alkyl polysaccharides, preferably alkyl polyglycosides and alkyl polypentosides; fatty acid methyl ester ethoxylates; polyhydroxy fatty acid amides; ether-capped poly(oxyalkylated) alcohol surfactants; alkyl and alkenyl furan sulfonates, and alkyl and alkenyl furan sulfates, and mixtures thereof.

[0092] Suitable nonionic surfactants are alkyl polyglucosides and / or alkyl alkoxylated alcohols.

[0093] Suitable nonionic surfactants include alkyl alkoxylated alcohols, preferably C 8~18 Alkyl alkoxylated alcohols, preferably C 8~18 Alkyl ethoxylated alcohols are mentioned, preferably alkyl alkoxylated alcohols having an average degree of alkoxylation of 1 to 50, preferably 1 to 30, or 1 to 20, or 1 to 10, preferably alkyl alkoxylated alcohols having an average degree of ethoxylation of 1 to 10, preferably 1 to 7, more preferably 1 to 5, and most preferably 3 to 7. 8~18 In one embodiment, the alkyl alkoxylated alcohol is a C alkoxylated alcohol having an average degree of ethoxylation of 7 to 10. 12~15The alkyl ethoxylated alcohols are alkyl alkoxylated alcohols. The alkyl alkoxylated alcohols may be linear or branched, substituted or unsubstituted. Suitable nonionic surfactants include those manufactured by BASF under the trade name Lutensol®. The alkyl alkoxylated sulfates may have a broad alkoxy distribution, for example, Alfonic 1214-9 ethoxylate, or a peaked alkoxy distribution, for example, Novel 1214-9, both of which are commercially available from Sasol.

[0094] Cationic surfactants: Suitable cationic surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and mixtures thereof.

[0095] Suitable cationic surfactants are quaternary ammonium compounds having the general formula: (R)(R1)(R2)(R3)N + X - where R is a straight or branched chain, substituted or unsubstituted C 6~18 R is an alkyl or alkenyl moiety, R and R are independently selected from methyl or ethyl moieties, R is a hydroxyl, hydroxymethyl, or hydroxyethyl moiety, and X is an anion that provides charge neutrality, preferred anions include halides, preferably chloride, sulfate, and sulfonate.

[0096] The fabric care compositions of the present invention may contain up to about 30%, alternatively from about 0.01% to about 20%, alternatively from about 0.1% to about 20%, by weight of the composition, of a cationic surfactant. For purposes of the present invention, cationic surfactants include those capable of providing fabric care benefits. Non-limiting examples of useful cationic surfactants include fatty amines, imidazoline quaternaries, and quaternary ammonium surfactants, preferably N,N-bis(stearoyl-oxy-ethyl)N,N-dimethylammonium chloride, N,N-bis(tallow oil-oxy-ethyl)N,N-dimethylammonium chloride, N,N-bis(stearoyl-oxy-ethyl)N-(2hydroxyethyl)N-methylammonium methyl sulfate; 1,2-di(stearoyl-oxy)3-trimethylammonium propane chloride; dicanola dimethyl ammonium chloride, di(hard) tallow dimethyl ammonium chloride, dicanola dimethyl ammonium methyl sulfate. 1-methyl-1-stearoylamidoethyl-2-stearoylimidazolinium methyl sulfate; 1-tallowylamidoethyl-2-tallowylimidazoline; N,N"-dialkyldiethylenetriamine; reaction products of glycolic acid with N-(2-hydroxyethyl)-1,2-ethylenediamine or N-(2-hydroxyisopropyl)-1,2-ethylenediamine esterified with fatty acids, wherein the fatty acid is (hydrogenated) tallow fatty acid, palm fatty acid, hydrogenated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid; polyglycerol esters (PGEs), oily sugar derivatives and wax emulsions, and mixtures of the above.

[0097] It will be understood that combinations of the softener actives disclosed above are suitable for use herein.

[0098] Amphoteric and zwitterionic surfactants: Suitable amphoteric or zwitterionic surfactants include amine oxides and / or betaines. Preferred amine oxides are alkyl dimethyl amine oxides or alkylamidopropyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides, especially coco dimethyl amine oxide. The amine oxides can have a straight-chain or mid-chain branched alkyl moiety. Typical straight-chain amine oxides include water-soluble amine oxides containing one R1 C8-18 alkyl moiety and two R2 and R3 moieties selected from the group consisting of C1-3 alkyl groups and C1-3 hydroxyalkyl groups. Preferably, the amine oxide is characterized by the formula R1-N(R2)(R3)O, where R1 is a C8-18 alkyl and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. Linear amine oxide surfactants may include, in particular, linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.

[0099] Other suitable surfactants include betaines, such as alkyl betaines, alkylamido betaines, amidoazolinium betaines, sulfobetaines (INCI sultaines), and phosphobetaines.

[0100] Leuco colorant diluent Another category of components in a leuco colorant composition can be diluents and / or solvents. The purpose of the diluent and / or solvent is often, but not limited to, improving flowability and / or reducing the viscosity of the leuco colorant. Water is often the preferred diluent and / or solvent due to its low cost and non-toxicity, but other solvents can be used as well. Preferred solvents are those that are low in cost and hazardous. Examples of suitable solvents include, but are not limited to, alkoxylated polymers such as ethylene glycol, propylene glycol, glycerin, polyethylene glycol, polypropylene glycol, copolymers of ethylene oxide and propylene oxide, Tween 20®, Tween 40®, Tween 80®, etc., and combinations thereof. Among polymers, copolymers of ethylene oxide and propylene oxide may be preferred. These polymers often feature a water cloud point, which can be useful for separating the product from water to remove undesirable water-soluble impurities. Examples of copolymers of ethylene oxide and propylene oxide include, but are not limited to, the PLURONIC® series of polymers by BASF and the TERGITOL™ series of polymers by Dow. These polymers can also act as nonionic surfactants when the leuco colorant composition is incorporated into the laundry care composition.

[0101] The laundry care compositions described herein may include one or more of the following non-limiting list of ingredients: fabric care benefit agents; detersive enzymes; deposition aids; rheology modifiers; builders; chelating agents; bleaching agents agent); bleach precursors; bleach accelerators; bleach catalysts; perfumes and / or perfume microcapsules; perfume-loaded zeolites; starch-encapsulated accords; polyglycerol esters; whitening agents; pearlizing agents; enzyme stabilizer systems; removal agents, including anionic dye fixatives, anionic surfactant complexing agents, and mixtures thereof; optical brighteners or fluorescent agents; polymers, including, but not limited to, soil release polymers and / or soil suspension polymers; dispersants; defoamers; non-aqueous solvents; fatty acids; suds suppressors, e.g., silicone suds suppressors; cationic starch; scum dispersants; direct dyes; colorants; opacifiers; antioxidants; hydrotropes, such as toluene sulfonate, cumene sulfonate, and naphthalene sulfonate; color patches; colored beads, spheres, or extrudates; mud softeners; antimicrobial agents. Additionally or alternatively, the composition may include a surfactant, a quaternary ammonium compound, and / or a solvent system. Quaternary ammonium compounds may be present in fabric enhancing compositions, such as fabric softeners, and are positively charged polyatomic ions of the structure NR4 + (R is an alkyl or aryl group).

[0102] tonal dye The composition may contain an additional fabric shading agent. Suitable fabric shading agents include dyes, dye-clay conjugates, and pigments. Suitable dyes 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) classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet, and Basic Red, or mixtures thereof. Preferred dyes include alkoxylated azothiophenes, Solvent Violet 13, Acid Violet 50, and Direct Violet 9.

[0103] Aesthetic colorants The composition may include one or more aesthetic colorants. Suitable aesthetic colorants include dyes, dye-clay conjugates, pigments, and Liquitint® polymeric colorants (Milliken & Company, Spartanburg, South Carolina, USA). In one embodiment, suitable dyes and pigments include small molecule dyes and polymeric dyes. The aesthetic colorant may include at least one chromophore component selected from the group consisting of acridine, anthraquinone, azine, azo, benzodifuran, benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoid, methane, methine, naphthalimide, naphthoquinone, nitro, nitroso, oxazine, phenothiazine, phthalocyanine (e.g., copper phthalocyanine), pyrazole, pyrazolone, quinolone, stilbene, styryl, triarylmethane (e.g., triphenylmethane), xanthene, and mixtures thereof.

[0104] In one embodiment of the invention, the aesthetic colorants include Liquitint® Blue AH, Liquitint® Blue BB, Liquitint® Blue 275, Liquitint® Blue 297, Liquitint® Blue BB, Cyan 15, Liquitint® Green 101, Liquitint® Orange 272, Liquitint® Orange 255, Liquitint® Pink AM, Liquitint® Pink AMC, Liquitint® Pink S Liquitint® Violet T, Liquitint® Violet 129, Liquitint® Violet LS, Liquitint® Violet 291, Liquitint® Yellow FT, Liquitint® Blue Buf, Liquitint® Pink AM, Liquitint® Pink PV, Acid Blue 80, Acid Blue 182, Acid Red 33, Acid Red 52, Acid Violet 48, Acid Violet 126, Acid Blue 9, Acid Blue 1, and mixtures thereof.

[0105] Enclosure The composition may include an encapsulated material. In one aspect, the encapsulant includes a core and a shell having an inner surface and an outer surface, the shell encapsulating the core. The core can comprise any laundry care aid, but typically the core may comprise a material selected from the group consisting of perfumes; whitening agents; color dyes; insect repellents; silicones; waxes; fragrances; vitamins; fabric softeners; skin care agents, in one aspect paraffin; enzymes; antibacterial agents; bleaching agents; sensates; and mixtures thereof, and the shell may comprise a material selected from the group consisting of polyethylene; polyamides, polyvinyl alcohol, optionally containing other co-monomers; polystyrene; polyisoprene; polycarbonates; polyesters; polyacrylates; aminoplasts (in one aspect, the aminoplasts may comprise polyureas, polyurethanes, and / or polyureaurethanes, and in one aspect, the polyureas may comprise polyoxymethylene urea and / or melamine formaldehyde); polyolefins; polysaccharides (in one aspect, the polysaccharides may comprise alginates and / or chitosan); gelatin; shellac; epoxy resins; vinyl polymers; water-insoluble inorganic materials; silicones; and mixtures thereof.

[0106] Preferred encapsulants include fragrances. Preferred encapsulants include a shell that may include melamine formaldehyde and / or crosslinked melamine formaldehyde. Other preferred capsules include polyacrylate-based shells. Preferred encapsulants are disclosed to include a core material and a shell at least partially surrounding the core material. At least 75%, 85%, or even 90% of the encapsulants may have a breaking strength of 0.2 MPa to 10 MPa and a benefit agent leakage rate of 0% to 20%, or even less than 10% or 5%, based on the total initial amount of encapsulated benefit agent. Preferably, at least 75%, 85%, or even 90% of the encapsulant may (i) have a particle size of 1 micrometer to 80 micrometers, 5 micrometers to 60 micrometers, 10 micrometers to 50 micrometers, or even 15 micrometers to 40 micrometers, and / or (ii) at least 75%, 85%, or even 90% of the encapsulant may have a particle wall thickness of 30 nm to 250 nm, 80 nm to 180 nm, or even 100 nm to 160 nm. A formaldehyde scavenger may be used with the encapsulant, for example, in a capsule slurry, and / or may be added to such a composition before, during, or after the encapsulant is added to the composition. Suitable capsules may be made according to the teachings of U.S. Patent Application Publication Nos. 2008 / 0305982 (A1) and / or 2009 / 0247449 (A1). Alternatively, suitable capsules can be purchased from Appleton Papers Inc. (Appleton, Wisconsin USA).

[0107] In a preferred embodiment, the composition may contain a deposition aid, preferably in addition to the encapsulating agent. Preferred deposition aids are selected from the group consisting of cationic and nonionic polymers. Suitable polymers include cationic starch, cationic hydroxyethyl cellulose, polyvinyl formaldehyde, locust bean gum, mannan, xyloglucan, tamarind gum, polyethylene terephthalate, and polymers containing dimethylaminoethyl methacrylate, optionally with one or more monomers selected from the group including acrylic acid and acrylamide.

[0108] fragrance A preferred composition of the present invention comprises a perfume. Typically, the composition comprises a perfume comprising one or more perfume raw materials selected from the group described in WO 08 / 87497. However, any perfume useful in laundry care compositions may be used. A preferred method of incorporating perfume into the composition of the present invention is via encapsulated perfume particles comprising either a water-soluble hydroxy compound, or melamine-formaldehyde or modified polyvinyl alcohol.

[0109] Odor-reducing materials The cleaning compositions of the present disclosure may include malodor-reducing materials. Such materials may reduce or even eliminate the perception of one or more malodors. These materials may be characterized by a calculated malodor reduction value ("MORV"), where MORV is calculated according to the test method set forth in WO 2016 / 049389.

[0110] As used herein, "MORV" is the calculated malodor reduction value for a target material. The MORV of a material indicates the ability of such material to reduce or even eliminate the detection of one or more malodors.

[0111] The cleaning compositions of the present disclosure may comprise one or more malodor reducing materials in a total amount of from about 0.00025% to about 0.5%, preferably from about 0.0025% to about 0.1%, more preferably from about 0.005% to about 0.075%, and most preferably from about 0.01% to about 0.05% by weight of the composition. The cleaning compositions may comprise from about 1 to about 20 malodor reducing materials, more preferably from 1 to about 15 malodor reducing materials, and most preferably from 1 to about 10 malodor reducing materials.

[0112] One, several, or each of the malodor-reducing materials may have an MORV of at least 0.5, preferably 0.5 to 10, more preferably 1 to 10, and most preferably 1 to 5. One, several, or each of the malodor-reducing materials may have a universal MORV, defined as all MORV values ​​of malodors tested as described herein being >0.5. The total amount of malodor-reducing materials may have a Blocker Index of less than 3, more preferably less than about 2.5, even more preferably less than about 2, and even more preferably less than about 1, and most preferably about 0. The total amount of malodor-reducing materials may have an average Blocker Index of from about 3 to about 0.001.

[0113] In the cleaning compositions of the present disclosure, the malodor reducing material may have a Fragrance Fidelity Index of less than 3, preferably less than 2, more preferably less than 1, and most preferably about 0, and / or the Fragrance Fidelity Index may average from 3 to about 0.001. As the Fragrance Fidelity Index increases, the malodor reducing material(s) continue to attenuate malodors but provide less and less fragrance benefit.

[0114] The cleaning compositions of the present disclosure may include a fragrance. The weight ratio of parts malodor-reducing composition to parts fragrance may be from about 1:20,000 to about 3000:1, preferably from about 1:10,000 to about 1,000:1, more preferably from about 5,000:1 to about 500:1, and most preferably from about 1:15 to about 1:1. As the ratio of parts malodor-reducing composition to parts perfume is narrowed, the malodor-reducing material(s) will continue to attenuate malodor, but will provide less and less fragrance benefit.

[0115] polymer The composition may comprise one or more polymers. Examples are optionally modified carboxymethylcellulose, modified polyglucans, poly(vinylpyrrolidone), 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.

[0116] The composition may contain one or more amphiphilic cleaning polymers. Such polymers have balanced hydrophilic and hydrophobic properties to remove grease particles from fabrics and surfaces. Suitable amphiphilic alkoxylated grease cleaning polymers contain a core structure with multiple alkoxylate groups attached to the core structure. These may include alkoxylated polyalkyleneimines, particularly ethoxylated polyethyleneimines, or polyethyleneimines with internal polyethylene oxide blocks and external polypropylene oxide blocks. Typically, these may be incorporated into the compositions of the present invention in amounts of 0.005% to 10% by weight, generally 0.5% to 8% by weight.

[0117] Zwitterionic polyamines: The composition may include a zwitterionic polyamine that is a modified hexamethylenediamine. The hexamethylenediamine modifications include: (1) one or two alkoxylation modifications per nitrogen atom of the hexamethylenediamine. The alkoxylation modification consists of replacing hydrogen atoms on the hexamethylenediamine nitrogen with (poly)alkoxylene chains having an average of about 1 to about 40 alkoxy moieties per modification, with the terminal alkoxy moieties of the alkoxylene chains being protected with hydrogen, C1-C4 alkyl, sulfate, carbonate, or a mixture thereof. (2) one C1-C4 alkyl moiety substitution and one or two alkoxylation modifications per nitrogen atom of the hexamethylenediamine. The alkoxylation modification consists of replacing hydrogen atoms with (poly)alkoxylene chains having an average of about 1 to about 40 alkoxy moieties per modification, with the terminal alkoxy moieties of the alkoxylene chains being protected with hydrogen, C1-C4 alkyl, or a mixture thereof. or (3) a combination of these.

[0118] Amphiphilic graft copolymers: Other suitable polymers include amphiphilic graft copolymers. Preferred amphiphilic graft copolymer(s) comprise (i) a polyethylene glycol backbone and (ii) at least one pendant moiety selected from polyvinyl acetate, polyvinyl alcohol, and mixtures thereof. An example of an amphiphilic graft copolymer is Sokalan HP22, supplied by BASF. Other 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 preferably about 6000, the weight ratio of polyethylene oxide to polyvinyl acetate is about 40 to 60, and there is not more than one grafting point per 50 ethylene oxide units. Typically, these are incorporated into the compositions of the present invention in an amount of 0.005 to 10% by weight, more usually 0.05 to 8% by weight.

[0119] Soil Release Polymer: The composition may include one or more soil release polymers, examples of which include soil release polymers having a structure defined by one of the following formulas (VI), (VII), or (VIII): (VI) -[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d (VII) -[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e (VIII) -[(OCHR 5 -CHR 6 ) c -OR 7 ] f (In the formula, a, b, and c are 1 to 200; d, e, and f are 1 to 50; Ar is 1,4-substituted phenylene; sAr is 1,3-substituted phenylene substituted at the 5-position with SO3Me; Me 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; 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 chain or branched C1-C 18 Alkyl, or straight or branched C2-C 30 Alkenyl or cycloalkyl groups having 5 to 9 carbon atoms, or C8 to C 30Aryl group or C6-C 30 It is an arylalkyl group.

[0120] Suitable soil release polymers are polyester soil release polymers such as Repel-o-tex polymers, including Repel-o-tex SF, SF-2, and SRP6, supplied by Rhodia. Other suitable soil release polymers include Texcare polymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN260, SRN300, and SRN325, supplied by Clariant. Other suitable soil release polymers are Marloquest polymers, such as Marloquest SL, supplied by Sasol. Known polymeric soil release agents, hereinafter "SRA(s)," may optionally be used in the present detergent compositions. If utilized, SRA(s) will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, and preferably from 0.2% to 3.0% by weight of the composition.

[0121] SRAs can include, for example, variously charged, e.g., anionic or even cationic (see U.S. Pat. No. 4,956,447), as well as uncharged, monomer units, and the structure can be linear, branched, or even star-shaped. Examples of SRAs are described in U.S. Patent Nos. 4,968,451, 4,711,730, 4,721,580, 4,702,857, 4,877,896, 3,959,230, 3,893,929, 4,000,093, 5,415,807, 4,201,824, 4,240,918, 4,525,524, 4,201,824, 4,579,681, and 4,787,989; European Patent Application Publication No. 2002-21999; 048, 279,134(A), 457,205(A), and German Patent No. 2,335,044.

[0122] Carboxylate polymers: The composition may include a carboxylate polymer, such as a maleate / acrylate random copolymer or a polyacrylate homopolymer. Suitable carboxylate polymers include polyacrylate homopolymers having a molecular weight of 4,000 Da to 9,000 Da, maleate / acrylate random copolymers having a molecular weight of 50,000 to 100,000 Da, or 60,000 to 80,000 Da.

[0123] Alternatively, these materials may comprise polyacrylates having one ethoxy side chain for every 7-8 acrylate units. The side chains have the formula -(CH2CH2O) 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. Molecular weights can vary but are typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.

[0124] Such carboxylate-based polymers can be advantageously used in the compositions herein at concentrations of about 0.1% to about 7% by weight. Suitable polymeric dispersants include carboxylate polymers such as maleate / acrylate random copolymers or polyacrylate homopolymers. Preferably, the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of 4,000 to 9,000 daltons, or a maleate / acrylate copolymer having a molecular weight of 60,000 to 80,000 daltons. Polymeric polycarboxylates and polyethylene glycols can also be used. Polyalkylene glycol-based graft polymers can be prepared from polyalkylene glycol-based compounds and monomeric materials, including carboxyl-containing monomers and optional additional monomers. Optional additional monomers not classified as carboxyl group-containing monomers include sulfonic acid group-containing monomers, amino group-containing monomers, allylamine monomers, quaternized allylamine monomers, N-vinyl monomers, hydroxyl group-containing monomers, vinyl aryl monomers, isobutylene monomers, vinyl acetate monomers, salts of any of these, derivatives of any of these, and mixtures thereof.

[0125] Alkoxylated polyamine-based polymers: The composition may contain an alkoxylated polyamine. Such materials include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and their sulfated versions. Polypropoxylated derivatives are also included. A wide variety of amines and polyaklyeneimines may be alkoxylated to various degrees and, optionally, further modified to provide the benefits described above. A useful example is a 600 g / mole polyethyleneimine core ethoxylated to 20 EO groups per NH. A preferred ethoxylated polyethyleneimine is PE-20, available from BASF.

[0126] Useful alkoxylated polyamine-based polymers include alkoxylated polyethyleneimine types having a polyalkyleneimine core with one or more side chains attached to at least one nitrogen atom in the polyalkyleneimine core, the alkoxylated polyalkyleneimine being (PEI) a -(EO) b -R1 empirical formula (I) (wherein a is the number average molecular weight (MW) of the polyalkyleneimine core of the alkoxylated polyethyleneimine) PEI ), which ranges from 100 to 100,000 daltons; b is the average degree of ethoxylation in the one or more side chains of the alkoxylated polyalkyleneimine, which ranges from 5 to 40; and R1 is independently selected from the group consisting of hydrogen, C1-C4 alkyl, and combinations thereof. Other suitable alkoxylated polyalkyleneimines include those having a polyalkyleneimine core with one or more side chains attached to at least one nitrogen atom in the polyalkyleneimine core, the alkoxylated polyalkyleneimine being: (PEI) o -(EO) m (PO) n -R2 or (PEI) o -(PO) n (EO) m -R2 empirical formula (II) (wherein o is the number average molecular weight (MW) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine) PEI ), which ranges from 100 to 100,000 daltons; m is the average degree of ethoxylation in the one or more side chains of the alkoxylated polyalkyleneimine, ranging from 10 to 50; n is the average degree of propoxylation in the one or more side chains of the alkoxylated polyalkyleneimine, ranging from 1 to 50; and R2 is independently selected from the group consisting of hydrogen, C1-C4 alkyl, and combinations thereof.

[0127] Cellulosic polymers: Cellulose-based polymers can be used in accordance with the present invention. Suitable cellulosic polymers are selected from alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyl alkyl celluloses, alkyl carboxyalkyl celluloses, and sulfoalkyl celluloses, and more preferably from carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixtures thereof. Suitable carboxymethyl celluloses have a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da. Suitable carboxymethyl celluloses have a degree of substitution greater than 0.65 and a blockiness greater than 0.45, as described, for example, in WO 09 / 154933.

[0128] The consumer products of the present invention may contain one or more cellulosic polymers, including those selected from alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, and alkyl carboxyalkyl celluloses. In one embodiment, the cellulose polymer is selected from the group consisting of carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose, methyl carboxymethyl 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. Examples of carboxymethyl cellulose polymers include carboxymethyl cellulose commercially available as Finnfix® GDA by CPKelco, hydrophobically modified carboxymethyl celluloses, such as the alkyl ketene dimer derivative of carboxymethyl cellulose commercially available as Finnfix® SH1 by CPKelco, and block carboxymethyl cellulose commercially available as Finnfix® V by CPKelco.

[0129] Cationic polymers: Cationic polymers can also be used in accordance with the present invention. Suitable cationic polymers have a cationic charge density of at least 0.5 meq / gm, in another embodiment at least 0.9 meq / gm, in another embodiment at least 1.2 meq / gm, and in yet another embodiment at least 1.5 meq / gm, but in one embodiment less than 7 meq / gm, and in another embodiment less than 5 meq / gm, at the pH of the intended use of the composition (generally ranging from pH 3 to pH 9, and in one embodiment from pH 4 to pH 8). As used herein, the "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. Such suitable cationic polymers generally have an average molecular weight of 10,000 to 10,000,000, in one embodiment 50,000 to 5,000,000, and in another embodiment 100,000 to 3,000,000.

[0130] Cationic polymers suitable for use in the compositions of the present invention contain cationic nitrogen-containing moieties, such as quaternary ammonium, or protonated cationic amino moieties. Any anionic counterion may be used in conjunction with the cationic polymer, as long as the polymer remains soluble in water, in the composition, or in the coacervate phase of the composition, and the counterion is physically and chemically compatible with the essential components of the composition or does not otherwise unduly impair the performance, stability, or aesthetics of the product. Non-limiting examples of such counterions include halides (e.g., chloride, fluoride, bromide, iodide), sulfate, and methyl sulfate.

[0131] Non-limiting examples of such polymers are described in CTFA Cosmetic Ingredient Dictionary, 3rd Edition, edited by Estrin, Crosley and Haynes (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, DC (1982)).

[0132] Particularly useful cationic polymers which may be used in accordance with the present invention include cationic cellulose, cationic guar, poly(acrylamide-co-diallyldimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide-co-methacrylamidopropyl-pentamethyl-1,3-propylene-2-ol-ammonium dichloride), poly(acrylamide-co-N,N-dimethylaminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethylaminoethyl acrylate), ...N-dimethylaminoethyl methacrylate) and its quaternized derivatives, poly(acrylamide-methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethylammonium chloride-co-acrylic acid), poly(diallyldimethylammonium chloride), poly(diallyldimethylammonium chloride-co-acrylic acid), poly(ethyl methacrylate-co-oleyl methacrylate-co-diethylaminoethyl methacrylate) and its quaternized derivatives, poly(ethyl methacrylate-co-dimethylaminoethyl methacrylate) and its quaternized derivatives, poly(hydroxypropyl acrylate-co-methacrylamidopropyltrimethylammonium chloride) and its quaternized derivatives, poly(hydroxyethyl acrylate-co-dimethylaminoethyl methacrylate) and its quaternized derivatives, poly(methyl acrylate cationic polymers including polymers selected from the group consisting of poly(vinylpyrrolidone-co-acrylamide-co-dimethylaminoethyl acrylate) and quaternized derivatives thereof, poly(methacrylate-co-methacrylamidopropyltrimethylammonium chloride), poly(vinylformamide-co-acrylic acid-co-diallyldimethylammonium chloride), poly(vinylformamide-co-diallyldimethylammonium chloride), poly(vinylpyrrolidone-co-acrylamide-co-vinylimidazole) and quaternized derivatives thereof, poly(vinylpyrrolidone-co-dimethylaminoethyl methacrylate) and quaternized derivatives thereof, poly(vinylpyrrolidone-co-methacrylamide-co-vinylimidazole) and quaternized derivatives thereof, poly(vinylpyrrolidone-co-vinylimidazole) and quaternized derivatives thereof, polyethyleneimine (including quaternized derivatives thereof), and mixtures thereof.

[0133] Other cationic polymers suitable for use in the present composition include polysaccharide polymers, cationic guar gum derivatives, quaternary nitrogen-containing cellulose ethers, synthetic polymers, etherified cellulose, guar and starch copolymers.When used, the cationic polymers herein are soluble in the composition or soluble in the complex coacervate phase formed in the composition by the above-mentioned cationic polymer and anionic, amphoteric and / or zwitterionic surfactant components.In addition, complex coacervates of cationic polymers can also be formed with other charged substances in the composition.

[0134] Suitable cationic polymers are described in U.S. Patent Nos. 3,962,418, 3,958,581, and U.S. Patent Application Publication No. 2007 / 0207109 A1.

[0135] DTIs (Defective Transfer Inhibitors) The composition may contain one or more dye transfer inhibitors. In one embodiment of the present invention, the inventors have surprisingly discovered that compositions containing a polymeric dye transfer inhibitor in addition to certain dyes exhibit improved performance. This is because, surprisingly, the polymeric dye transfer inhibitor prevents the dye from adhering. Suitable dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone, and polyvinylimidazole, or mixtures thereof. Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E, and Chromabond S-100 manufactured by Ashland Aqualon, and Sokalan HP165, Sokalan HP50, Sokalan HP53, Sokalan HP59, Sokalan® HP56K, and Sokalan® HP66 manufactured by BASF. The dye control agent may be selected from the group consisting of (i) sulfonated phenol / formaldehyde polymers, (ii) urea derivatives, (iii) polymers of ethylenically unsaturated monomers molecularly imprinted with a dye, (iv) fibers made of water-insoluble polyamides having an average diameter of about 2 μm or less, (v) polymers obtainable from the polymerization of benzoxazine monomer compounds, and (vi) combinations thereof. Other suitable DTIs are as described in WO 2012 / 004134. When present in the subject compositions, the dye transfer inhibitor may be present in a concentration of about 0.0001% to about 10%, about 0.01% to about 5%, or even about 0.1% to about 3% by weight of the composition.

[0136] Other water-soluble polymers: Examples of water-soluble polymers include, but are not limited to, polyvinyl alcohol (PVA), modified PVA, polyvinylpyrrolidone; PVA copolymers such as PVA / polyvinylpyrrolidone and PVA / polyvinylamine; partially hydrolyzed polyvinyl acetate; polyalkylene oxides such as polyethylene oxide; polyethylene glycol; acrylamide, acrylic acid; cellulose; alkylcellulose-based materials such as methylcellulose, ethylcellulose, and propylcellulose; cellulose ethers; cellulose esters; cellulose amides; polyvinyl acetate; polycarboxylic acids and salts; polyamino acids or peptides; polyamides, polyacrylamides; maleic acid / acrylic acid copolymers; polysaccharides including starch, modified starch; gelatin; alginates; xyloglucan; other hemicellulosic polysaccharides such as xylan, glucuronoxylan, arabinoxylan, mannan, glucomannan, and galactoglucomannan; and natural gums such as pectin, xanthan, and carrageenan, locust bean, arabic, tragacanth, and combinations thereof.

[0137] Oligoamines: Non-limiting examples of amines include, but are not limited to, etheramines, cyclic amines, polyamines, oligoamines (e.g., triamines, diamines, pentaamines, tetraamines), or combinations thereof. The compositions described herein may comprise an amine selected from the group consisting of oligoamines, etheramines, cyclic amines, and combinations thereof. In some aspects, the amine is not an alkanolamine. In some aspects, the amine is not a polyalkyleneimine.

[0138] Examples of suitable oligoamines include, but are not limited to, 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), tetraethylenetetraamine (TETA), tetraethylenetri ... Examples of suitable amines include tetraethylenepentamine (TEPA), tetrapropylenepentamine (TPPA), pentaethylenehexamine (PEHA), pentapropylenehexamine (PPHA), hexaethyleneheptamine (HEHA), hexapropyleneheptamine (HPHA), N,N'-bis(3-aminopropyl)ethylenediamine, 1,1,4,7,7-pentamethyldiethylenetriamine (M5-DETA), dipropylenetriamine (DPTA), or mixtures thereof, most preferably diethylenetriamine (DETA). DETA may be preferred due to its low molecular weight and / or relatively low manufacturing costs.

[0139] The oligoamines of the present disclosure may have a molecular weight of about 100 to about 1200 Da, or about 100 to about 900 Da, or about 100 to about 600 Da, or about 100 to about 400 Da, preferably about 100 to about 250 Da, and most preferably about 100 to about 175 Da, or even about 100 to about 150 Da. For purposes of this disclosure, molecular weight is determined using the free base form of the oligoamine.

[0140] Etheramines: The cleaning compositions described herein may contain an etheramine in an amount of from about 0.1% to about 10%, or from about 0.2% to about 5%, or from about 0.5% to about 4% by weight of the composition.

[0141] The etheramines of the present disclosure may have a weight average molecular weight of less than about 1000 grams / mole, or from about 100 to about 800 grams / mole, or from about 200 to about 450 grams / mole, or from about 290 to about 1000 grams / mole, or from about 290 to about 900 grams / mole, or from about 300 to about 700 grams / mole, or from about 300 to about 450 grams / mole. The etheramines of the present disclosure may have a weight average molecular weight of from about 150, or about 200, or about 350, or about 500 grams / mole to about 1000, or about 900, or about 800 grams / mole.

[0142] Alkoxylated phenolic compounds: The cleaning composition of the present disclosure may include an alkoxylated phenolic compound. The alkoxylated phenolic compound may be selected from the group consisting of an alkoxylated polyarylphenol compound, an alkoxylated polyalkylphenol compound, an alkoxylated monoalkylphenol, and mixtures thereof. The alkoxylated phenolic compound may be an alkoxylated polyarylphenol compound. The alkoxylated phenolic compound may be an alkoxylated polyalkylphenol compound.

[0143] The alkoxylated phenolic compound may be present in the cleaning composition at a concentration of from about 0.2% to about 10% or from about 0.5% to about 5% by weight of the cleaning composition.

[0144] The alkoxylated phenolic compound may have a weight average molecular weight of 280-2880.

[0145] enzyme Preferably, the composition contains one or more enzymes. Preferred enzymes provide cleaning performance and / or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, mannanase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and amylase, or mixtures thereof. A typical combination is an enzyme cocktail, which may include, for example, a protease and a lipase together with an amylase. When present in the composition, the additional enzymes may be present at an enzyme protein concentration of from about 0.00001% to about 2%, from about 0.0001% to about 1%, or even from about 0.001% to about 0.5% by weight of the composition.

[0146] Proteases The compositions of the present invention can include proteases in addition to the proteases of the present invention. A mixture of two or more proteases, especially when used 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.

[0147] 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 subtilisin (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. Suitable proteases include chemically or genetically modified variants of the aforementioned suitable proteases. In one aspect, suitable proteases may be serine proteases, such as alkaline microbial proteases and / or trypsin-type proteases. Examples of suitable neutral or alkaline proteases include: (a) Subtilisins (EC 3.4.21.62), in particular WO 2004067737, WO 2015091989, WO 2015091990, WO 2015024739, WO 2015143360, U.S. Pat. Nos. 6,312,936 (B1), 5,679,630, 4,760,025, German Patent Publication Nos. 102006022216 (A1), 102006022224 (A1), WO 2015089447, WO 2015089441, WO 2016066756, WO 2016066757, WO 2016069 Bacillus species, such as B. lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, B. pumilus, B. gibsonii, and B. akibaii, as described in US Patent Nos. 557, 2016069563, 2016069569, and 2016174234, specifically those derived from the genus Bacillus, including those with mutations S9R, A15T, V66A, A188P, V199I, Q239R, and N255D (savinase numbering system). (b) Trypsin- or chymotrypsin-type proteases, such as trypsin (e.g., of porcine or bovine origin), including the Fusarium proteases described in WO 89 / 06270 and the chymotrypsin proteases from Cellulomonas described in WO 05 / 052161 and WO 05 / 052146. (c) Metalloproteases, in particular those derived from Bacillus amyloliquefaciens as described in WO 07 / 044993(A2), those derived from Bacillus, Brevibacillus, Thermoactinomyces, Geobacillus, Paenibacillus, Lysinibacillus or Streptomyces species as described in WO 2014194032, WO 2014194054 and WO 2014194117, those derived from Kluyvera aluminosa as described in WO 2015193488 and those derived from Streptomyces and Lysobacter as described in WO 2016075078. (d) A protease having at least 90% identity to the subtilase from Bacillus sp. TY145, NCIMB 40339, described in WO 92 / 17577 (Novozymes A / S), including variants of this Bacillus sp. TY145 subtilase described in WO 2015024739 and WO 2016066757.

[0148] Particularly preferred additional proteases for the detergent of the present invention exhibit at least 90%, preferably at least 95%, more preferably at least 98%, even more preferably at least 99%, especially 100% identity to the wild-type enzyme from Bacillus lentus and are present at the following positions: S9R, A15T, V68A, N76D, N87S, S99D, S99SD, S99A, S101G, S101M, S103A, V104N / I, G118V, G118R, S128L, P1 and / or M222S (using the BPN' numbering system and amino acid abbreviations exemplified in WO 00 / 37627, incorporated herein by reference).

[0149] Most preferably, the additional protease is selected from the group of proteases that comprise the following mutations (BPN numbering system) relative to either PB92 wild type (SEQ ID NO: 2 of WO 08 / 010925) or subtilisin 309 wild type (sequence according to the PB92 backbone but containing the natural mutation N87S): (i) G118V + S128L + P129Q + S130A (ii)S101M+G118V+S128L+P129Q+S130A (iii)N76D+N87R+G118R+S128L+P129Q+S130A+S188D+N248R (iv)N76D+N87R+G118R+S128L+P129Q+S130A+S188D+V244R (v)N76D+N87R+G118R+S128L+P129Q+S130A (vi) V68A+N87S+S101G+V104N (vii)S99AD (viii)S9R+A15T+V68A+N218D+Q245R

[0150] Suitable commercially available additional protease enzymes include those sold by Novozymes A / S (Denmark) under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase®, Coronase®, Blaze®, Blaze Ultra® and Esperase®; and those sold under the trade names Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase®, Ultimase® and Purafect those sold by DuPont under the trade names Opticlean® and Optimase® by Solvay Enzymes; and those available from Henkel / Kemira, namely, BLAP (the sequence of which is shown in Figure 29 of U.S. Pat. No. 5,352,604 and which has the mutations S99D+S101R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I) and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D); and KAP (Bacillus alkalophilus subtilisin with mutations A230V+S256G+S259N) from Kao.

[0151] Commercially available proteases selected from the group consisting of Properase®, Blaze®, Ultimase®, Everlase®, Savinase®, Excellase®, Blaze Ultra®, BLAP and BLAP variants are particularly preferred for use herein in combination with the variant proteases of the invention.

[0152] 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.

[0153] 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 variants. 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). Preferred amylases include: (a) variants described in U.S. Pat. No. 5,856,164 and WO 99 / 23211, WO 96 / 23873, WO 00 / 60060, WO 06 / 002643, and WO 2017 / 192657, in particular the following positions: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 170, 180, 190, 210, 220, 230, 240, 250, 260, 270, 280, 290, 310, 320, 330, 340, 350, 360, 370, 380, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920 8, 182, 186, 193, 202, 214, 231, 246, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, and preferably D183 * and G184 * Variants that also contain deletions of (b) SEQ ID NO: 4 in WO 06 / 002643, variants exhibiting at least 85%, preferably 90% identity to the wild-type enzyme from Bacillus sp. SP722, in particular variants in which positions 183 and 184 are deleted, and variants as described in WO 00 / 60060, WO 2011 / 100410 and WO 2013 / 003659, in particular those with one or more substitutions at the following positions relative to SEQ ID NO: 4 in WO 06 / 002643, which is incorporated herein by reference: 51, 52, 54, 109, 304, 140, 189, 134, 195, 206, 243, 260, 262, 284, 347, 439, 469, 476 and 477. (c) Variants exhibiting at least 95% identity to the wild-type enzyme from Bacillus sp. 707 (SEQ ID NO: 7 in U.S. Pat. No. 6,093,562), particularly those containing one or more of the following mutations: M202, M208, S255, R172, and / or M261. Preferably, the amylase contains one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N, and / or R172Q. Particularly preferred are those containing the M202L or M202T mutation. (d) a variant described in WO 09 / 149130, preferably SEQ ID NO: 1 or SEQ ID NO: 2 in WO 09 / 149130, which shows at least 90% identity to the wild-type enzyme derived from Geobacillus Stearophermophilus or a truncated version thereof. (e) a variant described in WO 10 / 115021, in particular SEQ ID NO: 2 in WO 10 / 115021, which exhibits at least 75%, or at least 85%, or at least 90%, or at least 95% identity with the alpha-amylase from Bacillus sp. TS-23. (f) Variants exhibiting at least 89% identity to SEQ ID NO: 1 in WO 2016 / 091688, in particular those containing a deletion at positions H183+G184 and further containing one or more mutations at positions 405, 421, 422, and / or 428. (g) Variants described in WO2014099523, in particular those exhibiting at least 60% amino acid sequence identity with "PcuAmyl α-amylase" from Paenibacillus curdlanolyticus YK9 (SEQ ID NO: 3 in WO2014099523). (h) Variants described in WO2014099523, particularly those exhibiting at least 60% amino acid sequence identity with the "CspAmy2 amylase" from a Cytophaga species (SEQ ID NO: 1 or 6 in WO2014164777). (i) A variant showing at least 85% identity with AmyE from Bacillus subtilis (SEQ ID NO: 1 in WO 2009 / 149271). (j) A variant showing at least 90% identity to the wild-type amylase from Bacillus sp. KSM-K38 with accession number AB051102. (k) variants described in WO2016180748, in particular those exhibiting at least 80% identity with the mature amino acid sequence of AAI10 from Bacillus species as set forth in SEQ ID NO: 7 in WO2016180748, those exhibiting at least 80% identity with the mature amino acid sequence of amylase from Alicyclobacillus species as set forth in SEQ ID NO: 8 in WO2016180748, and those exhibiting at least 80% identity with the mature amino acid sequence of SEQ ID NO: 13 in WO2016180748, in particular those having the following mutations: * , N54S, V56T, K72R, G109A, F113Q, R116Q, W167F, Q172G, A174S, G184T, N195F, V206L, K391A, P473R, G476K. (l) Variants described in WO2018060216, in particular those showing at least 70% identity to SEQ ID NO: 4 in WO2018060216, the mature amino acid sequence of the fusion molecule of Bacillus amyloliquefaciens and Bacillus licheniformis. In particular, those containing one or more substitutions at positions H1, N54, V56, K72, G109, F113, R116, T134, W140, W159, W167, Q169, Q172, L173, A174, R181, G182, D183, G184, W189, E194, N195, V206, G255, N260, F262, A265, W284, F289, S304, G305, W347, K391, Q395, W439, W469, R444, F473, G476, and G477.

[0154] Preferably, the amylase is a genetically engineered enzyme in which one or more amino acids susceptible to bleaching oxidation are replaced with amino acids less susceptible to oxidation. In particular, methionine residues are preferably substituted with any other amino acid. In particular, the methionine most susceptible to oxidation is preferably substituted. Preferably, the methionine at position 202 in SEQ ID NO: 11 is substituted. Preferably, the methionine at this position is substituted with threonine or leucine, preferably leucine.

[0155] Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL®, ATLANTIC®, ACHIEVE ALPHA®, AMPLIFY® PRIME, INTENSA®, and BAN® (Novozymes A / S, Bagsvaerd, Denmark), KEMZYM® AT 9000 (Biozym Biotech Trading GmbH, Wehlistrasse 27b A-1200 Wien, Austria), RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE®, and PREFERENZ. Examples include the S (registered trademark) series (including PREFERENZ S1000 (registered trademark) and PREFERENZ S2000 (registered trademark)), PURASTAR OXAM (registered trademark) (DuPont, Palo Alto, California), and KAM (registered trademark) (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku, Tokyo 103-8210, Japan).

[0156] 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.

[0157] 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.

[0158] 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 variants thereof. Chemically modified or engineered variants are also suitable. Examples of suitable lipases include lipases from Humicola (synonym Thermomyces), such as H. lanuginosa (T. lanuginosus).

[0159] The lipase may be a "first cycle lipase," such as those described in WO 06 / 090335 and WO 13 / 116261. In one aspect, the lipase is a first wash lipase, preferably a variant of the wild-type lipase from Thermomyces lanuginosus, including the T231R and / or N233R mutations. Preferred lipases include those sold under the trade names Lipex®, Lipolex®, and Lipoclean® by Novozymes (Bagsvaerd, Denmark).

[0160] Other suitable lipases include, for example, Liprl 139 as described in WO 2013 / 171241, TfuLip2 as described in, for example, WO 2011 / 084412 and WO 2013 / 033318, Pseudomonas stutzeri lipase as described in, for example, WO 2018228880, Microbulbifer thermotolerans lipase as described in, for example, WO 2018228881, Sulfobacillus acidocaldarius lipase as described in, for example, EP 3299457, acidocaldarius lipases, such as LIP062 lipase as described in WO2018209026, PinLip lipase as described in WO2017036901, and Absidia species lipases as described in WO2017005798.

[0161] Suitable lipases are variants of SEQ ID NO: 5, including: (a) Substitution T231R (b) Substitution N233R or N233C (c) at least three additional substitutions selected from E1C, D27R, N33Q, G38A, F51V, G91Q, D96E, K98L, K98I, D111A, G163K, H198S, E210Q, Y220F, D254S, I255A, and P256T; wherein the positions correspond to those of SEQ ID NO: 5, and the lipase variant has at least 90% but less than 100% sequence identity to a polypeptide having the amino acid sequence of SEQ ID NO: 5, and the variant has lipase activity. One preferred lipase is a variant of SEQ ID NO:5 containing the following substitutions: T231R, N233R, D27R, G38A, D96E, D111A, G163K, D254S, and P256T. One preferred lipase is a variant of SEQ ID NO:5 containing the following substitutions: T231R, N233R, N33Q, G91Q, E210Q, I255A.

[0162] Suitable lipases are commercially available from Novozymes, for example as Lipex Evity 100L, Lipex Evity 200L (both liquid ingredients) and Lipex Evity 105T (granules), which have a different structure to the products Lipex 100L, Lipex 100T and Lipex Evity 100T, which are outside the scope of the present invention.

[0163] cellulase Consumer products can contain cellulases of bacterial or fungal origin, including chemically modified or genetically engineered variants of the protein. Suitable cellulases include those derived 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.), and KAC-500® (Kao Corporation). Preferred cellulases include the following: a) A variant exhibiting at least 60% identity to SEQ ID NO: 2 in WO 20171084560. 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. The bacterial cleaning cellulase may be a glycosyl hydrolase having enzymatic activity on amorphous cellulose substrates, the glycosyl hydrolase being 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 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 described in U.S. Pat. No. 6,268,197, or variants thereof, Bacillus agarose haerens, and the like. a GH family 5 glycosyl hydrolase (wild-type) from Bacillus agaradhaerens or a variant thereof, a GH family 5 glycosyl hydrolase (wild-type) from Paenibacillus or a variant thereof, such as XYG1034 and XYG1022 described in U.S. Pat. No. 6,630,340; a GH family 74 glycosyl hydrolase (wild-type) from Jonesia sp. or a variant thereof, such as XYG1020 described in WO 2002 / 077242; and a GH family 74 glycosyl hydrolase (wild-type) from Trichoderma Reesei or a variant thereof, such as the enzyme described in more detail in SEQ ID NO:2 of U.S. Pat. No. 7,172,891. Suitable bacterial cleaning cellulases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A / S, Bagsvaerd, Denmark).

[0164] 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.

[0165] 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. 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. Further preferred mannanases include those sold under the trade names Mannaway® (both Novozymes A / S, Bagsvaerd, Denmark), Purabrite®, Effectenz®, Preferenz® (Genencor International Inc, Palo Alto, California), and Biotouch® (AB Enzymes, Darmstadt, Germany).

[0166] Pectate lyase Other preferred enzymes include pectate lyases sold under the trade names Pectawash®, Pectaway®, and Xpect®.

[0167] Nuclease enzymes The composition may comprise a nuclease enzyme. A nuclease enzyme is an enzyme capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids. The nuclease enzyme herein is preferably a deoxyribonuclease or ribonuclease enzyme or a functional fragment thereof. A functional fragment or portion refers to a portion of a nuclease enzyme that catalyzes the cleavage of phosphodiester bonds in the DNA backbone, and thus is a region of the nuclease protein that retains catalytic activity. It therefore includes truncated but functional versions of the enzyme and / or variants and / or derivatives and / or homologs in which its function is maintained. Preferably, the nuclease enzyme is a deoxyribonuclease preferably selected from any of the following classes: EC 3.1.21.x (where x = 1, 2, 3, 4, 5, 6, 7, 8 or 9), EC 3.1.22.y (where y = 1, 2, 4 or 5), EC 3.1.30.z (where z = 1 or 2), EC 3.1.31.1, and mixtures thereof. All nuclease enzymes may contain trace amounts of superoxide dismutase.

[0168] Galactanase The enzyme system can include an extracellular polymer-degrading enzyme, including an endo-beta-1,6-galactanase enzyme. The term "endo-beta-1,6-galactanase" or "polypeptide with endo-beta-1,6-galactanase activity" refers to endo-beta-1,6-galactanase activity (EC 3.2.1.164) from glycoside hydrolase family 30 that catalyzes the hydrolytic cleavage of 1,6-3-D-galactooligosaccharides with a degree of polymerization (DP) greater than 3 and their acidic derivatives bearing a 4-O-methyl glucosyl uronate or glucosyl uronate group at the non-reducing end. For purposes of the present disclosure, endo-beta-1,6-galactanase activity is determined in Assay I according to the procedure described in WO2015185689. Suitable examples from the EC3.2.1.164 classification are described in WO2015185689, e.g., mature polypeptide SEQ ID NO: 2.

[0169] 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, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, and 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 combination with amylases. Detergent enzymes are described in more detail in U.S. Patent No. 6,579,839.

[0170] Xanthan endoglucanase and xanthan lyase The term xanthan endoglucanase refers to an enzyme exhibiting endo-beta-1,4-glucanase activity that, together with a suitable xanthan lyase enzyme, is capable of catalyzing the hydrolysis of the 1,4-linked β-D-glucose polymer backbone of xanthan gum. A xanthan endoglucanase according to the present invention has endo-beta-1,4-glucanase activity and has a polypeptide having at least 60% identity to SEQ ID NO: 1. SEQ ID NO: 1 corresponds to the amino acid sequence of a xanthan endoglucanase endogenous to Paenibacillus sp. 62047. The term "xanthan lyase" refers to an enzyme that cleaves the β-D-mannosyl-β-D-1,4-glucuronosyl bond in xanthan, and has been described in the literature. Xanthan lyase is classified as EC 4.2.2.12 according to enzyme nomenclature and is known to be produced by many xanthan-degrading bacteria, including species of the genera Bacillus, Corynebacterium, and Paenibacillus. The xanthan lyase according to the present invention has xanthan lyase activity and comprises a polypeptide having at least 60% identity to SEQ ID NO: 2. SEQ ID NO: 2 corresponds to the amino acid sequence of xanthan lyase endogenous to species of the genus Paenibacillus.

[0171] bleach It may be preferred for the composition to include one or more bleaching agents. Suitable bleaching agents other than bleach catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, and mixtures thereof. Generally, when a bleaching agent is used, the compositions of the present invention may comprise from about 0.1% to about 50%, or even from about 0.1% to about 25%, by weight of the subject composition, of the bleaching agent or mixture of bleaching agents. Examples of suitable bleaching agents include: (1) Photobleaches, such as sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanine, xanthene dyes, thioxanthone, and mixtures thereof. (2) Preformed Peracids: Suitable preformed peracids include, but are not limited to, preformed peroxyacids or salts thereof, typically compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, e.g., Oxone®, and mixtures thereof.

[0172] Particularly preferred peroxyacids are phthalimido-peroxy-alkanoic acids, especially ε-phthalimidoperoxyhexanoic acid (PAP). Preferably, the peroxyacid or its salt has a melting point in the range of 30°C to 60°C. (3) Hydrogen peroxide sources, for example, inorganic perhydrate salts, including alkali metal salts such as sodium salts of perborates (usually monohydrate or tetrahydrate), percarbonates, persulfates, perphosphates, persilicates, and mixtures thereof. When used, inorganic perhydrate salts are typically present in amounts of 0.05 to 40% or 1 to 30% by weight of the total fabric care and home care product, and are typically incorporated into such fabric care and home care products as crystalline solids that can be coated. Suitable coatings include inorganic salts, such as alkali metal silicates, carbonates, or borates, or mixtures thereof, or organic materials, such as water-soluble or dispersible polymers, waxes, oils, or fatty soaps. (4) Bleach activators having the formula R—(C═O)—L, where R is an alkyl group, optionally branched, having 6 to 14 carbon atoms, or 8 to 12 carbon atoms, if the bleach activator is hydrophobic, or less than 6 carbon atoms, or even less than 4 carbon atoms, if the bleach activator is hydrophilic, and L is a leaving group. Examples of suitable leaving groups are benzoic acid and its derivatives, especially benzenesulfonate. Suitable bleach activators include dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or its salts, 3,5,5-trimethylhexanoyloxybenzenesulfonate, tetraacetylethylenediamine (TAED), and nonanoyloxybenzenesulfonate (NOBS). (5) Bleaching catalyst. The compositions of the present invention may contain one or more bleaching catalysts capable of accepting an oxygen atom from a peroxyacid and / or its salt and transferring the oxygen atom to an oxidizable substrate. Suitable bleaching 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 α-amino-ketones, and mixtures thereof. One particularly preferred catalyst is an acylhydrazone type such as 4-(2-(2-((2-hydroxyphenylmethyl)methylene)-hydrazinyl)-2-oxoethyl)-4-methyl chloride. (6) The composition may preferably contain a catalytic metal complex. One preferred type of metal-containing bleach catalyst is a catalyst system containing a transition metal cation of defined bleach catalytic activity, such as a cation of copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese.

[0173] Optionally, the compositions herein can be catalyzed by a manganese compound. Such compounds and use levels are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent No. 5,576,282. In some embodiments, no additional oxidant source is present in the composition, and molecular oxygen from the air provides the oxidizing source.

[0174] Cobalt bleach catalysts useful herein are known and are described, for example, in US Pat. Nos. 5,597,936 and 5,595,967.

[0175] builder Preferably, the composition may include one or more builders or builder systems. When builders are used, the compositions of the present invention typically include at least 1%, 2% to 60% builder. It may be preferable for the composition to include low levels of phosphate and / or zeolite, e.g., 1 to 10 or 5% by weight. The composition may even be substantially free of strong builders. By substantially free of strong builders, it is meant that zeolite and / or phosphate are "not intentionally added." Typical zeolite builders include zeolite A, zeolite P, and zeolite MAP. A typical phosphate builder is sodium tripolyphosphate.

[0176] organic acid The detergent composition may comprise one or more organic acids selected from the group consisting of acetic acid, adipic acid, aspartic acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, citric acid, formic acid, glutaric acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, lactic acid, maleic acid, malic acid, malonic acid, oxydiacetic acid, oxydisuccinic acid, succinic acid, sulfamic acid, tartaric acid, tartaric acid disuccinic acid, tartaric acid-succinic acid, or mixtures thereof. Preferably, the detergent composition may comprise an organic acid selected from the group consisting of acetic acid, lactic acid, and citric acid.

[0177] chelating agents Preferably, the composition includes a chelating agent and / or a crystal growth inhibitor. Suitable molecules include copper, iron, and / or manganese chelating agents and mixtures thereof. Suitable molecules include hydroxamic acids, aminocarboxylates, aminophosphonates, succinates, salts thereof, and mixtures thereof. Non-limiting examples of chelating agents suitable for use herein include ethylenediaminetetraacetic acid, N-(hydroxyethyl)ethylenediaminetriacetic acid, nitrilotriacetic acid, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetic acid, diethylenetriaminepentaacetic acid, ethanoldiglycine, ethylenediaminetetrakis(methylenephosphonate), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), ethylenediaminedisuccinate (EDDS), hydroxyethanedimethylenephosphonic acid (HEDP), methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), N,N-dicarboxymethylglutamic acid (GLDA), and salts thereof, and mixtures thereof. Other non-limiting examples of chelating agents for use in the present invention can be found in U.S. Patent Nos. 7,445,644, 7,585,376, and U.S. Patent Application Publication No. 2009 / 0176684(A1). Other suitable chelating agents for use herein are the commercially available DEQUEST series, as well as chelating agents manufactured by Monsanto, DuPont, and Nalco, Inc. Still other suitable chelating agents include pyridinyl N-oxide types.

[0178] Optical brighteners Commercially available optical brighteners suitable for the present disclosure 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.

[0179] The optical brightener may be selected from the group consisting of disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (whitening agent 15, sold under the trade name Tinopal AMS-GX by BASF), disodium 4,4'-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (sold under the trade name Tinopal UNPA-GX by BASF), disodium 4,4'-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (sold under the trade name Tinopal 5 BM-GX by BASF). More preferably, the optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate or disodium 2,2'-([1,1'-biphenyl]-4,4'-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid. The optical brightener may be added in particulate form or as a premix with a suitable solvent, such as a nonionic surfactant, propanediol.

[0180] Enzyme Stabilizers The composition may preferably contain an enzyme stabilizer. Any conventional enzyme stabilizer may be used, for example, by having a water-soluble source of calcium and / or magnesium ions present in the final fabric care and home care product that provides calcium and / or magnesium ions to the enzyme. In the case of aqueous compositions containing proteases, reversible protease inhibitors such as boron compounds including borates, i.e., preferably 4-formylphenylboronic acid, phenylboronic acid and their derivatives, or compounds such as calcium formate, sodium formate, and 1,2-propanediol, may be added to further improve stability.

[0181] solvent: The solvent system in the composition of the present invention can be a solvent system containing only water or a mixture of organic solvents, either free of water or preferably containing water. The composition can optionally contain an organic solvent. Suitable organic solvents include C 4~14 Ethers and diethers, glycols, alkoxylated glycols, C6-C 16 Glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C8-C 14 Alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof, are included. Preferred organic solvents include 1,2-propanediol, 2,3-butanediol, ethanol, glycerol, ethoxylated glycerol, dipropylene glycol, methylpropanediol, and mixtures thereof, such as 2-ethylhexanol, 3,5,5-trimethyl-1-hexanol, and 2-propylheptanol. The solvent may be a polyethylene or polypropylene glycol ether of glycerin. Other lower alcohols, such as C1-C4 alkanolamines, may also be used, such as monoethanolamine and triethanolamine. While a solvent system may be absent, for example, in anhydrous solid embodiments of the present invention, it is more typically present in a concentration of the organic solvent ranging from about 0.1% to about 98% by weight of the liquid detergent composition, preferably at least about 1% to about 50%, more usually from about 5% to about 25%, or alternatively from about 1% to about 10% by weight. These organic solvents may be used with or without water.

[0182] Structured Liquids: In some embodiments of the present invention, the composition is in the form of a structured liquid. Such structured liquids may be internally structured to form structure through primary components (e.g., surfactant materials) and / or externally structured by using secondary components (e.g., polymers, clays, and / or silicate materials) to provide a three-dimensional matrix structure, for example, for use as a thickener. The composition may contain a structuring agent, preferably 0.01% to 5% by weight, or 0.1% to 2.0% by weight. Examples of suitable structuring agents are set forth in U.S. Patent Application Publication Nos. 2006 / 0205631 (A1), 2005 / 0203213 (A1), U.S. Patent Nos. 7,294,611, and 6,855,680. The structuring agent is typically selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, cellulosic materials, microfiber cellulose, hydrophobically modified alkali-swellable emulsions such as Polygel W30 (3VSigma), biopolymers, xanthan gum, gellan gum, hydrogenated castor oil, derivatives of hydrogenated castor oil, such as non-ethoxylated derivatives, and mixtures thereof, particularly hydrogenated castor oil, derivatives of hydrogenated castor oil, microfiber cellulose, hydroxy-functional crystalline materials, long-chain aliphatic alcohols, 12-hydroxystearic acid, clays, and mixtures thereof. One preferred structuring agent is described in U.S. Patent No. 6,855,680, which defines suitable hydroxy-functional crystalline materials in detail. Preferred is hydrogenated castor oil. Some structuring agents have thread-like structural systems with a range of aspect ratios. Another preferred structurant is cellulose-based and may be derived from a number of sources including biomass, wood pulp, citrus fiber, and the like.

[0183] Conditioning Agents: Suitable conditioning agents include high-melting-point fatty compounds.The 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.Suitable conditioning agents also include nonionic polymers and conditioning oils, such as hydrocarbon oils, polyolefins, and fatty acid esters.

[0184] Suitable conditioning agents include those characterized generally as silicones (e.g., silicone oils, polyoils, 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 dispersed particles in the aqueous surfactant matrix herein. The compositions of the present invention may also contain 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.

[0185] Probiotics: The composition may also include probiotics such as those described in WO 2009 / 043709.

[0186] Foam Booster: If high foaming is desired, the composition may preferably contain a foam booster. A suitable example is C 2 , which is preferably incorporated at a concentration of 1% to 10%. 10 ~C 16 Alkanolamine or C 10 ~C 14 It is an alkyl sulfate. 10 ~C 14Monoethanolamides and diethanolamides exemplify typical classes of such foam boosters. It is also beneficial to use such foam boosters in conjunction with high-foaming co-surfactants, such as the amine oxides, betaines, and sultaines mentioned above. If desired, water-soluble magnesium and / or calcium salts, such as MgCl, MgSO, CaCl, and CaSO, may be added, typically at concentrations of 0.1% to 2%, to provide additional foam and enhance grease removal.

[0187] Foam suppressor: Compounds for reducing or suppressing foam formation may be incorporated into water-soluble unit-dose articles. Foam suppression can be particularly important in so-called "high-concentration wash processes" and in front-loading washing machines. Examples of suds suppressors include monocarboxylic fatty acids and their soluble salts, high molecular weight hydrocarbons such as paraffins, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C18-C40 ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point below about 100°C, silicone suds suppressors, and secondary alcohols. A preferred fatty acid blend may be a mixture enriched with 2-alkyl fatty acids, preferably 2-methyloctanoic acid, or a fatty acid mixture enriched with 2-alkyl fatty acids.

[0188] Further suitable antifoaming agents are those derived from phenylpropylmethyl-substituted polysiloxanes.

[0189] 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.

[0190] 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.

[0191] Pearlizing Agents: Non-limiting examples of pearlescent agents include: mica; titanium dioxide coated mica, bismuth oxychloride, fish scales, monoesters and diesters of alkylene glycols. The pearlescent agent may be ethylene glycol distearate (EGDS).

[0192] Opacifiers: In one embodiment, the composition may include an opacifier. As used herein, an "opacifier" is a substance added to a material to make the following system opaque. In a preferred embodiment, the opacifier is Acusol, available from Dow Chemicals. Acusol opacifiers are provided in liquid form at specific % solids. As supplied, Acusol opacifiers have a pH range of 2.0-5.0 and particle sizes in the range of 0.17-0.45 um. In a preferred embodiment, Acusol OP303B and 301 can be used.

[0193] In yet another embodiment, the opacifier may be an inorganic opacifier. Preferably, the inorganic opacifier may be TiO2, ZnO, talc, CaCo3, and combinations thereof. The opacifier-microsphere composite material is easily formed at a preselected specific gravity, and therefore the material has little tendency to separate.

[0194] Hydrotropes: The compositions may optionally contain an effective amount of a hydrotrope to render the composition compatible with water, i.e., about 0% to 15%, or about 1% to 10%, or about 3% to about 6%. Suitable hydrotropes for use herein include anionic hydrotropes, such as those disclosed in U.S. Patent No. 3,915,903, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium, and ammonium toluene sulfonate, sodium, potassium, and ammonium cumene sulfonate, and mixtures thereof.

[0195] Antioxidants: The composition may optionally contain from about 0.001 to about 2% by weight of an antioxidant present in the composition. Preferably, the antioxidant is present at a concentration in the range of 0.01 to 0.08% by weight. Mixtures of antioxidants may also be used.

[0196] Antioxidants are substances such as those described in Kirk-Othmer (Vol. 3, p. 424) and Ullmann's Encyclopedia (Vol. 3, p. 91).

[0197] One class of antioxidants that may be used in the present invention are alkylated phenols having the general formula:

[0198] [ka] (Wherein, R is C1 to C 22 (R1 is a C3-C6 branched alkyl, preferably tert-butyl; and x is 1 or 2.) Hindered phenol compounds are a preferred class of alkylated phenols having this formula. Examples of such hindered phenol antioxidants include 2,6-bis(1-methylpropyl)phenol; 2,6-bis(1,1-dimethylethyl)-4-methyl-phenol (hydroxybutylated toluene, also known as "BHT"); 2-(1,1-dimethylethyl)-1,4-benzenediol; 2,4-bis(1,1-dimethylethyl)-phenol; 2,6-bis(1,1-dimethylethyl)-phenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, methyl ester; 2-(1,1-dimethyl 2-(1,1-dimethylethyl)-4,6-dimethyl-phenol;3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 1,1'-[2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl] ester;3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, octadecyl ester, 2,2'-methylenebis[6-(1,1-dimethylethyl)-4-methylphenol N,N'-1,6-Hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanamide;N ... 4-Hydroxybenzoic acid, hexadecyl ester; P-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylphosphonic acid, diethyl ester; 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; 3,5-bis(1,1-5 dimethylethyl)-4-hydroxybenzenepropanoic acid, 2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]hydrazide;3-(1,1-dimethylethyl)-4-hydroxy-5-methylbenzenepropanoic acid, 1,1'-[1,2-ethanediylbis(oxy-2,1-ethanediyl)] ester; 4-[(dimethylamino)methyl]-2,6-bis(1,1-dimethylethyl)phenol; 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)phenol; 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 1,1'-(thiodi-2,1-ethanediyl) 3,5-Bis(1,1-dimethylethyl)-4-hydroxybenzoic acid, 2,4-bis(1,1-dimethylethyl)phenyl ester;3,5-Bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 1,1'-(1,6-hexanediyl) ester;3-(1,1-Dimethylethyl)-4-hydroxy-5-methylbenzenepropanoic acid, 1,1'-[2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2,2-dimethyl-2,1-ethanediyl)] ester;3-(1,1 -dimethylethyl)-b-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-b-methylbenzenepropanoic acid, 1,1'-(1,2-ethanediyl) ester;2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioic acid, 1,3-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester;3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 1-[2-[3-[3,5-bis(1,1-dimethylethyl) -4-Hydroxyphenyl]-1-oxopropoxy]ethyl]-2,2,6,6-tetramethyl-4-piperidinyl ester;3,4-Dihydro-2,5,7,8-tetramethyl-2-[(4R,8R)-4,8,12-trimethyltridecyl]-(2R)-2H-1-benzopyran-6-ol;2,6-Dimethylphenol;2,3,5-Trimethyl-1,4-benzenediol;2,4,6-Trimethylphenol;2,3,6-Trimethylphenol;4,4'-(1-Methylethylidene)-bis[2,6-dimethylphenol];These may include, but are not limited to, 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; 4,4'-methylenebis[2,6-dimethylphenol]; and mixtures thereof.

[0199] Preferably, the hindered phenol antioxidant contains at least one phenolic -OH group with at least one C3 to C6 branched alkyl in the ortho position relative to the at least one phenolic -OH group. More preferably, the hindered phenol antioxidant is an ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid, and most preferably a C1 to C22 linear alkyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid. Commercially available C1-C22 linear alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid include RALOX®, a methyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid manufactured by Raschig USA (Texas, USA), and TINOGARD® TS, an octadecyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid manufactured by BASF (Ludwigshafen, Germany).

[0200] Furthermore, the antioxidant used in the composition may be selected from the group consisting of 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. It should be noted that ethoxyquin (1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) is sold under the name Raluquin™ by the Raschig™ company.

[0201] Other types of antioxidants that can be used in the compositions are 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox™) and 1,2-benzisothiazolin-3-one (Proxel GXL™).

[0202] A further class of antioxidants that may be suitable for use in the compositions are benzofuran or benzopyran derivatives having the formula:

[0203] [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. 19 alkyl, R6 is a C1-C6 alkyl, R7 is hydrogen or a 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. The cleaning compositions of the present disclosure may include a tannin selected from the group consisting of gallotannins, ellagitannins, complex tannins, condensed tannins, and combinations thereof.

[0204] Sanitizer: The compositions of the present invention may also include ingredients to provide hygiene and / or malodor benefits, such as one or more of zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac®, polyethyleneimine (such as Lupasol® from BASF) and zinc complexes thereof, silver and silver compounds, particularly those designed to slow release Ag+ or nanosilver dispersions.

[0205] The cleaning compositions of the present invention may also contain antimicrobial agents. Cationic active ingredients may include, but are not limited to, n-alkyldimethylbenzylammonium chloride, alkyldimethylethylbenzylammonium chloride, dialkyldimethyl quaternary ammonium compounds such as didecyldimethylammonium chloride, N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate, dioctyldidecylammonium chloride (including quaternary species such as benzethonium chloride, alkylpyridinium chloride, and quaternary ammonium compounds with inorganic or organic counterions such as bromine), carbonate salts, or other moieties containing dialkyldimethylammonium carbonate, as well as antimicrobial amines such as chlorhexidine gluconate, PHMB (polyhexamethylene biguanide), biguanide salts, substituted biguanide derivatives, organic salts of quaternary ammonium-containing compounds, or inorganic salts of quaternary ammonium-containing compounds, or mixtures thereof. More preferably, the antimicrobial agent is selected from the group consisting of 4-4'-dichloro-2-hydroxydiphenyl ether ("diclosan"), 2,4,4'-trichloro-2'-hydroxydiphenyl ether ("triclosan"), and combinations thereof. Most preferably, the antimicrobial agent is 4-4'-dichloro-2-hydroxydiphenyl ether, commercially available from BASF under the trade name Tinosan® HP100.

[0206] package Any conventional packaging may be used, and the packaging may be wholly or partially transparent so that the consumer can see the color of the laundry care composition that may be caused by or contributed to the color of the dye essential to the present invention. Part or all of the packaging may contain an ultraviolet absorbing compound.

[0207] When in liquid form, laundry care compositions of the present invention may be aqueous (typically having a total water content of more than 2 wt. %, or even more than 5 or 10 wt. %, up to 90 or up to 80 or 70 wt. % total water content) or non-aqueous (typically having a total water content of less than 2 wt. % total water content). Typically, compositions of the present invention are in the form of an aqueous solution or homogeneous dispersion or suspension of surfactant, shading dye, and certain other ingredients (some of which may be in normally solid form) combined with the normally liquid components of the composition, e.g., alcohol ethoxylate nonionic liquid, aqueous liquid carrier, and any other normally liquid optional ingredients. Such solutions, dispersions, or suspensions have acceptable phase stability. When the laundry care compositions of the present invention are in liquid form, preferably their viscosity is from 1 to 1500 centipoise (1 to 1500 mPa s) at 20 s-1 and 21°C. * s), more preferably 100 to 1000 centipoise (100 to 1000 mPa * s), most preferably 200 to 500 centipoise (200 to 500 mPa *The viscosity can be measured by conventional methods. Viscosity may be measured using a TA Instruments AR550 rheometer with a plate steel spindle of 40 mm diameter and 500 μm gap size. The high shear viscosity at 20 s-1 and the low shear viscosity at 0.05 s-1 can be obtained from a 3-minute log shear rate sweep of 0.1 s-1 to 25 s-1 at 21°C. The preferred rheology described herein can be achieved by using an internal structuring agent with the detergent ingredients or by using an external rheology modifier. More preferably, the high shear rate viscosity of the laundry care composition, e.g., liquid detergent composition, is about 100 centipoise to 1500 centipoise, more preferably 100 to 1000 cps. The high shear rate viscosity of the unit dose laundry care composition, e.g., liquid detergent composition, is 400 to 1000 cps. Laundry care compositions, such as laundry softening compositions, typically have a high shear rate viscosity of 10 to 1000, more preferably 10 to 800 cps, and most preferably 10 to 500 cps. Hand dishwashing compositions have a high shear rate viscosity of 300 to 4000 cps, more preferably 300 to 1000 cps.

[0208] The liquid compositions herein, preferably laundry care compositions, can be prepared by combining the components in any conventional order and mixing, e.g., stirring, the resulting combination of components to form a phase-stable liquid laundry care composition. In the process of preparing such compositions, a liquid matrix is ​​formed containing at least most, or even substantially all, of the liquid components, such as nonionic surfactants, non-surface-active liquid carriers, and other optional liquid components, and the liquid components are thoroughly mixed by applying shear agitation to the liquid combination. For example, high-speed agitation using a mechanical agitator can be usefully used. While maintaining shear agitation, any anionic surfactants and substantially all of the solid-state components can be added. Agitation of the mixture can be continued, and if necessary, increased at this point, to form a solution or homogeneous dispersion of insoluble solid particles within the liquid phase. After some or all of the solid-state materials have been added to the agitated mixture, any enzyme particles, e.g., enzyme prills, are incorporated. As a variation of the above-described composition preparation procedure, one or more of the solid components may be added to the stirred mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components. After all of the composition components have been added, stirring of the mixture is continued for a time sufficient to form a composition having the required viscosity and phase stability characteristics. This often involves stirring for between about 30 and 60 minutes.

[0209] Pouch In a preferred embodiment of the present invention, the composition is provided in either a unit dose form, a tablet form, or a liquid / solid (optionally granular) / gel / paste form, preferably held within a water-soluble film (known as a pouch or pod). The composition may be a laundry cleaning composition, an automatic dishwashing composition, a hard surface cleaning composition, or a combination thereof. The composition may be enclosed in a single-compartment pouch or a multi-compartment pouch. Multi-compartment pouches are described in more detail in EP 2133410(A). When the composition is present in a multi-compartment pouch, the composition of the present invention may be present in one or more compartments, i.e., a dye may be present in one or more compartments, optionally in all compartments. Non-shading dyes or pigments or other aesthetic agents may also be used in one or more compartments. In one embodiment, the composition is present in one compartment of a multi-compartment pouch.

[0210] Preferred film materials are polymeric materials. Film materials can be obtained, for example, by casting, blow molding, extrusion, or blow-extrusion of polymeric materials, as is known in the art. Preferred polymers, copolymers, or derivatives thereof suitable for use as pouch materials are selected from polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamides, maleic acid / acrylic acid copolymers, polysaccharides including starch and gelatin, and natural gums such as xanthan and cara gum. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and most preferably polyvinyl alcohol, polyvinyl alcohol copolymers, and hydroxypropylmethylcellulose (HPMC), and combinations thereof. Preferably, the concentration of polymer, e.g., PVA polymer, in the pouch material is at least 60%. The polymer may have any weight-average molecular weight, preferably about 1,000 to 1,000,000, more preferably about 10,000 to 300,000, and even more preferably about 20,000 to 150,000. Mixtures of polymers may also be used as pouch materials. This can be beneficial for controlling the mechanical and / or dissolution properties of the compartment or pouch depending on the application and required needs. Suitable mixtures include, for example, mixtures in which one polymer has a higher aqueous solubility and / or a higher mechanical strength than another polymer.Also suitable are mixtures of polymers with different weight-average molecular weights, such as a mixture of PVA or its copolymers with a weight-average molecular weight of about 10,000 to 40,000, preferably about 20,000, and PVA or its copolymers with a weight-average molecular weight of about 100,000 to 300,000, preferably about 150,000. Also suitable herein are polymer blend compositions containing hydrolytically degradable, water-soluble polymer blends, such as a polymer blend of polylactide and polyvinyl alcohol obtained by blending polylactide and polyvinyl alcohol, typically containing about 1 to 35% by weight of polylactide and about 65 to 99% by weight of polyvinyl alcohol. Preferred for use herein are polymers that are about 60% to about 98% hydrolyzed, preferably about 80% to about 90% hydrolyzed, to improve the solubility properties of the material.

[0211] Of course, different film materials and / or films of different thicknesses may be used to make the compartments of the present invention. An advantage of choosing different films is that the resulting compartments may exhibit different solubility or release characteristics.

[0212] The most preferred film materials are the PVA films known as MonoSol product reference numbers M8630, M8900, H8779, and those described in U.S. Pat. Nos. 6,166,117 and 6,787,512, and PVA films of corresponding solubility and deformation characteristics.

[0213] The film materials herein may also contain one or more additive-containing components. For example, it may be beneficial to add plasticizers such as glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol, and mixtures thereof. Other additives include functional detergent additives delivered to the wash water, such as organic polymer dispersants.

[0214] Solid form: As mentioned above, laundry care composition can be in solid form.Suitable solid form includes tablet and particle shape, for example, granular particles, flakes or sheets.Various techniques for forming such detergent composition in solid form are well known in the art and can be used herein.

[0215] Fibrous water-soluble unit dose articles: As used herein, the phrases "water-soluble unit dose article," "water-soluble fibrous structure," and "water-soluble fibrous element" mean that the unit dose article, fibrous structure, and fibrous element are miscible with water. In other words, the unit dose article, fibrous structure, or fibrous element can form a homogeneous solution with water at ambient conditions. "Ambient conditions," as used herein, means 23°C ± 1.0°C and 50% ± 2% relative humidity. The water-soluble unit dose article may contain insoluble materials that are dispersible at a suspended mean particle size of less than about 20 micrometers or less than about 50 micrometers under aqueous wash conditions.

[0216] The fibrous water-soluble unit dose can include any of the disclosures found in U.S. Patent Application Nos. 15 / 880,594, filed January 26, 2018, 15 / 880,599, filed January 26, 2018, and 15 / 880,604, filed January 26, 2018, which are incorporated by reference in their entireties. Preferred water-soluble fibrous structures include particles having a ratio of linear alkylbenzene sulfonate to alkyl ethoxylated sulfate or alkyl sulfate of greater than 1.

[0217] These fibrous water-soluble unit dose articles can dissolve under various washing conditions, such as low temperature, low water volume, and / or short wash cycles, or cycles where consumers overload their washing machines, especially with items having high water absorption capacity, while delivering sufficient active agent to exert the intended effect on the target consumer substrate (with performance similar to that of today's liquid products). Furthermore, the water-soluble unit dose articles described herein can be economically manufactured by spinning fibers containing the active agent. The water-soluble unit dose articles described herein also have improved cleaning performance.

[0218] Method of Use. The compositions of the present invention prepared as described above can be used to form aqueous cleaning / treatment solutions for use in laundering / treating fabrics. Generally, an effective amount of such a composition is added to water, for example, in a conventional automatic fabric washing machine, to form such an aqueous laundry solution. The aqueous laundry solution thus formed is then contacted, typically under agitation, with the fabrics to be laundered / treated with the solution. An effective amount of the liquid detergent composition herein to be added to water to form an aqueous laundry solution can include an amount sufficient to form about 500 to 7,000 ppm of the composition in the aqueous laundry solution, or about 1,000 to 3,000 ppm of the laundry care composition herein is provided in the aqueous wash solution.

[0219] Typically, the wash liquor is formed by contacting the laundry care composition with an amount of wash water such that the concentration of the laundry care composition in the wash liquor is greater than 0 g / L to 5 g / L, or 1 g / L to 4.5 g / L, or 4.0 g / L, or 3.5 g / L, or 3.0 g / L, or 2.5 g / L, or even 2.0 g / L, or even 1.5 g / L. The method of laundering fabrics or textiles may be carried out in a top load or drum load automatic washing machine, or may be used in hand laundry applications. In these applications, the wash liquor formed, and the concentration of the laundry detergent composition in the wash liquor, is that of the main wash cycle. When determining the volume of the wash liquor, any water input during any optional rinse step is not included.

[0220] The wash liquor may contain 40 liters or less of water, or 30 liters or less, or 20 liters or less, or 10 liters or less, or 8 liters or less, or even 6 liters or less of water. The wash liquor may contain from greater than 0 liters to 15 liters, or from 2 liters to 12 liters, or even up to 8 liters of water. Typically, 0.01 kg to 2 kg of fabrics are added to the wash liquor per liter of wash liquor. Typically, 0.01 kg or more, or 0.05 kg or more, or 0.07 kg or more, or 0.10 kg or more, or 0.15 kg or more, or 0.20 kg or more, or 0.25 kg or more of fabrics are added to the wash liquor per liter of wash liquor. Optionally, 50 g or less, or 45 g or less, or 40 g or less, or 35 g or less, or 30 g or less, or 25 g or less, or 20 g or less, or even 15 g or less, or even 10 g or less of the composition is contacted with water to form a wash liquor. Such compositions are typically used at a concentration of about 500 ppm to about 15,000 ppm in solution. When the wash solvent is water, the water temperature typically ranges from about 5° C. to about 90° C., and when the site includes fabric, the water to fabric ratio is typically about 1:1 to about 30:1. Typically, the pH of a wash liquor containing the laundry care composition of the present invention is 3 to 11.5.

[0221] In one aspect, such a method is disclosed that includes the steps of optionally washing and / or rinsing the surface or fabric, contacting the surface or fabric with any of the compositions disclosed herein, and then optionally washing and / or rinsing the surface or fabric, together with an optional drying step.

[0222] Such surface or fabric drying can be accomplished by any one of the common means used in either domestic or industrial environments. The fabric may include any fabric that can be laundered under normal consumer or commercial conditions. The present invention is suitable for cellulosic substrates, and in some embodiments, is also suitable for treating synthetic fabrics, such as polyester and nylon, as well as blended fabrics and / or fibers containing synthetic and cellulosic fabrics and / or fibers. Examples of synthetic fabrics are polyester and nylon, which may be present in blends with cellulosic fibers, such as polycotton fabrics. The pH of the solution is typically 7 to 11, more commonly 8 to 10.5. The composition is typically used at a concentration of 500 ppm to 5,000 ppm in solution. Water temperatures typically range from about 5°C to about 90°C. The water to fabric ratio is typically about 1:1 to about 30:1.

[0223] 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 available from DuPont under the trade name SONTARA® and from James River Corp under the trade name POLY WEB®. [Example]

[0224] [Table 7] 1. The chelating agent is diethylenetriaminepentaacetic acid 2PE-20, commercially available from BASF 3 The optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbene disulfonate, and preservative 2 is phenoxyethanol. 4 Preservative 1 is BIT, commercially available as Proxel from Lonza 5 Preservative 2 is phenoxyethanol 6 Foam suppressor 1 is DC1520 available from Dow Corning 7 Foam suppressor 2 is AF-8017, commercially available from Dow The eight-tone dye is Liquitint Violet 200, available from Milliken.

[0225] Stain removal Technical stain swatches of CW120 cotton containing CFT ASTM Dust Sebum PCS94, CFT Discriminating Sebum PCS132, and APD Grass CW120 GSRTGR001 were purchased from Advanced Product Design Co., Inc. (Cincinnati, OH). The swatches were washed in a Whirlpool® drum-type high-efficiency washing machine (standard 18 liter wash cycle) using a water hardness of 7 grains / gallon and washed at 77°F. The total amount of liquid detergent used in the test was 43 grams.

[0226] Image analysis was used to compare each stain to a control sample of unstained fabric. Software converted the resulting images to standard color values, compared them to reference values ​​based on the commonly used Macbeth color retention chart, and assigned a color value to each stain (stain level). Eight replicates of each were made. Stain removal from the swatches was measured as follows.

[0227]

number

[0228] [Table 8]

[0229] These results demonstrate the surprising stain removal benefits of the compositions of the present invention (used in compositions B, D, and F) against sebum and grass when compared to branched alkyl sulfates in conventional liquid detergent compositions A, C, and E.

[0230] [Table 9]

[0231] [Table 10]

[0232] Stain Removal Index Method The method involves using a tergotometer to simulate washing fabrics in a washing machine. The test formulation was used to wash the test fabrics along with clean knitted cotton ballast and eleven 6 cm x 6 cm SBL2004 stain squares (60 g). The SBL2004 sheets were purchased from WFK Testgewebe GmbH and cut into 6 cm x 6 cm squares. The wash test consisted of two internal replicates and four external replicates for each stain type and treatments A-H listed above.

[0233] A tergotometer pot containing 1 L of test wash solution + test fabric, stain squares, and ballast at 25°C and 7 US gpg was agitated at 208 rpm for 12 minutes and spun dry. The fabrics were then rinsed in 7 US gpg water at 15°C for 5 minutes at 167 rpm and spun dry. After rinsing, the fabrics were dried on high for 70 minutes before analysis. Image analysis was used to compare each stain to a control of unstained fabric. Software converted the resulting images to standard color values ​​and compared them to reference values ​​based on the commonly used Macbeth color retention chart, assigning a color value to each stain (stain level). Eight replicates of each were made.

[0234] Stain removal from the swatches was measured as follows.

[0235]

number

[0236] [Table 11]

[0237] [Table 12]

[0238] These results demonstrate the surprising stain removal advantage of the compositions of the present invention (used in compositions B, D, F, and H) for PCS132 Sebum and PCS94 Dust Sebum when compared to branched alkyl sulfates in conventional liquid detergent compositions A, C, E, and G.

[0239] Foaming promotion

[0240] [Table 13]

[0241] The foam production and foam mileage of the test cleaning compositions herein are measured by using a foam cylinder tester (SCT). The SCT has a set of eight cylinders. Each cylinder is typically a Lexan plastic cylinder 30 cm long and 8.8 cm inside diameter, with an adhesive rule attached to the outside. The cylinders are rotated together at a speed of 20-22 revolutions per minute (rpm). This method is used to assay the performance of the test cleaning compositions to obtain a reading of their foam-producing ability as well as the foam robustness in the presence of the test soil.

[0242] Dissolve 18.6 g of the test cleaning composition in 500 g of water with a water hardness of approximately 15 gpg, heated to approximately 140°F, to form a sample solution containing the test cleaning composition product at a surfactant concentration of approximately 360 ppm; pour approximately 300 mL of the sample solution into SCT cylinders, filling each cylinder to the 5.5 cm adhesive ruler mark with the sample solution. The temperature of the sample solution will decrease over time. The target temperature of the sample solution in the cylinder is 107°F to 115°F. Place the rubber stoppers and secure the cylinders in place. Rotate the cylinders for 2 minutes. Secure in an upright position. Record the initial foam height (i.e., the height of the foam + liquid sample solution). Calculate the foam height generated by subtracting the height of the liquid sample solution alone (5.5 cm) from the total foam height. Continue rotating the cylinders, and record the total foam height every 2 minutes for a total of 20 minutes. This data represents the foam production of the test cleaning composition. Open the rubber stoppers of each cylinder. Add 10.00g of test soil to each cylinder. Test soil preparation is performed as follows: Disperse 3.60g of oleic acid (Acros Organics CAS#112-80-1) into 596.40g of Crisco canola oil using an IKA RW20 overhead mixer equipped with a blade until a homogeneous mixture is obtained. Replace the rubber stopper. Record the initial foam height and rotate the cylinder for 1 minute. Secure in an upright position. Record the initial foam height (i.e., height of foam + liquid sample solution). Calculate the foam height generated by subtracting the height of the liquid sample solution alone (5.5cm) from the total foam height. Continue rotating the cylinder and record the total foam height every minute for a total of 15 minutes. This data represents the foam durability of the test cleaning composition.

[0243] Data is graphed as foam production or foam durability (cm) against time (min). Area under the curve (AUC) is calculated using the foam production or foam durability versus time data and a trapezoidal rule calculation.

[0244]

number

[0245] Results are reported as area under the curve (AUC) indexed against the relevant control. Data will be labeled as "AUC Foam Production Index" or "AUC Foam Durability Index." The higher the AUC index, the better the results. Table 8 demonstrates the surprising advantage in foam production of inventive compositions B, D, and F over comparative compositions A, C, and E. Furthermore, inventive compositions B and F have a surprising advantage in foam durability over comparative compositions A and E.

[0246] [Table 14] The viscosity of the composition is measured according to the following procedure.

[0247] The rheological profile of liquid detergent compositions is evaluated via a so-called shear sweep flow continuous ramp method, with increasing shear rates from an initial shear rate of 0.1 1 / s to a final shear rate of 1200 1 / s at a constant temperature of 20°C. The instrument used for the measurements is a programmable rheometer (i.e., TA Instruments AR2000®) equipped with a Peltier plate, with a heating rate of 20°C / min, a minimum accuracy of 0.1°C, and a standard temperature range of 0-200°C. The instrument uses a spindle with a 1000 μm cutting height and a 40 mm, 2° steel cone-plate geometry. A pre-shear conditioning step is performed at 10 1 / s for 10 seconds, allowing the sample to equilibrate for 1 minute before conducting the actual shear sweep test. The typical shear sweep phase duration is 3 minutes, with data logging at 32 points per decade. The results may be reported graphically via an XY scatter chart with the X-axis having a logarithmic scale at 0.2 and 20 seconds per second. In particular, the results may be reported at 20 s at 20°C.

[0248] [Table 15]

[0249] procedure: The alkyl sulfate paste was diluted to the appropriate concentration using deionized water and mixed on a vortex mixer in a 20 mL vial. The sample was then placed at 40°C and checked / remixed daily until complete conversion. The sample was cooled to room temperature and visually inspected under crossed polarized light for birefringence.

[0250] Physical stability of sodium alkyl sulfates in water.

[0251] [Table 16] * Concentrations are weight percent of active material in deionized water.

[0252] The results demonstrate the surprising and unexpected stability of the branched C15 alkyl sulfates of the present disclosure relative to the branched C15 alkyl sulfates disclosed in U.S. Pat. No. 9,493,725.

[0253] Paste formulation results: Another point of differentiation in physical stability is evident when the alkyl sulfates of the present invention are mixed with solvents such as propylene diol (p-diol) and ethanol. In this example, the surfactant is diluted to the target activity with water, p-diol (16% in the final mixture), and ethanol (3% in the final mixture). A C15 alkyl sulfate composition at 42% actives based on material from U.S. Pat. No. 9,493,725 is unstable at room temperature and phase separates within 24 hours. A C15 alkyl sulfate composition based on material from Example 3 is stable at 43.6% actives using the same solvent system.

[0254] [Table 17] * The weight percentages shown are based on 100% active surfactant.

[0255] The results demonstrate the surprising and unexpected stability of the branched C15 alkyl sulfates of the present disclosure relative to the branched C15 alkyl sulfates disclosed in U.S. Pat. No. 9,493,725.

[0256] Other examples of liquid formulations for containing

[0257] [Table 18-1]

[0258] [Table 18-2] 1 C12-15 EO2.5S alkyl ethoxy sulfate, where the alkyl portion of the AES contains approximately 13.9-14.6 carbon atoms 2 PE-20 commercially available from BASF 3 The nuclease enzyme is as claimed in co-pending European Patent Application No. 19219568.3 4. Antioxidant 1 is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, methyl ester [6386-38-5] 5 Antioxidant 2 is Tinogard TS, commercially available from BASF 6 The sanitizer is Tinosan HP 100, available from BASF. 7 Defoamer blend supplied by Dow Corning, 80-92% ethylmethyl, methyl(2-phenylpropyl)siloxane, 5-14% MQ resin in octyl stearate, 3-7% modified silica. 8 The optical brightener is 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonic acid disodium salt or 2,2'-([1,1'-biphenyl]-4,4'-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid disodium salt.

[0259] [Table 19-1]

[0260] [Table 19-2] 1 Novel peaked 1214-9 nonionic ethoxylate commercially available from Sasol 2 PE-20 commercially available from BASF 3 The nuclease enzyme is as claimed in co-pending European Patent Application No. 19219568.3 4. Antioxidant 1 is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, methyl ester [6386-38-5] 5 Antioxidant 2 is Tinogard TS, commercially available from BASF 6 The sanitizer is Tinosan HP100, commercially available from BASF.

[0261] [Table 20] * The nuclease enzyme is as claimed in co-pending European patent application 19219568.3. ** The chelating agent is HEDP, GLDA, or DTPA.

[0262] [Table 21]

[0263] [Table 22]

[0264] [Table 23]

[0265] A. A detergent composition comprising from about 0.1% to about 99% by weight of the composition of a first surfactant, the first surfactant being a surfactant isomer of Formula I A mixture of and a surfactant of formula II Or It becomes essential,

[0266] [ka] About 50% to about 100% by weight of the first surfactant has m+n=11 surfactants isomers, and about 25% of the mixture weight %~about 50 weight % surfactant isomer of Formula I having n=0, and about 0.001% to about 25% by weight of the first surfactant is a surfactant of Formula II, and X is a hydrophilic moiety. B. The detergent composition of claim 1, further comprising from about 0.1% to about 99% by weight of the composition of a second surfactant, the second surfactant being a surfactant isomer of Formula III: A mixture of and a surfactant of formula IV Or It becomes essential,

[0267] [ka] About 50% to about 100% by weight of the second surfactant has m+n=9 surfactants isomer, and about 0.001% to about 25% by weight of the second surfactant is a surfactant of Formula IV, where X is a hydrophilic moiety. C. Approximately 15% of the mixture weight %~about 40 weight % of the surfactant isomer of formula I having n=1. D. Approximately 60% of the mixture weight %~about 90 weight The detergent composition of any of paragraphs A-C, wherein % of the surfactant isomer of formula I has n<3. E. about 90% of the first surfactant weight %~about 100 weight % have m+n=11 surfactants The detergent composition of any of paragraphs A-D, which is an isomer. F. The first surfactant Agent about 15% to about 40% by weight of the compound of formula I, where n=1; surfactants isomer, and the first surfactant Agent about 5% to about 20% by weight of the compound of formula I, wherein n=2; surfactants The detergent composition of any of paragraphs A-E, which is an isomer. G. The first surfactant is represented by Formula I, wherein n is 6 or greater surfactants The detergent composition of any of paragraphs A-F, which is isomer-free. H. Up to about 30% of the mixture weight The detergent composition of any of paragraphs A-G, wherein % of the surfactant isomer of formula I has n>2. I. The first surfactant of the surfactants The agent , up to about 20% by weight of Formula II surfactants The detergent composition of any of paragraphs A-H, comprising: JX is a class of amines including sulfates, alkoxylated alkyl sulfates, sulfonates, amine oxides, polyalkoxylates, polyhydroxy moieties, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates. 2. The detergent composition of any of paragraphs A-I, wherein X is selected from the group consisting of glycerol ethers, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, alkylated quaternary ammonium compounds, alkylated / polyhydroxyalkylated quaternary ammonium compounds, alkylated / polyhydroxylated oxypropyl quaternary ammonium compounds, imidazolines, 2-yl-succinates, sulfonated alkyl esters, sulfonated fatty acids, and mixtures thereof. K. The detergent composition of any of paragraphs A-J, further comprising an auxiliary cleaning additive selected from the group consisting of builders, organic polymeric compounds, enzymes, enzyme stabilizers, one or more solvents, bleaching systems, brighteners, colorants, chelating agents, suds suppressors, conditioning agents, humectants, fragrances, fillers or carriers, alkalinity systems, pH control systems, and buffering agents, and mixtures thereof. L. The detergent composition of any of paragraphs B-K, further comprising from about 0.1% to about 99% by weight of the composition of a second surfactant, the second surfactant consisting essentially of a mixture of a surfactant isomer of Formula III and a surfactant of Formula IV. M. Approximately 25% of the mixture weight %~about 50 weight The detergent composition of any of paragraphs B-L, wherein % of the surfactant isomer of formula III has n=0. N. Approximately 15% of the mixture weight %~about 40 weight The detergent composition of any of paragraphs BM, wherein % of the surfactant isomer of formula III has n=1. O. Approximately 50% of the mixture weight %~about 90 weight The detergent composition of any of paragraphs BN, wherein % of the surfactant isomer of formula III has n<3. P. about 90% of the second surfactant weight %~about 100 weight % have m+n=9 surfactants The detergent composition of any of paragraphs B through O, comprising an isomer. Q. The second surfactant Agent about 25% to about 50% by weight of the compound of formula III, where n=0; surfactants isomer, and the second surfactant Agent about 15% to about 40% by weight of the compound of formula III, where n=1; surfactants isomer, and the second surfactant Agent about 5% to about 20% by weight of the compound of formula III, wherein n=2; surfactants The detergent composition of any of paragraphs B-P, which is an isomer. R. Maximum of about 35% of the mixture weight The detergent composition of any of paragraphs BQ, wherein % of the surfactant isomer of formula III has n>2. S. The second surfactant of the surfactants The agent , up to about 20% by weight of formula IV surfactants The detergent composition according to any one of paragraphs B to R, comprising: T.30 weight %~99 weight % of said first surfactant and about 0.5 weight %~about 20 weight % of the second surfactant. U.60 weight %~99 weight % of said first surfactant; and 0.5 weight %~10 weight% of the second surfactant. V. The detergent composition of any of paragraphs B through U, wherein the ratio of the second surfactant to the first surfactant is from 0.5:10 to 4:10. W. The detergent composition of any of paragraphs B-V, further comprising a third surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, or mixtures thereof, or the detergent composition of any of paragraphs B-V, further comprising an anionic surfactant selected from alkyl benzene sulfonates, alkoxylated alkyl sulfates, alkyl sulfates, and mixtures thereof. X. The detergent composition of any of paragraphs A-W, in a form selected from the group consisting of a granular detergent, a detergent bar, a liquid laundry detergent, a gel detergent, a single-phase or multi-phase unit dose detergent, a detergent contained in a single-phase or multi-phase or multi-compartment water-soluble pouch, a multi-compartment non-dissolving package, a liquid hand dish composition, a laundry pre-treatment product, a detergent contained on or in a porous substrate or a nonwoven sheet, an automatic dishwashing detergent, a hard surface cleaner, a fabric softener composition, and mixtures thereof. Y. The detergent composition of any of paragraphs A-X, in the form of a fibrous product, incorporated into the fibers, incorporated into particles incorporated into the fibrous product, or a combination thereof. Z. approx. 0.01 weight %~about 5 weight % structuring agent, the structuring agent being selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, cellulosic materials, microfiber cellulose, hydrophobically modified alkali swellable emulsions, biopolymers, xanthan gum, gellan gum, hydrogenated castor oil, derivatives of hydrogenated castor oil derivatives, and mixtures thereof. AA. The detergent composition of any of paragraphs A-Z, wherein from about 0.1% to about 100% of the carbon content of the first surfactant, the second surfactant, or combination thereof, is derived from renewable resources. The detergent composition of any of paragraphs A-AA, wherein BB.X is neutralized with sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, calcium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diamine, polyamine, primary amine, secondary amine, tertiary amine, amine-containing surfactant, or combinations thereof. CC. A method for pretreating or treating soiled fabrics, comprising contacting the soiled fabrics with any of the detergent compositions described in A-BB.

[0268] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0269] All documents cited herein, including 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.

[0270] 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. A liquid laundry detergent composition comprising from 0.1% to 99% by weight of said composition of a first surfactant, said first surfactant consisting essentially of a mixture of surfactant isomers of Formula I and a surfactant of Formula II: 【Chemistry 1】 In Formula I and Formula II, m+n=11; 25% to 50% by weight of the mixture of surfactant isomers of formula I have n=0, and 0.001% to 25% by weight of the first surfactant is a surfactant of formula II, where X is a hydrophilic moiety; A liquid laundry detergent composition wherein said first surfactant does not contain a surfactant isomer of formula I where n is 6 or greater.

2. 10. The liquid laundry detergent composition of claim 1, wherein from 15% to 40% by weight of the mixture of surfactant isomers of formula I have n=1.

3. A liquid laundry detergent composition according to claim 1 or 2, wherein from 60% to 90% by weight of the mixture of surfactant isomers of formula I have n<3.

4. 4. A liquid laundry detergent composition according to any one of claims 1 to 3, wherein from 5% to 20% by weight of the first surfactant is a surfactant isomer of formula I where n=2.

5. A liquid laundry detergent composition according to any preceding claim, wherein up to 30% by weight of the mixture of surfactant isomers of formula I have n>2.

6. further comprising 0.1% to 99% by weight of the composition of a second surfactant, wherein the second surfactant consists essentially of a mixture of surfactant isomers of Formula III and a surfactant of Formula IV; 【Chemistry 2】 6. A liquid laundry detergent composition according to any one of claims 1 to 5, wherein in Formula III and Formula IV, m+n=9, and 0.001% to 25% by weight of the second surfactant is a surfactant of Formula IV, and X is a hydrophilic moiety.

7. 7. The liquid laundry detergent composition of claim 6, wherein from 25% to 50% by weight of the mixture of surfactant isomers of Formula III have n=0.

8. A liquid laundry detergent composition according to claim 6 or 7, wherein from 15% to 40% by weight of the mixture of surfactant isomers of formula III has n=1.

9. A liquid laundry detergent composition according to any one of claims 6 to 8, wherein from 50% to 90% by weight of the mixture of surfactant isomers of formula III has n<3.

10. 7. The liquid laundry detergent composition of claim 6, wherein 25% to 50% by weight of the second surfactant is a surfactant isomer of Formula III where n=0, 15% to 40% by weight of the second surfactant is a surfactant isomer of Formula III where n=1, and 5% to 20% by weight of the second surfactant is a surfactant isomer of Formula III where n=2.

11. A liquid laundry detergent composition according to any one of claims 6 to 10, wherein up to 35% by weight of the mixture of surfactant isomers of formula III have n>2.

12. X is a sulfate, alkoxylated alkyl sulfate, sulfonate, amine oxide, polyalkoxylate, polyhydroxy moiety, phosphate ester, glycerol sulfonate, polygluconate, polyphosphate ester, phosphonate, sulfosuccinate, sulfosuccaminates, polyalkoxylated carboxylate, glucamide, taurinate, sarcosinate, glycinate, isethionate, dialkanolamide, monoalkanolamide, monoalkanolamide sulfate, diglycolamide, diglycolamide sulfate, glycerol ester, glycerol ester sulfate 12. The liquid laundry detergent composition of claim 1, wherein the surfactant is selected from the group consisting of esters, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, alkylated quaternary ammonium compounds, alkylated / polyhydroxyalkylated quaternary ammonium compounds, alkylated / polyhydroxylated oxypropyl quaternary ammonium compounds, imidazolines, 2-yl-succinates, sulfonated alkyl esters, sulfonated fatty acids, and mixtures thereof.

13. The liquid laundry detergent composition of claim 12, wherein X is a sulfate.

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