Biodegradable chelating agents and methods for fabric care

Abstract

Biodegradable chelating agents may be incorporated into a variety of fabric care compositions and delivery forms. The fabric care composition may comprise at least one component according to Formula 7, as well as combinations and salts thereof, wherein: R1 is a hydroxyl group, a C1-C6 carboxyl group, a linear or branched C1-C6 alkyl group; a linear or branched C2-C6 alkenyl group; or a linear or branched C2-C6 alkynyl group; a is 0 to 5; r2 is a fused C1-C6 cycloalkyl group, a fused C1-C6 cycloalkyloxy group, or a fused C1-C6 cycloalkenyl group; b is 0 to 4; r3 is oxygen or hydroxyl; and c is 0 to 4. # imgabs0 #

Description

Technical Field

[0001] The present disclosure relates generally to chelators and methods for using chelators, and more particularly to biodegradable chelators and methods. Background Art

[0002] The discussion of shortcomings and needs existing in the art prior to the present disclosure is in no way an admission that one skilled in the art recognized such shortcomings and needs prior to the present disclosure.

[0003] Phosphonate chelates can be used in various fabric care compositions to improve soil removal. Phosphonate chelates can improve soil removal via heavy metal chelation; in this regard, useful phosphonate chelates tend to have a higher binding efficiency with iron (III) than with calcium. One such phosphonate chelate is 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), also known as etidronic acid or etidronate, as shown in Formula 1.

[0004]

[0005] Another phosphonate chelating agent is diethylenetriaminepentamethylenephosphonic acid (DTPMP), as shown in Formula 2.

[0006]

[0007] Some phosphonate chelating agents are not readily biodegradable and may be subject to some wastewater treatments. Such phosphonate chelating agents may cause adverse effects on aquatic life. Therefore, there is a need to replace phosphonate chelating agents in various fabric care compositions with more biodegradable materials that are preferably free of phosphorus.

[0008] Biodegradable alternatives to existing phosphonate chelators include amino acid derivative complexing agents and stereoisomers and mixtures thereof. Methylglycine diacetic acid and its salt (MGDA) as shown in Formula 3 have been used to replace phosphonate chelators.

[0009]

[0010] Similarly, L-glutamic acid, N,N-diacetic acid and its salt (GLDA) and its salt as shown in Formula 4 have been used to replace phosphonate chelating agents.

[0011]

[0012] Unfortunately, neither MGDA nor GLDA match HEDP in terms of stain removal performance.Therefore, there remains a need to replace phosphonate chelating agents in various fabric care compositions with more biodegradable materials that preferably do not contain phosphorus. Summary of the invention

[0013] Various embodiments address the above-mentioned problems and provide biodegradable chelating agents that can be incorporated into a variety of fabric care compositions and delivery forms and provide similar or improved results compared to traditional chelating agents.

[0014] Various embodiments are directed to liquid detergent compositions comprising at least one component according to Formula 7, as well as combinations thereof and salts thereof:

[0015]

[0016] in:

[0017] R1 is hydroxyl, C1-C6 carboxyl, straight or branched C1-C6 alkyl; straight or branched C2-C6 alkenyl; or straight or branched C2-C6 alkynyl;

[0018] a is 0 to 5;

[0019] R2 is a fused C1-C6 cycloalkyl group, a fused C1-C6 cycloalkoxy group or a fused C1-C6 cycloalkenyl group;

[0020] b is 0 to 4;

[0021] R3 is oxygen or hydroxy; and

[0022] c is 0 to 4.

[0023] Various embodiments relate to a single unit dose detergent comprising a liquid detergent composition. Various embodiments relate to a method for treating stains on fabrics, the method comprising washing the fabrics in a wash liquor comprising a liquid detergent composition. Various embodiments relate to the use of a liquid detergent composition for treating stains on fabrics.

[0024]

[0011] These and other features, aspects and advantages of the various embodiments will become better understood with reference to the following description, drawings and appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Many aspects of the present disclosure can be better understood with reference to the following drawings.

[0026] Figure 1 is a side cross-sectional view of a water-soluble pouch article containing the composition therein.

[0027] It should be understood that the various embodiments are not limited to the examples shown in the drawings. DETAILED DESCRIPTION

[0028] Introduction and Definitions

[0029] The present disclosure is written to describe the present invention to those of ordinary skill in the art, and those of ordinary skill in the art will understand that the present disclosure is not limited to the specific examples or embodiments described. Examples and embodiments are single instances of the present invention, which will make the larger scope obvious to those of ordinary skill in the art. Unless otherwise defined, all technical terms and scientific terms used herein have the same meaning as those commonly understood by those of ordinary skill in the art. It should also be understood that the terms used herein are not only for the purpose of describing examples and embodiments, and are not intended to be limiting, because the scope of the present disclosure will be limited only by the appended claims.

[0030] Unless otherwise expressly stated, all features disclosed in this specification (including any attached claims, abstracts and drawings) may be replaced by alternative features for the same, equivalent or similar purposes. Therefore, unless otherwise expressly stated, each feature disclosed is only an example of a general series of equivalent or similar features. The examples and embodiments described herein are only for illustrative purposes, and those of ordinary skill in the art will propose various modifications or changes according to these examples and embodiments, and these modifications or changes will be included in the spirit and scope of this application. Without substantially departing from the spirit and principles of the present disclosure, many changes and modifications may be made to the embodiments of the present disclosure. All such modifications and changes are intended to be included in the scope of the present disclosure herein. For example, unless otherwise specified, the present disclosure is not limited to specific materials, reagents, reaction materials, manufacturing processes, etc., because they may vary. It should also be understood that the terms used herein are only used for the purpose of describing specific embodiments and are not intended to be limited. It is also possible in the present disclosure that steps may be performed in different orders that are logically possible.

[0031] All numerical values ​​herein are assumed to be modified by the term "about", whether or not explicitly stated. The term "about" generally refers to a numerical range that one skilled in the art considers equivalent to the value (e.g., having the same function or result). In many cases, the term "about" may include numerical values ​​that are rounded to the nearest significant figure.

[0032] In everyday usage, indefinite articles (such as "a") precede countable nouns, and uncountable nouns almost never take indefinite articles. Thus, it must be noted that, as used in this specification and the claims that follow, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a carrier" includes a plurality of carriers. In particular, when a singular countable noun is listed as an element in a claim, this specification will generally use phrases such as "single." For example, "a single carrier."

[0033] Unless otherwise indicated, all percentages indicating the amount of a component in a composition represent the percentage by weight of the component based on the total weight of the composition. The term "mole percent" generally refers to the percentage of the number of moles of a particular component to the total number of moles in a mixture. The sum of the mole fractions of each component in a solution is equal to 1.

[0034] Where a numerical range is provided, it is understood that every intervening value (to one-tenth of the unit of the lower limit unless the context clearly dictates otherwise) between the upper and lower limits of that range, as well as any other stated or intervening values ​​in the stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the disclosure, subject to any explicitly excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding one or both of those included limits are also encompassed within the disclosure.

[0035] Throughout this specification and the claims that follow, reference will be made to a number of terms that are defined to have the following meanings, unless a contrary intention is apparent.

[0036] "Standard temperature and pressure" generally refers to 25°C and 1 atmosphere. Standard temperature and pressure may also be referred to as "ambient conditions". Unless otherwise indicated, parts are by weight, temperatures are in °C, and pressures are at or near atmospheric pressure. The terms "elevated temperature" or "elevated temperature" generally refer to temperatures of at least 100°C.

[0037] "Average size" refers to particle size. The particle size of a spherical object can be clearly and quantitatively defined by its diameter. However, typical material objects may be irregularly shaped and non-spherical. There are several ways to extend the above quantitative definitions to apply to non-spherical particles. Existing definitions are based on replacing a given particle with an imaginary sphere having one of the same properties as the particle. Volume-based particle size is equal to the diameter of a sphere with the same volume as the given particle. Area-based particle size is equal to the diameter of a sphere with the same surface area as the given particle. Weight-based particle size is equal to the diameter of a sphere with the same weight as the given particle. Hydrodynamic or aerodynamic particle size is equal to the diameter of a sphere with the same drag coefficient as the given particle.

[0038] "Mixing" refers to a unit operation in industrial process engineering that involves the manipulation of a heterogeneous physical system with the goal of making it more homogeneous. Mixing is performed to allow heat and / or mass transfer between one or more streams, components, or phases.

[0039] "Disposed on" refers to a positional state indicating that one object or material is arranged in a position adjacent to that of another object or material. The term does not require or exclude the presence of intervening objects, materials, or layers.

[0040] "Compositions" include fabric care compositions for hand washing, machine washing and other purposes, and include fabric care additive compositions and compositions suitable for soaking and / or pre-treating fabrics. They can take the form of, for example, laundry detergents, fabric pretreaters, fabric conditioners and / or other washing, rinsing, dryer added products and sprays. Compositions in liquid form can be in an aqueous carrier. In other aspects, the fabric care composition is in the form of a granular detergent or a dryer added fabric softener tablet. Unless otherwise specified, the term includes multi-purpose or "heavy duty" detergents in granular or powder form, especially cleaning detergents; multi-purpose detergents in liquid, gel or paste form, especially the so-called heavy duty liquid (HDL) type; liquid delicate fabric detergents; cleaning adjuvants, such as bleach additives and "stain removal sticks" or pre-treatment products loaded with substrates, dry and wet wipes and pads, nonwoven substrates and sponges; and sprays and fine mists. Various dosage forms can be used. The composition can be provided in a single unit dose (SUD) package or pouch, including a foil or plastic pouch or a water-soluble pouch, such as a polyvinyl alcohol (PVA) pouch; a metering ball or container; a container with an easy-to-open closure (such as a pull tab, a screw cap, a foil or plastic cap, etc.); or other containers known in the art. The composition can be a compact composition containing less than about 15%, or less than about 10%, or less than about 7% water.

[0041] "Unit dose" or "single unit dose" means an amount of the fabric care composition suitable for treating one load of laundry, such as from about 0.05 g to about 100 g, or from 10 g to about 60 g, or from about 20 g to about 40 g.

[0042] "Liquids" include free-flowing liquids as well as pastes, gels, foams and mousses. Non-limiting examples of liquids include light-duty and heavy-duty liquid detergent compositions, fabric enhancers, detergent gels typically used for laundry, bleaching agents and laundry additives. Gases (e.g., suspended bubbles) or solids (e.g., particles) may be contained in the liquid.

[0043] As used herein, "solid" includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include: granules, microcapsules, beads, pellets, and pearlescent beads. Solid compositions can provide technical benefits, including, but not limited to, whole wash process benefits, pre-treatment benefits, and / or aesthetic benefits.

[0044] It has been unexpectedly discovered that tropolone and its derivatives such as hinokitiol can match or exceed the performance of HEDP in stain removal for various fabric care applications such as liquid laundry detergents and single unit dose (SUD) applications. Thus, various embodiments meet the need to replace phosphonate chelating agents in fabric care compositions with phosphorus-free biodegradable materials.

[0045] Various embodiments are directed to chelating compositions comprising tropolone, tropolone derivatives, and salts thereof. Tropolone is also known as 2-hydroxycyclohepta-2,4,6-trien-1-one and is

[0046] As shown in formula 5.

[0047]

[0048] Hinokitiol is a tropol derivative, also known as 2-hydroxy-6-(propan-2-yl)cyclohepta-2,4,6-trien-1-one, as shown in Formula 6.

[0049]

[0050] Various embodiments relate to chelating compositions comprising components according to Formula 7

[0051]

[0052] Regarding formula 7,

[0053] R1 can be a hydroxyl group, a C1-C6 carboxyl group, a straight or branched C1-C6 alkyl group; a straight or branched C2-C6 alkenyl group; or a straight or branched C2-C6 alkynyl group;

[0054] a can be 0 to 5;

[0055] R2 may be a fused C1-C6 cycloalkyl, a fused C1-C6 cycloalkoxy or a fused C1-C6 cycloalkenyl;

[0056] b can be 0 to 4;

[0057] R3 may be oxygen or hydroxyl; and

[0058] c can be 0 to 4.

[0059] It should be understood that the component according to Formula 7 can be tropolone or hinokitiol. When a, b and c are 0, Formula 7 can represent tropolone. When R1 is a branched C3 alkyl, a is 1, b is 0 and c is 0, Formula 7 can represent hinokitiol. The component according to Formula 7 can also be a variety of other compounds.

[0060] For example, the component according to Formula 7 can be γ-thujacetin as shown in Formula 8.

[0061]

[0062] The component according to Formula 7 may be α-thujasuline as shown in Formula 9.

[0063]

[0064] The component according to Formula 7 may be red phenol as shown in Formula 10.

[0065]

[0066] The component according to Formula 7 may be penicillic acid as shown in Formula 11.

[0067]

[0068] The component according to Formula 7 may be penicillanic acid as shown in Formula 12.

[0069]

[0070] Various embodiments relate to salts of tropolone or tropolone derivatives and all components according to Formula 7, including but not limited to sodium and / or potassium salts.

[0071] Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordination bonds between a ligand and a metal atom. Without being bound by theory, the decontamination efficacy of a composition comprising one or more chelating agents may depend at least in part on the ability of the chelating agent to bind to iron, which may be present in some stains (such as fruit or beverage stains). Several factors may affect the ability of a chelating agent to bind iron. These factors may include the pKa of the chelating agent compared to the wash pH, ​​and the affinity of the chelating agent to bind to other metals, materials or compositions in the wash.

[0072] Various embodiments can provide or employ compositions comprising one or more chelating agents having a pKa less than the wash pH. For example, the chelating agent can have a pKa of about 8, less than about 8, about 7, less than about 7, or in the range of about 5 to about 7, according to various embodiments.

[0073] Various embodiments may provide or employ compositions comprising one or more chelating agents that exhibit specific binding efficiency with a particular material. The binding efficiency may be expressed as a binding constant. The binding constant (also referred to as a formation constant or stability constant) is the equilibrium constant for complex formation in solution. It is a measure of the strength of interaction between agents that form a complex together. As an example, various stains may comprise catechins as shown in Formula 13.

[0074]

[0075] As shown in Table 1, this catechin may have a binding efficiency of about 3.5 with calcium and about 19.2 with iron, and competes with chelating agents for binding to these substances. Therefore, chelating agents according to various embodiments may be selected to ensure a lower binding efficiency with calcium and a higher binding efficiency with iron at wash pH.

[0076] Various embodiments can provide or employ compositions comprising one or more chelators having a calcium binding efficiency of about 2.0 to about 7.0, or about 2.2 to about 6.8, or about 2.5 to about 3.5, or about 2.7 to about 3.1, or less than about 6.8. A calcium binding efficiency of less than about 6.8 indicates that the chelator is less likely to bind calcium than HEDP, as shown in Table 1.

[0077] Various embodiments may provide or employ compositions comprising one or more chelators having an iron binding efficiency of about 10 to about 20, or about 10.5 to about 14.1, or about 11 to about 12.9, greater than about 10, as shown in Table 1.

[0078]

[0079] In Table 1, the reaction between metal and ligand is expressed as logK(β 110 ) description. In this context, K is the equilibrium constant for the reaction between the ligand and the metal. The higher the K, the more metal is bound. This is illustrated in the following examples.

[0080]

[0081] β represents the binding efficiency and accepts some subscripts (β mlh ) to indicate how much metal (m), ligand (l), and proton (h) are involved. 110 Indications involve one metal, one ligand, and no protons.

[0082] Liquid detergent composition

[0083] Various embodiments relate to liquid detergent compositions comprising at least one component according to Formula 7, combinations thereof, and salts. At least one component can be present in an amount of greater than about 0% to about 10% by weight, or about 0.5% to about 9.5% by weight, or about 0.5% to about 9.5% by weight, or about 1.0% to about 9.0% by weight, or about 1.5% to about 8.5% by weight, or about 2.0% to about 8.0% by weight, or about 2.5% to about 7.5% by weight, or about 3.0% to about 7.0% by weight, or about 3.5% to about 6.5% by weight, or about 4.0% to about 6.0% by weight, or about 4.5% to about 5.5% by weight, or about 4.0% to about 5.0% by weight of the liquid detergent composition.

[0084] It should be understood that, in addition to at least one component according to Formula 7, the liquid detergent composition may also include a variety of other components. For example, the liquid detergent composition may include a surfactant. The liquid detergent composition may be a laundry detergent composition. Liquid "laundry detergent composition" may include any composition intended to clean fabrics in a washing machine or hand-washing environment. Except for hand washing in a bucket or basin, for example, the liquid laundry detergent composition can be used in high-efficiency and standard washing machines. It should be understood that the liquid detergent composition may encompass preparations that are considered to be heavy-duty liquid (HDL) detergent compositions or stain pretreatment compositions, such as those terms used in the art.

[0085] The detergent composition may be free of synthetic preservatives. Examples of synthetic preservatives include methylisothiazolinone and benzisothiazolinone.

[0086] Surfactants

[0087] The detergent composition may contain from about 5% to about 75%, or from about 5% to about 70%, or from about 5% to about 65%, or from about 5% to about 55%, or from about 5% to about 50%, or from about 10% to about 45%, or from about 10% to about 40% of a surfactant, by weight of the detergent composition. The surfactant may be an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant, or a combination thereof.

[0088] Anionic surfactants may include, for example, alkylbenzene sulfonates, methyl ester sulfonates, alkyl ether carboxylates, alkyl sulfates, alkyl alkoxylated sulfates, or combinations thereof. The alkylbenzene sulfonates may include linear alkylbenzene sulfonates. The linear alkylbenzene sulfonates may contain a small amount of branched alkylbenzene sulfonates as a byproduct of the manufacturing process, but this is generally less than about 5%. The linear alkylbenzene sulfonates may be present, for example, at a level of 0.5% to about 30% by weight of the liquid detergent composition. The linear alkylbenzene sulfonates may be selected from, for example, alkylbenzene sulfonic acid, C 10 To C16 Alkylbenzenesulfonic acid alkali metal salt or amine salt. 10 To C 16 The linear alkylbenzene sulfonate surfactant may contain more than 50% C 12 , greater than 60%, greater than 70% C 12 , more preferably greater than 75%. The linear alkylbenzene sulfonate may contain C 10 -C 16 Alkylbenzene sulfonate, C 11 -C 14 Alkylbenzene sulfonate or a mixture thereof. The alkylbenzene sulfonate may be an amine-neutralized alkylbenzene sulfonate, an alkali metal-neutralized alkylbenzene sulfonate or a mixture thereof. The amine includes, for example, monoethanolamine, triethanolamine, monoisopropanolamine or a mixture thereof. The alkali metal or alkaline earth metal includes, for example, sodium, potassium, magnesium or a mixture thereof.

[0089] Another acceptable anionic surfactant comprises an alkyl sulfate anionic surfactant. The alkyl sulfate anionic surfactant may include, for example, alkyl sulfate, alkoxylated alkyl sulfate or a mixture thereof. The alkyl sulfate anionic surfactant may be a primary alkyl sulfate anionic surfactant or a secondary alkyl sulfate anionic surfactant or a mixture thereof, such as sodium lauryl sulfate. Alkoxylated alkyl sulfate may include ethoxylated alkyl sulfate, propoxylated alkyl sulfate, mixed ethoxylated / propoxylated alkyl sulfate or a mixture thereof. The ethoxylated alkyl sulfate may have an average ethoxylation degree between 0.1 and 5 or between 0.5 and 3. The ethoxylated alkyl sulfate may have an average alkyl chain length between 8 and 18, more preferably between 10 and 16, and most preferably between 12 and 15. The alkyl portion of the ethoxylated alkyl sulfate may include, 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 include alkyl moieties having 14 or more carbon atoms, 14 to 18 or 14 to 17 or 14 to 16 or 14 to 15 carbon atoms.

[0090] The alkyl ether carboxylates may be straight chain or branched. They may have an average carbon chain length of from about 10 to about 26, from about 10 to about 20, or from about 16 to about 18. The alkyl ether carboxylates may have an average ethoxylation level of from about 2 to about 20, from about 7 to about 13, from about 8 to about 12, or from about 9.5 to about 10.5. The acid form or the salt form may be used. The alkyl chain may contain one cis or trans double bond. Commercial alkyl ether carboxylates are available from, for example, Kao Huntsman and Clariant

[0091] The alkyl chain of the alkyl sulfate anionic surfactant may be linear, branched or a mixture thereof. The branched alkyl sulfate anionic surfactant may be a branched primary alkyl sulfate, a branched secondary alkyl sulfate or a mixture thereof, preferably a branched primary alkyl sulfate, wherein the branch is preferably at the 2-position, or alternatively may be further present under the alkyl chain, or may be multi-branched, wherein the branch is distributed over the alkyl chain. The weight average degree of branching of the alkyl sulfate anionic surfactant may be from 0% to 100%, preferably from 0% to 95%, more preferably from 0% to 60%, most preferably from 0% to 20%. Alternatively, the weight average degree of branching of the alkyl sulfate anionic surfactant may be from 70% to 100%, preferably from 80% to 90%. Preferably, the alkyl chain is selected from materials of natural origin, materials of synthetic origin or mixtures thereof. Preferably, the material of synthetic origin comprises oxo-synthesized material, Ziegler-synthesized material, Guerbet-synthesized material, Fischer-Tropsch-synthesized material, isoalkyl-synthesized material or mixtures thereof, preferably oxo-synthesized material.

[0092] Branched 2-alkyl primary alkyl alcohol sulfates and 2-alkyl primary alkyl alcohol ethoxy sulfates with specific alkyl chain length distribution can provide increased detergency (especially in cold water). 2-alkyl branched alcohols (and 2-alkyl branched alkyl sulfates and 2-alkyl branched alkyl ethoxy sulfates and other surfactants derived from them) are positional isomers, wherein the position of the hydroxymethyl group (composed of a methylene bridge (-CH2-unit) connected to a hydroxyl (-OH) group) on the carbon chain is different. Therefore, 2-alkyl branched alkyl alcohols are generally composed of a mixture of positional isomers. In addition, it is well known that fatty alcohols (such as 2-alkyl branched alcohols) and surfactants are characterized by chain length distribution. In other words, fatty alcohols and surfactants are generally composed of a blend of molecules with different alkyl chain lengths (although a single chain length intercept can be obtained). It is noteworthy that the 2-alkyl primary alcohols described herein cannot be obtained by simply blending commercially available materials, and it can have a specific alkyl chain length distribution and / or a specific fraction of certain positional isomers. Specifically, a distribution of about 50% to about 100% by weight of surfactants having m+n=11 is not achievable by blending commercially available materials.

[0093] The detergent composition may comprise a mixture of surfactant isomers of Formula 14 and a surfactant of Formula 15:

[0094] (14)

[0095] (15)CH3-(CH2) m+n+3 -X

[0096] wherein about 50% to about 100% by weight of the first surfactant is an isomer having m+n=11; wherein about 25% to about 50% of the mixture of surfactant isomers of formula 14 has n=0; wherein about 0.001% to about 25% by weight of the first surfactant is a surfactant of formula 15; and wherein X is a hydrophilic moiety.

[0097] X can be neutralized, for example, with 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.

[0098] X can be selected from sulfates, alkoxylated alkyl sulfates, sulfonates, amine oxides, polyalkoxylates, polyhydroxy moieties, phosphates, glycerol sulfonates, polyglucose salts, polyphosphates, phosphonates, sulfosuccinates, sulfosuccinamates, polyalkoxylated carboxylates, glucamides, taurates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamide, diglycolamide sulfates, glycerides, glyceride sulfates, glycerol ethers, glycerol ether sulfates, polyglyceryl ethers, polyglyceryl ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkane sulfonates, amidopropyl betaines, alkylated quaternary ammonium salts, alkylated / polyhydroxylated alkylated quaternary ammonium salts, alkylated / polyhydroxylated oxypropyl quaternary ammonium salts, imidazolines, 2-hydroxy-succinates, sulfonated alkyl esters, sulfonated fatty acids, and mixtures thereof.

[0099] Anionic surfactants may also be biosurfactants. Anionic biosurfactants may include, for example, rhamnolipids. Rhamnolipids may have a single rhamnose sugar ring or two sugar rings.

[0100] The detergent composition may also contain a nonionic surfactant. The nonionic surfactant may include alcohol alkoxylates, oxy alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, alkyl polyglucosides or mixtures thereof. Preferably, the nonionic surfactant may include, for example, alkoxylated alcohol nonionic surfactants, alkyl polyglucosides nonionic surfactants and mixtures thereof. Preferably, the alkoxylated alcohol nonionic surfactant is a linear or branched primary or secondary alkyl alkoxylated nonionic surfactant, preferably an alkyl alkoxylated nonionic surfactant, preferably an alkyl ethoxylated nonionic surfactant, preferably containing an average of about 9 to about 15 carbon atoms in its alkyl chain, preferably about 10 to about 16 carbon atoms, more preferably about 12 to about 15 carbon atoms; and having an average of about 5 to about 12, preferably about 6 to about 10, most preferably about 7 to about 8 or about 9 to about 10 ethylene oxide units per mole of alcohol. For example, the nonionic surfactant may include an ethoxylated nonionic surfactant, wherein the ethoxylated nonionic surfactant having an average carbon chain length of about 10 to about 16 includes an ethoxylated nonionic surfactant having an average carbon chain length of about 12 to about 14 and an average ethoxylation level of about 9 and a second ethoxylated nonionic surfactant having an average carbon chain length of about 14 to about 15 and an average ethoxylation level of about 7.

[0101] The nonionic surfactant may have the formula R(OC2H4) n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon groups containing from about 8 to about 16 carbon atoms and may be linear or branched, and n has an average value of from about 5 to about 15. For example, the additional nonionic surfactant may be selected from ethoxylated alcohols having an average of from about 12 to 14 carbon atoms in the alcohol (alkyl) portion and an average degree of ethoxylation of from about 7 to 9 moles of ethylene oxide per mole of alcohol.

[0102] Additional non-limiting examples include the formula R(OC2H4) n OH, wherein R comprises an alkylphenyl group, wherein the alkyl group comprises from about 8 to about 12 carbon atoms, and n has an average value of from about 5 to about 15, C 12 -C 18 Alkyl ethoxylates, such as those from Shell Nonionic surfactant; C 14 -C 22 Mid-chain branched alcohol; C 14 -C 22 Medium Chain Branched Alkyl Ethoxylate, BAE x, wherein x is 1 to 30. The nonionic ethoxylated alcohol surfactants herein may also contain residual alkoxylation catalysts, which may be considered as residues or impurities of the reaction. It may also contain various impurities or by-products of the alkoxylation reaction. The impurities may vary depending on the catalyst used and the reaction conditions. Impurities include alkyl ethers, such as dialkyl ethers, such as didodecyl ether; glycols, such as diethylene glycol, triethylene glycol, pentaethylene glycol, other polyethylene glycols.

[0103] The nonionic ethoxylated alcohol may be a narrow range ethoxylated alcohol. The narrow range ethoxylated alcohol may have the following general formula (I):

[0104]

[0105] Wherein R is selected from saturated or unsaturated, linear or branched C 10 -C 16 alkyl groups, and wherein greater than 90% of n is 0≤n≤15. In addition, the average value of n may be between about 4 and about 14, preferably between about 6 and about 10, wherein less than about 10% by weight of the alcohol ethoxylates are ethoxylates with n<7, and between 10% by weight and about 20% by weight of the alcohol ethoxylates are ethoxylates with n=8.

[0106] The composition may comprise an average value of n of about 10. The composition may have the following ranges for each of the following n: n=0 is up to 5%, each of n=1, 2, 3, 4, 5 is up to 2%, n=6 is up to 4%, n=7 is up to 10%, n=8 is between 12% and 20%, n=9 is between 15% and 25%, n=10 is between 15% and 30%, n=11 is between 10% and 20%, n=12 is up to 10%, and n>12 is up to 10%. The composition may have between 30% and 70% of n=9 to 10. The composition may have greater than 50% of its composition consisting of n=8 to 11.

[0107] R is selected from saturated or unsaturated, linear or branched C10-C16 alkyl groups, wherein the average value of n is between about 6 and about 10. R may also be selected from saturated or unsaturated, linear or branched C8-C 16 Alkyl groups, wherein more than 90% of n is 0≤n≤15, and wherein the average value of n is between about 5 and about 10, wherein less than about 20% by weight of the alcohol ethoxylates are ethoxylates with n<8. R may also be selected from saturated or unsaturated, linear or branched C 10 -C 16Alkyl groups wherein greater than 90% of n is 0≤n≤15, and wherein the average value of n is between about 6 and about 10, wherein less than about 10% by weight of the alcohol ethoxylates are ethoxylates with n<7, and between 10% by weight and about 20% by weight of the alcohol ethoxylates are ethoxylates with n=8.

[0108] The alcohol ethoxylates described herein are generally not a single compound as shown in their general formula (I), but rather they comprise a mixture of several homologs having different polyalkylene oxide chain lengths and molecular weights. Among the homologs, those having a total number of alkylene oxide units per mole of alcohol that is closer to the most common alkylene oxide adducts are ideal; homologs having a total number of alkylene oxide units that is much lower or much higher than the most common alkylene oxide adducts are less ideal. In other words, a "narrow range" or "peaked" alkoxylated alcohol composition is ideal. A "narrow range" or "peaked" alkoxylated alcohol composition refers to an alkoxylated alcohol composition having a narrow distribution of mole numbers of alkylene oxide additions.

[0109] A "narrow range" or "peaked" alkoxylated alcohol composition may be ideal for a selected application. Homologs within a selected target distribution range may have an appropriate lipophilic-hydrophilic balance for a selected application. For example, in the case of an ethoxylated alcohol product comprising an average ratio of 5 ethylene oxide (EO) units per molecule, homologs having a desired lipophilic-hydrophilic balance may be in the range of 2EO to 9EO. Homologs having shorter EO chain lengths (<2EO) or longer EO chain lengths (>9EO) may be undesirable for applications where surfactants with an EO / alcohol ratio of 5 are typically selected because such longer and shorter homologs are too lipophilic or too hydrophilic for the application utilizing the product. Therefore, it is advantageous to develop alkoxylated alcohols having a peaked distribution.

[0110] The narrow range alkoxylated alcohol compositions of the present disclosure may have an average degree of ethoxylation of from about 0 to about 15, e.g., from about 4 to about 14, from about 5-10, from about 8-11, and from about 6-9. The narrow range alkoxylated alcohol compositions of the present disclosure may have an average degree of ethoxylation of 10. The narrow range alkoxylated alcohol compositions of the present disclosure may have an average degree of ethoxylation of 9. The narrow range alkoxylated alcohol compositions of the present disclosure may have an average degree of ethoxylation of 5.

[0111] The alkyl polyglucoside surfactant may be selected from C10-C16 alkyl polyglucoside surfactants. The alkyl polyglucoside surfactant may have a number average degree of polymerization of 0.1 to 3.0, preferably 1.0 to 2.0, more preferably 1.2 to 1.6. The alkyl polyglucoside surfactant may comprise a blend of a short chain alkyl polyglucoside surfactant and a medium chain to long chain alkyl polyglucoside surfactant, wherein the short chain alkyl polyglucoside surfactant has an alkyl chain containing 10 or less carbon atoms, and the medium chain to long chain alkyl polyglucoside surfactant has an alkyl chain containing greater than 10 carbon atoms to 18 carbon atoms, preferably 12 to 14 carbon atoms.

[0112] Short-chain alkyl polyglucoside surfactants have a unimodal chain length distribution between C8-C10, medium-chain to long-chain alkyl polyglucoside surfactants have a unimodal chain length distribution between C10-C18, and medium-chain alkyl polyglucoside surfactants have a unimodal chain length distribution between C12-C14. In contrast, C8 to C18 alkyl polyglucoside surfactants generally have a unimodal distribution of alkyl chains between C8 and C18, such as C8 to C16, etc. Therefore, the combination of short-chain alkyl polyglucoside surfactants and medium-chain to long-chain or medium-chain alkyl polyglucoside surfactants has a wider chain length distribution than non-blended C8 to C18 alkyl polyglucoside surfactants, or even a bimodal distribution. Preferably, the weight ratio of short-chain alkyl polyglucoside surfactants to long-chain alkyl polyglucoside surfactants is 1: 1 to 10: 1, preferably 1.5: 1 to 5: 1, more preferably 2: 1 to 4: 1. It has been found that blends of such short chain alkyl polyglucoside surfactants and long chain alkyl polyglucoside surfactants result in faster dissolution of the detergent solution in water and improved initial foaming, while also improving foam stability.

[0113] C10-C16 alkyl polyglucosides are commercially available from several suppliers (e.g., surfactants; and 600CSUP, 650EC, 600CSUP / MB and 650EC / MB). 215UP is the preferred short chain APG surfactant. 600CSUP is the preferred medium to long chain APG surfactant.

[0114] The detergent composition may also contain amphoteric and / or zwitterionic surfactants. Suitable amphoteric or zwitterionic surfactants include amine oxides and / or betaines. Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amidopropyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides, and especially coconut dimethyl amine oxide. The amine oxide may have a straight chain or intermediate branched alkyl portion. Typical straight chain amine oxides include water-soluble amine oxides containing one R4C8 to C 18 An alkyl moiety and two R5 and R6 moieties selected from the group consisting of a C1 to C3 alkyl group and a C1 to C3 hydroxyalkyl group. Preferably, the amine oxide is characterized by formula 16

[0115] R4-N(R5)(R6)O(16)

[0116] Where R4 is C8 to C 18 alkyl, and R5 and R6 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl. Specifically, the linear amine oxide surfactant may include a linear C 10 -C 18 Alkyl dimethyl amine oxide and linear C8-C 12 Alkoxyethyl dihydroxyethyl amine oxide.

[0117] Other suitable ionic surfactants include betaines, such as alkyl betaines, alkyl amido betaines, amidazolinium betaines, sulfobetaines (sulfobetaines), and phosphobetaines, or combinations thereof.

[0118] spices

[0119] The detergent composition may also contain perfume. The perfume may be present, for example, at a level of from about 0.2% to about 6.0%, or from about 0.2% to about 5.0%, or from about 0.2% to about 4%, or from about 0.2% to about 3%, or from about 0.2% to about 2.0%.

[0120] water

[0121] The detergent composition also includes water. Water may be present, for example, at a level of from about 5% to about 95% by weight of the composition.

[0122] pH

[0123] The detergent composition may have a pH of from about 5.0 to about 12, preferably 6.0-10.0, more preferably 8.0 to 10, wherein the pH of the detergent composition is measured at 10% dilution in deionized water at 20°C.

[0124] Auxiliary ingredients

[0125] Compositions according to various embodiments may include one or more adjunct ingredients. The non-limiting list of adjuncts provided below is suitable for use in the compositions of the present invention and may be desirably incorporated in certain embodiments, for example to aid or enhance the performance of treating the substrate to be cleaned, or to alter the aesthetics of the composition, as in the case of colorants, dyes, etc. Suitable adjunct materials include, but are not limited to, polymers such as cationic polymers, surfactants, builders, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersants, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structural elasticizers, fabric softeners, carriers, hydrotropes, processing aids, and / or pigments.

[0126] The liquid detergent composition may contain one or more adjunct ingredients. The adjunct ingredients may include, for example, color care agents; organic solvents; aesthetic dyes; hueing dyes; leuco dyes; sunscreens, such as those commercially available under the Acusol trade name; brighteners, including FWA49, FWA15, and FWA36; dye transfer inhibitors, including PVNO, PVP, and PVPVI dye transfer inhibitors; builders, including citric acid and fatty acids; other chelating agents (i.e., chelating agents other than those according to Formula 7); enzymes; perfume capsules; preservatives; antioxidants, including sulfites, such as potassium sulfite or potassium bisulfite salts and those commercially available under the Ralox trade name; antibacterial and antiviral agents, including 4,4'-dichloro-2-hydroxydiphenyl ether, such as Tinosan available from BASF Corporation. HP100; anti-mite actives such as benzyl benzoate; structurants including hydrogenated castor oil; silicone-based defoamer materials; electrolytes including inorganic electrolytes such as sodium chloride, potassium chloride, magnesium chloride and calcium chloride and related sodium, potassium, magnesium and calcium sulfate salts, and organic electrolytes such as sodium, potassium, magnesium and calcium carbonate salts, bicarbonates, carboxylates such as formates, citrates and acetates; pH adjusters including sodium hydroxide, hydrogen chloride and alkanolamines including monoethanolamine, diethanolamine, triethanolamine and monoisopropanolamine; probiotics; sanitation agents such as zinc ricinoleate, thymol, quaternary ammonium salts such as Polyethyleneimine (such as BASF ) and their zinc complexes, silver and silver compounds, cationic biocides including octyldecyldimethylammonium chloride, dioctyldimethylammonium chloride, didecyldimethylammonium chloride, dispersants, cleaning polymers, dextran or mixtures thereof.

[0127] The organic solvent may include alcohols and / or polyols. For example, the organic solvent may include ethanol, propanol, isopropanol, sugar alcohols, ethylene glycol, glycol ethers, or combinations thereof. The organic solvent may include polyethylene glycol, especially low molecular weight polyethylene glycols such as PEG 200 and PEG 400; diethylene glycol; glycerol; 1,2-propylene glycol; polypropylene glycol, including dipropylene glycol and tripropylene glycol and low molecular weight polypropylene glycols such as PPG400, or mixtures thereof.

[0128] The enzyme may comprise, for example, a protease, an amylase, a cellulase, a mannanase, a lipase, a xyloglucanase, a pectate lyase, a nuclease, or a mixture thereof.

[0129] The composition may comprise one or more polymers. Examples are optionally modified carboxymethylcellulose, modified polydextran, poly(vinyl pyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinyl pyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic acid / acrylic acid copolymers and lauryl methacrylate / acrylic acid copolymers.

[0130] The composition may comprise one or more amphiphilic cleaning polymers. Such polymers have balanced hydrophilicity and hydrophobicity so that they remove grease particles from fabrics and surfaces. Suitable amphiphilic alkoxylated grease cleaning polymers include a core structure and a plurality of alkoxylate groups attached to the core structure. These may comprise alkoxylated polyalkyleneimines, especially ethoxylated polyethyleneimines or polyethyleneimines having internal polyethylene oxide blocks and external polypropylene oxide blocks. Typically, these may be incorporated into the composition of the present invention in an amount of 0.005 wt % to 10 wt %, typically 0.5 wt % to 8 wt %.

[0131] The composition may include a zwitterionic polyamine which is a modified hexamethylenediamine. The modification of the hexamethylenediamine includes: (1) one or two alkoxylation modifications per nitrogen atom of the hexamethylenediamine. The alkoxylation modification consists of replacing the hydrogen atom on the nitrogen of the hexamethylenediamine with a (poly)alkyleneoxy chain having an average of about 1 to about 40 alkoxy moieties per modification, wherein the terminal alkoxy moiety of the alkyleneoxy chain is terminated with hydrogen, C1-C4 alkyl, sulfate, carbonate or a mixture thereof; (2) per nitrogen atom of the hexamethylenediamine, one C1-C4 alkyl moiety is substituted and one or two alkoxylation modifications. The alkoxylation modification consists of replacing the hydrogen atom with a (poly)alkyleneoxy chain having an average of about 1 to about 40 alkoxy moieties per modification, wherein the terminal alkoxy moiety of the alkyleneoxy chain is terminated with hydrogen, C1-C4 alkyl or a mixture thereof; or (3) a combination thereof.

[0132] Other suitable polymers include amphiphilic graft copolymers. Preferred one or more amphiphilic graft copolymers include (i) a polyethylene glycol backbone; and (ii) and at least one side group portion 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 a plurality of polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is preferably about 6000, and the weight ratio of polyethylene oxide to polyvinyl acetate is about 40 to 60, and there is less than or equal to 1 grafting point per 50 ethylene oxide units. Typically, these can be incorporated into the composition of the present invention in an amount of 0.005% to 10% by weight, more typically 0.05% to 8% by weight.

[0133] The composition may include one or more soil release polymers. Examples include soil release polymers having a structure defined by one of the following formulas (17), (18) or (19):

[0134] (17)-[(OCHR7-CHR8) g -O-OC-Ar-CO-] d

[0135] (18)-[(OCHR9-CHR 10 ) h -O-OC-sAr-CO-] e

[0136] (19)-[(OCHR 11 -CHR 12 ) i -OR 13 ] f

[0137] in:

[0138] d, e and f are 1 to 50;

[0139] g, h and i are 1 to 200;

[0140] Ar is 1,4-substituted phenylene;

[0141] sAr is 1,3-substituted phenylene substituted at position 5 with SO3Me;

[0142] Me is Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, wherein the alkyl group is C1-C 18 Alkyl or C2-C 10Hydroxyalkyl or mixtures thereof;

[0143] R7, R8, R9, R 10 , R 11 and R 12 Independently selected from H or C1-C 18 n-alkyl or C1-C 18 isoalkyl; and

[0144] R 13 A straight or branched C1-C 18 Alkyl, or straight or branched C2-C 30 alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or a C8-C 30 Aryl group, or C6-C 30 Arylalkyl group.

[0145] 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.

[0146] Known polymeric soil release agents, hereinafter referred to as "SRA" or "SRA's", can optionally be employed in the detergent compositions herein. If used, SRA's will generally comprise from 0.01% to 10.0%, typically 0.1% to 5%, preferably 0.2% to 3.0% by weight of the compositions.

[0147] SRA's can include, for example, a variety of charged, such as anionic or even cationic (see U.S. Pat. No. 4,956,447), and uncharged monomer units, and the structure can be linear, branched or even star-shaped. Examples of SRA's are described in U.S. Pat. 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.

[0148] The composition may comprise 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 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.

[0149] 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, wherein m is 2 to 3, and n is 6 to 12. Side chain esters are attached to the polyacrylate "backbone" to provide a "comb-type" polymer structure. The molecular weight may vary, but is generally 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.

[0150] In the compositions herein, such carboxylate-based polymers can be advantageously utilized at levels 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 made from polyalkylene glycol-based compounds and monomeric materials, wherein the monomeric materials include monomers containing carboxyl groups and one or more 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 aromatic monomers, isobutylene monomers, vinyl acetate monomers, salts of any of these, derivatives of any of these, and mixtures thereof.

[0151] The composition may include alkoxylated polyamines. Such materials include, but are not limited to, ethoxylated polyethylene imine, ethoxylated hexamethylene diamine, and sulfated versions thereof. Polypropoxylated derivatives may also be included. Various amines and polyalkylene imines may be alkoxylated to varying degrees and optionally further modified to provide the above mentioned beneficial effects. A useful example is 600 g / mol of a polyethylene imine core ethoxylated to 20 EO groups / NH. A preferred ethoxylated polyethylene imine is PE-20 available from BASF.

[0152] Useful alkoxylated polyamine-based polymers include alkoxylated polyethyleneimines of the type, wherein the alkoxylated polyalkyleneimine has a polyalkyleneimine core having one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein the alkoxylated polyalkyleneimine has the following empirical formula (20):

[0153] (20)(PEI) j -(EO) k -R 14 ,

[0154] Wherein j is the average number average molecular weight (MW) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine PEI ) and is in the range of 100 Daltons to 100,000 Daltons, wherein k is the average degree of ethoxylation in the side chain or chains of the alkoxylated polyalkyleneimine and is in the range of 5 to 40, and wherein R 14 Independently selected from the group consisting of hydrogen, C1-C4 alkyl, and combinations thereof.

[0155] Other suitable alkoxylated polyalkyleneimines include those wherein the alkoxylated polyalkyleneimines have a polyalkyleneimine core having one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein the alkoxylated polyalkyleneimines have the following empirical formula (21):

[0156] (21)(PEI) o -(EO) m (PO) n -R 15 or (PEI) o -(PO) n (EO) m -R 15 , where o is the average number average molecular weight (MW) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine PEI ) and in the range of 100 Daltons to 100,000 Daltons, wherein m is the average degree of ethoxylation in the one or more side chains of the alkoxylated polyalkyleneimine, which is in the range of 10 to 50, wherein n is the average degree of propoxylation in the one or more side chains of the alkoxylated polyalkyleneimine, which is in the range of 1 to 50, and wherein R 15 Independently selected from the group consisting of hydrogen, C1-C4 alkyl, and combinations thereof.

[0157] Cellulosic polymers can be used according to the present invention. Suitable cellulosic polymers are selected from alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, alkyl carboxyalkyl celluloses, sulfonic acid alkyl celluloses, more preferably selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof. Suitable carboxymethyl celluloses have a carboxymethyl degree of 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 of greater than 0.65 and a blockiness of greater than 0.45, for example, as described in WO09 / 154933.

[0158] The consumer products of the present invention may also include one or more cellulosic polymers, including those selected from the group consisting of alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, alkyl carboxyalkyl celluloses. In one aspect, the cellulosic polymer is selected from the group consisting of carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixtures thereof. In one aspect, the carboxymethyl cellulose has a degree of substitution of carboxymethyl groups of 0.5 to 0.9 and a molecular weight of 100,000 to 300,000 Da. Examples of carboxymethyl cellulose polymers are available under the trade name GDA is commercially available from CPKelko as carboxymethyl cellulose, hydrophobically modified carboxymethyl cellulose, for example under the trade name SH1 is an alkyl ketene dimer derivative of carboxymethyl cellulose commercially available from CPKelco, or under the trade name V is a segmented carboxymethyl cellulose commercially available from CPKelco.

[0159] Cationic polymers can also be used according to the present invention. At the pH at which the composition is to be used (the pH is generally in the range of pH 3 to pH 9, and in one embodiment between pH 4 and pH 8), suitable cationic polymers have a cationic charge density of at least 0.5 meq / gm, at least 0.9 meq / gm in another embodiment, at least 1.2 meq / gm in another embodiment, at least 1.5 meq / gm in another embodiment, but also less than 7 meq / gm in one embodiment, and less than 5 meq / gm in another embodiment. 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. The average molecular weight of such suitable cationic polymers is typically between 10,000 and 10 million, between 50,000 and 5 million in one embodiment, and between 100,000 and 3 million in another embodiment.

[0160] Suitable cationic polymers useful in the compositions herein may contain cationic nitrogen-containing moieties (such as quaternary ammonium) or cationic protonated amino moieties. Any anionic counterions may be used in conjunction with the cationic polymers, so long as the polymer remains soluble in water, in the composition, or in the coacervate phase of the composition, and so long as the counterion is physically and chemically compatible with the essential components of the composition, or in other words does not unduly impair product performance, stability, or aesthetics. Non-limiting examples of such counterions include halides (e.g., chloride, fluoride, bromide, iodide), sulfate, and methylsulfate.

[0161] Non-limiting examples of such polymers are described in the CTFA Cosmetic Ingredient Dictionary, 3rd Edition, Estrin, Crosley and Haynes, eds., (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, DC (1982)).

[0162] Particularly useful cationic polymers that can be used include the following, wherein the cationic polymer comprises a polymer selected from the group consisting of cationic cellulose, cationic guar gum, poly(acrylamide-co-diallyldimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide-co-methacrylamidopropyl-pentamethyl-1,3-propen-2-ol-diammonium chloride), poly(acrylamide-co-N,N-dimethylaminoethyl acrylate) and quaternized derivatives thereof, poly(acrylamide-co-N,N-dimethylaminoethyl methacrylate) and quaternized derivatives thereof, 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 quaternized derivatives thereof, poly(ethyl methacrylate-co- -dimethylaminoethyl methacrylate) and its quaternized derivatives, poly(hydroxypropyl acrylate-co-methacrylamide propyltrimethylammonium chloride) and its quaternized derivatives, poly(hydroxyethyl acrylate-co-dimethylaminoethyl methacrylate) and its quaternized derivatives, poly(methacrylamide-co-dimethylaminoethyl acrylate) and its quaternized derivatives, poly(methacrylate-co-methacrylamide propyltrimethylammonium chloride), poly(vinyl formamide-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, and including quaternized derivatives thereof, and mixtures thereof.

[0163] Other suitable cationic polymers for use in the composition include polysaccharide polymers, cationic guar gum derivatives, cellulose ethers containing quaternary nitrogen, synthetic polymers, copolymers of etherified cellulose, guar gum and starch. When the cationic polymers herein are used, the cationic polymers used are dissolved in the composition or in the complex coacervate phase in the composition, the coacervate phase being formed by the cationic polymers described herein above and the anionic surfactant, amphoteric surfactant and / or zwitterionic surfactant component. Complex coacervates of cationic polymers may also be formed with other charged species in the composition.

[0164] Suitable cationic polymers are described in US Pat. Nos. 3,962,418, 3,958,581, and US Publication No. 2007 / 0207109A1.

[0165] The composition may include one or more dye transfer inhibitors. In one embodiment of the invention, the inventors have surprisingly found that, in addition to the specified dye, a composition comprising a polymeric dye transfer inhibitor provides improved performance. This is surprising because these polymers prevent dye deposition. Suitable dye transfer inhibitors include, but are not limited to, polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinyl oxazolidones and polyvinyl imidazoles, or mixtures thereof. Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and Chromabond S-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, Sokalan HP53, Sokalan HP59, HP 56K, HP 66. The dye control agent may be selected from (i) sulfonated phenol / formaldehyde polymers; (ii) urea derivatives; (iii) polymers of ethylenically unsaturated monomers wherein the polymer molecules are printed with dyes; (iv) fibers composed of water-insoluble polyamides wherein the fibers have an average diameter of no more than about 2 μm; (v) polymers obtainable by polymerizing benzoxazine monomer compounds; and (vi) combinations thereof. Other suitable DTIs are described in WO2012 / 004134. When present in the subject composition, the dye transfer inhibitor may be present at a level of from about 0.0001% to about 10%, from about 0.01% to about 5%, or even from about 0.1% to about 3%, by weight of the composition.

[0166] Examples of water-soluble polymers include, but are not limited to, polyvinyl alcohol (PVA), modified PVA; polyvinyl pyrrolidone; PVA copolymers such as PVA / polyvinyl pyrrolidone and PVA / polyvinyl amine; partially hydrolyzed polyvinyl acetate; polyalkylene oxides such as ethylene oxide; polyethylene glycol; acrylamide; acrylic acid; cellulose, alkyl celluloses such as methyl cellulose, ethyl cellulose and propyl cellulose; cellulose ethers; cellulose esters; cellulose amides; polyvinyl acetate; polycarboxylic acids and salts; polyamino acids or peptides; polyamides; polyacrylamide; copolymers of maleic acid / acrylic acid; polysaccharides including starch, modified starch; gelatin; alginates; xyloglucans, other hemicellulose polysaccharides including xylans, glucuronoxylans, arabinoxylans, mannans, glucomannans and galactoglucomannans; natural gums such as pectin, xanthan gum, carrageenan, locust bean gum, gum arabic, gum tragacanth; and combinations thereof.

[0167] The composition may include a fabric screening agent. Suitable fabric screening agents include dyes, dye-clay conjugates and pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of: dyes belonging to the color index (CI) categories 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 azothiophene, solvent violet 13, acid violet 50 and direct violet 9.

[0168] Encapsulation

[0169] The composition may include an encapsulate. The composition may include, for example, an encapsulate of about 0.05% to about 5%, or about 0.05% to about 5%, or about 0.1% to about 5%, or about 0.2% to about 2%, by weight of the composition. The composition may include enough encapsulates to provide the composition with about 0.05% to about 10%, or about 0.1% to about 5%, or about 0.1% to about 2% of fragrance by weight of the composition. The encapsulate may include a shell and a core. The core may be surrounded by the shell.

[0170] When discussing the amount or weight percentage of encapsulates herein, this refers to the sum of the shell material and the core material.

[0171] The encapsulates may have a volume weighted median encapsulate size of about 0.5 microns to about 100 microns, or even 10 microns to 100 microns, preferably about 1 micron to about 60 microns, or even 10 microns to 50 microns, or even 20 microns to 45 microns, or alternatively 20 microns to 60 microns.

[0172] Single unit dose (SUD) detergent compositions

[0173] According to various embodiments, any of the compositions described herein may be provided in a water-soluble single unit dose (SUD) pouch, as described in U.S. Pat. No. 10,513,588 B2, entitled “Water-Soluble Polyvinyl Alcohol Film With Plasticizer Blend, Related Methods, And Related Articles,” to Friedrich et al., which is incorporated by reference in its entirety.

[0174] SUD packs and pouches may comprise at least one sealed compartment which may be filled with an active ingredient, such as a detergent, to prepare a metered dose pouch.The pouch may comprise a single compartment or multiple compartments. Figure 1 A kind of article is shown, wherein water-soluble pouch 100 is formed by water-soluble polymer films 10, 20 sealed at interface 30. One or two films in film 10, 20 include PVOH polymer and first plasticizer, second plasticizer and third plasticizer. Film 10, 20 defines internal pouch container volume 40, and this internal pouch container volume contains any desired composition 50 released into aqueous environment. Composition 50 is not particularly limited, for example, including any of the various cleaning compositions described below. In an embodiment (not shown) including multiple compartments, each compartment may contain the same and / or different compositions. Then, the composition may be in any suitable form, including but not limited to liquid, solid and their combination (for example solid suspended in liquid). In some embodiments, pouch includes first compartment, second compartment and third compartment, each compartment contains different first composition, second composition and third composition respectively.

[0175] SUD bags and pouches may be made from a water-soluble film including a polyvinyl alcohol (PVOH) polymer and a combination of plasticizers. The water-soluble film may include a polyvinyl alcohol (PVOH) polymer and a combination of at least three plasticizers.

[0176] Polyvinyl alcohol (PVOH) polymer can include one or more PVOH homopolymers, one or more PVOH copolymers and their combinations. The PVOH polymer of water-soluble film is not particularly limited, and it can include a single PVOH homopolymer, a single PVOH copolymer, or a blend of a PVOH homopolymer, a copolymer, or their combinations. In some aspects, the water-soluble film can include a water-soluble polymer except the PVOH polymer. In one class of embodiments, the PVOH polymer will be a partially or completely hydrolyzed PVOH homopolymer, including vinyl alcohol monomer units and optional vinyl acetate monomer units. In another embodiment, the PVOH polymer will be a partially or completely hydrolyzed PVOH copolymer, including anionic monomer units, vinyl alcohol monomer units and optional vinyl acetate monomer units. In various embodiments, the anionic monomer can be one or more of the following: vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the foregoing (e.g., sodium, potassium or other alkali metal salts), esters of the foregoing (e.g., methyl, ethyl or other C1-C4 or C6 alkyl esters), and combinations thereof (e.g., multiple types of anionic monomers or equivalent forms of the same anionic monomer). For example, the anionic monomer may include one or more acrylamidomethylpropanesulfonic acid (e.g., 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid) and alkali metal salts thereof (e.g., sodium salt). Similarly, the anionic monomer may include one or more of monomethyl maleate and alkali metal salts thereof (e.g., sodium salt). Examples of non-PVOH water-soluble polymers include polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxide, polyacrylamide, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polyamide, gelatin, methylcellulose, carboxymethylcellulose and salts thereof, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, starch, modified starch, guar gum, gum arabic, xanthan gum, carrageenan and polyacrylates and salts thereof.

[0177] The combination of plasticizers can include dipropylene glycol as the first plasticizer, sugar alcohol (such as sorbitol) as the second plasticizer and polyol (such as glycerol) as the 3rd plasticizer.Sugar alcohol plasticizer can be such as isomalt, maltitol, sorbitol, xylitol, erythritol, adonitol, galactitol, pentaerythritol or mannitol.In a specific aspect, sugar alcohol plasticizer can be sorbitol or a plasticizer containing sorbitol, such as isomalt.Polyol plasticizer can be such as glycerol, diglycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, at most 400MW, neopentyl glycol, propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, trimethylolpropane or polyether polyol.In a specific aspect, polyol plasticizer can be glycerol, propylene glycol or 1,3-propylene glycol, such as glycerol. In one class of embodiments, the water soluble film includes a polyvinyl alcohol (PVOH) polymer and a plasticizer blend including dipropylene glycol as a first plasticizer, sorbitol as a second plasticizer, and glycerin as a third plasticizer.

[0178] In some embodiments, the water-soluble film may include at least one plasticizer (e.g., as a second plasticizer, a third plasticizer, or other) that is generally solid at room temperature and / or a common temperature, storage temperature, or transportation temperature, for example, a plasticizer that is solid in the range of about 10°C or 20°C to about 30°C, 40°C, or 50°C and / or has a melting point above this range (e.g., a melting point lower than a common film-forming process temperature (such as casting) but higher than a common temperature, storage temperature, or transportation temperature). Examples of such solid plasticizers include sorbitol (95°C melting point) and trimethylolpropane (58°C melting point). Additionally or alternatively, the water-soluble film may include at least one plasticizer (e.g., as a second plasticizer, a third plasticizer, or other) that is generally liquid at room temperature and / or a common temperature, storage temperature, or transportation temperature, for example, a liquid in the range of about 10°C or 20°C to about 30°C, 40°C, or 50°C and / or has a melting point lower than this range.

[0179] In some examples, the water-soluble unit dose article includes at least one water-soluble film oriented to create at least one unit dose interior compartment, wherein the at least one unit dose interior compartment contains a detergent composition. The water-soluble film and detergent composition are described in more detail below.

[0180] In some examples, the consumer product includes a container and at least one water-soluble unit dose product, at least two water-soluble unit dose products in some cases, at least 20 water-soluble unit dose products in some cases, and at least 30 water-soluble unit dose products in some cases. In some examples, the water-soluble unit dose product is in the form of a pouch. In some examples, the water-soluble unit dose product contains a single dose of the composition, and its volume is sufficient to provide benefits in the final application. In some examples, the water-soluble unit dose product includes a water-soluble film, and the water-soluble film is formed so that the unit dose product includes at least one internal compartment surrounded by the water-soluble film. The at least one compartment includes a cleaning composition. The water-soluble film is sealed so that the cleaning composition does not leak out of the compartment during storage. However, when the water-soluble unit dose product is added to water, the water-soluble film dissolves and releases the contents in the internal compartment into the washing liquid.

[0181] The unit dose article may include more than one compartment, at least two compartments, or at least three compartments, or at least four compartments, or even at least five compartments. The compartments may be arranged in a superimposed orientation, i.e. one is positioned on top of another. Alternatively, the compartments may be positioned in a side-by-side orientation, i.e. one is oriented next to another. The compartments may be oriented in a "tire and rim" arrangement, i.e. the first compartment is positioned close to the second compartment, but the first compartment at least partially surrounds the second compartment, but does not completely enclose the second compartment. Alternatively, a compartment may be completely enclosed in another compartment. In some examples, the unit dose article includes at least two compartments, one of which is smaller than the other compartment. In some examples, the unit dose article includes at least three compartments, two of which may be smaller than the third compartment, and in some examples, the smaller compartment is superimposed on the larger compartment. In some examples, the superimposed compartments are oriented side by side. In some examples, each individual unit dose article may have a weight between 10g and 40g, or even between 15g and 35g. Water-soluble film can be dissolved or dispersed in water.Before being formed into unit dose article, water-soluble film has the thickness of 20 microns to 150 microns in some examples, has the thickness of 35 microns to 125 microns in other examples, has the thickness of 50 microns to 110 microns in other examples, has the thickness of about 76 microns in some examples.Exemplary water-soluble film material comprises polymeric material.The film material can be obtained by, for example, casting, blowing, extruding or blowing extrusion of polymeric material.In some examples, the water-soluble film comprises polyvinyl alcohol homopolymer or polyvinyl alcohol copolymer, for example, the blend of polyvinyl alcohol homopolymer and / or polyvinyl alcohol copolymer, wherein polyvinyl alcohol copolymer is selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymer, particularly carboxylated anionic polyvinyl alcohol copolymer, for example, the blend of polyvinyl alcohol homopolymer and carboxylated anionic polyvinyl alcohol copolymer, or two or more preferably the blend of two kinds of polyvinyl alcohol homopolymer.In another example, the water-soluble film comprises single polyvinyl alcohol polymer, more preferably carboxylated anionic polyvinyl alcohol copolymer. In some examples, the water-soluble film is those supplied by Monosol with trade references M8630, M8900, M8779, M8310. In some examples, the film may be opaque, transparent or translucent. The film may include a printed area. The printed area may be implemented using techniques such as flexographic printing or inkjet printing. The film may contain an aversive agent, such as a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate, or mixtures thereof. Example levels of aversive agents include, but are not limited to, 1 ppm to 5000 ppm, 100 ppm to 2500 ppm, or 250 ppm to 2000 ppm. The water-soluble film or the water-soluble unit dose article or both may be coated with a lubricant.In some examples, the lubricant is selected from talc, zinc oxide, silica, siloxane, zeolite, silicic acid, alumina, sodium sulfate, potassium sulfate, calcium carbonate, magnesium carbonate, sodium citrate, sodium tripolyphosphate, potassium citrate, potassium tripolyphosphate, calcium stearate, zinc stearate, magnesium stearate, starch, modified starch, clay, kaolin, gypsum, cyclodextrin, or a mixture thereof.

[0182] In some examples, the detergent product comprises a detergent composition. The detergent composition can be a laundry detergent composition, an automatic dishwashing composition, a hard surface cleaning composition, or a combination thereof. The detergent composition can comprise a solid, a liquid, or a mixture thereof. The term "liquid" includes a gel, a solution, a dispersion, a paste, or a mixture thereof. The solid can be a powder. The so-called powder herein means that the detergent composition can comprise solid particles or can be a single homogeneous solid. In some examples, the powder detergent composition comprises particles. This means that the powder detergent composition comprises separate solid particles, which are different from solids as a single homogeneous solid. The particles can be free-flowing or can be compacted. The laundry detergent composition can be used in a fabric hand washing operation or can be used in an automatic machine fabric washing operation, such as in an automatic machine fabric washing operation. Exemplary laundry detergent compositions include non-soap surfactants, wherein the non-soap surfactants include anionic non-soap surfactants and non-ionic surfactants. In some examples, the laundry detergent composition comprises non-soap surfactants between 10% and 60%, or between 20% and 55%, by weight of the laundry detergent composition. Exemplary weight ratios of non-soap anionic surfactant to non-ionic surfactant are 1:1 to 20:1, 1.5:1 to 17.5:1, 2:1 to 15:1, or 2.5:1 to 13:1. Exemplary non-soap anionic surfactants include linear alkylbenzene sulfonates, alkyl sulfate anionic surfactants, or mixtures thereof. Exemplary weight ratios of linear alkylbenzene sulfonates to alkyl sulfate anionic surfactants are 1:2 to 9:1, 1:1 to 7:1, 1:1 to 5:1, or 1:1 to 4:1. Exemplary linear alkylbenzene sulfonates are C 10 -C 16 Alkylbenzene sulfonic acid, or C 11 -C 14Alkylbenzene sulfonic acid. By "linear" herein is meant that the alkyl group is linear. Exemplary alkyl sulfate anionic surfactants may comprise alkoxylated alkyl sulfates or non-alkoxylated alkyl sulfates or mixtures thereof. Exemplary alkoxylated alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants. Exemplary alkyl sulfate anionic surfactants may comprise ethoxylated alkyl sulfate anionic surfactants having a molar average ethoxylation degree of 1 to 5, 1 to 3, or 2 to 3. Exemplary alkyl sulfate anionic surfactants may comprise non-ethoxylated alkyl sulfates and ethoxylated alkyl sulfates, wherein the molar average ethoxylation degree of the ethoxylated alkyl sulfates is 1 to 5, 1 to 3, or 2 to 3. The alkyl fraction of the exemplary alkyl sulfate anionic surfactant is derived from a fatty alcohol, an oxo alcohol, a Guerbet alcohol, or a mixture thereof. In some examples, the laundry detergent composition comprises between 10% and 50%, between 15% and 45%, between 20% and 40%, or between 30% and 40% of a non-soap anionic surfactant, by weight of the laundry detergent composition. In some examples, the non-ionic surfactant is selected from alcohol alkoxylates, oxo alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, or mixtures thereof. In some examples, the laundry detergent composition comprises between 0.01% and 10%, between 0.01% and 8%, between 0.1% and 6%, or between 0.15% and 5% of a non-ionic surfactant, by weight of the liquid laundry detergent composition. In some examples, the laundry detergent composition comprises soap between 1.5% and 20%, between 2% and 15%, between 3% and 10%, or between 4% and 8%, in some examples, a fatty acid salt, in some examples, an amine-neutralized fatty acid salt, wherein in some examples, the amine is an alkanolamine, for example, selected from monoethanolamine, diethanolamine, triethanolamine or a mixture thereof, in some examples, monoethanolamine. In some examples, the laundry detergent composition is a liquid laundry detergent composition. In some examples, the liquid laundry detergent composition may comprise less than 15%, or less than 12% water by weight of the liquid laundry detergent composition. In some examples, the laundry detergent composition is a liquid laundry detergent composition comprising a non-aqueous solvent selected from 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, sorbitol, polyethylene glycol or a mixture thereof. In some examples, the liquid laundry detergent composition comprises a non-aqueous solvent between 10% and 40%, or between 15% and 30%, by weight of the liquid laundry detergent composition. In some examples, the laundry detergent composition includes a perfume.In some examples, the laundry detergent composition comprises adjunct ingredients, which may be selected from self-cleaning agents (including citrate), (encapsulated) enzymes (including but not limited to proteases, amylases, lipases, cellulases, mannanases, xyloglucanases, DNA enzymes and mixtures thereof), bleaches, bleaching catalysts, aesthetic dyes, hueing dyes, brighteners, cleaning polymers (including alkoxylated polyamines and polyethyleneimines), soil release polymers, fabric conditioning polymers (including polyquaternium 10 (CathEC)), other surfactants (including amine oxides and solvents), chelating agents (including aminocarboxylates and aminophosphonate chelating agents), dye transfer inhibitors, encapsulated fragrances, polycarboxylates, structurants, pH adjusters, antioxidants, preservatives, antimicrobial agents (including Tinosan HP100), probiotics and mixtures thereof. In some examples, the laundry detergent composition has a pH between 6 and 10, between 6.5 and 8.9, or between 7 and 8, wherein the pH of the laundry detergent composition is measured at a product concentration of 10% in deionized water at 20°C. When the laundry detergent composition is a liquid, the laundry detergent composition may be Newtonian or non-Newtonian. In some examples, the liquid laundry detergent composition is non-Newtonian. Without being bound by theory, non-Newtonian liquids have different properties from Newtonian liquids, more specifically, the viscosity of non-Newtonian liquids depends on the shear rate, while Newtonian liquids have a constant viscosity that is independent of the applied shear rate. The reduction in viscosity when shear is applied to non-Newtonian liquids is considered to further facilitate the dissolution of liquid detergents. The liquid laundry detergent composition described herein may have any suitable viscosity, depending on factors such as formulation ingredients and composition purposes.

[0183] combination

[0184] Various embodiments relate to :

[0185] 1. A liquid detergent composition, comprising:

[0186] At least one component according to any one or more of Formula 7 to Formula 12:

[0187]

[0188] in:

[0189] R1 is hydroxyl, C1-C6 carboxyl, straight or branched C1-C6 alkyl; straight or branched C2-C6 alkenyl; or straight or branched C2-C6 alkynyl;

[0190] a is 0 to 5;

[0191] R2 is a fused C1-C6 cycloalkyl, a fused C1-C6 cycloalkoxy or a fused C1-C6 cyclo

[0192] alkenyl;

[0193] b is 0 to 4;

[0194] R3 is oxygen or hydroxy; and

[0195] c is 0 to 4,

[0196] and combinations and salts thereof;

[0197]

[0198]

[0199] 2. The liquid detergent composition according to 1, wherein at least one component according to Formula 7 is tropolone or a salt thereof.

[0200] 3. The liquid detergent composition according to any one of 1 or 2, wherein the at least one component according to Formula 7 is hinokitiol or a salt thereof.

[0201] 4. A liquid detergent composition according to any one of 1 to 3, wherein the pKa of the at least one component is about 8, preferably about 8 or less, more preferably about 7.5 or less, even more preferably from about 5 to about 8, even more preferably from about 5.0 to about 7.5, even more preferably from about 5.0 to about 7.25, or most preferably from about 5.0 to about 7.0.

[0202] 5. A liquid detergent composition according to any one of 1 to 4, wherein the calcium binding efficiency of the at least one component is less than about 7, preferably from about 2 to about 7.0, from about 2 to about 6.8, from about 2.0 to about 6.5, from about 2.0 to about 6.0, from about 2.0 to about 5.5, from about 2.0 to about 5.0, from about 2.0 to about 4.5, from about 2.0 to about 4.5, from about 2.0 to about 4.0, more preferably from about 2.5 to about 3.5 or from about 2.7 to about 3.1.

[0203] 6. A liquid detergent composition according to any one of 1 to 5, wherein the iron binding efficiency of the at least one component is greater than about 10, from about 10 to about 20, or from about 10.5 to about

[0204] 14.1, or from about 11 to about 12.9.

[0205] 7. A liquid detergent composition according to any one of 1 to 6, wherein the at least one component is present in an amount of greater than about 0% to about 10% by weight, or from about 0.5% to about 9.5%, or from about 0.5% to about 9.5% by weight, or from about 1.0% to about 9.0% by weight, or from about 1.5% to about 8.5% by weight, or from about 2.0% to about 8.0% by weight, or from about 2.5% to about 7.5% by weight, or from about 3.0% to about 7.0% by weight, or from about 3.5% to about 6.5% by weight, or from about 4.0% to about 6.0% by weight, or from about 4.5% to about 5.5% by weight, or from about 4.0% to about 5.0% by weight of the liquid detergent composition.

[0206] 8. The liquid detergent composition according to any one of 1 to 7, further comprising a surfactant, the surfactant comprising an anionic surfactant,

[0207] Nonionic surfactant or a combination thereof.

[0208] 9. The liquid detergent composition according to 8, wherein the surfactant is an anionic surfactant comprising sodium lauryl sulfate, linear alkylbenzene sulfonic acid, branched 2-alkyl primary alkyl alcohol sulfate, alkyl sulfate or a combination thereof;

[0209] Alkylbenzene sulfonates are more preferred.

[0210] 10. A single unit dose detergent comprising the liquid detergent composition according to any one of 1 to 9.

[0211] 11. A method for treating stains on fabric, the method comprising:

[0212] The fabrics are washed in a wash liquor comprising a liquid detergent composition comprising at least one component according to one or more of Formulae 7 to 12:

[0214]

[0215] in:

[0216] R1 is hydroxyl, C1-C6 carboxyl, straight or branched C1-C6 alkyl; straight or branched C2-C6 alkenyl; or straight or branched C2-C6 alkynyl;

[0217] a is 0 to 5;

[0218] R2 is a fused C1-C6 cycloalkyl group, a fused C1-C6 cycloalkoxy group or a fused C1-C6 cycloalkenyl group;

[0219] b is 0 to 4;

[0220] R3 is oxygen or hydroxy; and

[0221] c is 0 to 4,

[0222] and combinations and salts thereof;

[0223]

[0224]

[0225] 12. A method for pretreating stains on fabric, the method comprising:

[0226] A liquid detergent composition is applied to the fabric, the liquid detergent composition comprising at least one component according to one or more of Formula 7 to Formula 12:

[0227]

[0228] in:

[0229] R1 is hydroxyl, C1-C6 carboxyl, straight or branched C1-C6 alkyl; straight or branched C2-C6 alkenyl; or straight or branched C2-C6 alkynyl;

[0230] a is 0 to 5;

[0231] R2 is a fused C1-C6 cycloalkyl group, a fused C1-C6 cycloalkoxy group or a fused C1-C6 cycloalkenyl group;

[0232] b is 0 to 4;

[0233] R3 is oxygen or hydroxyl; and c is 0 to 4, and combinations and salts thereof;

[0234]

[0235]

[0236] 13. The method according to any one of 11 to 12, wherein the at least one component according to formula 7 is tropolone or a salt thereof.

[0237] 14. The method according to any one of 11 to 13, wherein the at least one component according to Formula 7 is hinokitiol or a salt thereof.

[0238] 15. The method according to any one of 11 to 14, wherein the pKa of at least one component is

[0239] is about 8, preferably about 8 or less, more preferably about 7.5 or less, and even more preferably about 5

[0240] to about 8, even more preferably from about 5.0 to about 7.5, even more preferably from about 5.0 to about 7.25,

[0241] Or most preferably from about 5.0 to about 7.0.

[0242] 16. The method of any one of 11 to 15, wherein the at least one component has a calcium binding efficiency of less than about 7, preferably about 2 to about 7.0, about 2 to about 6.8, about 2.0 to about 6.5, about 2.0 to about 6.0, about 2.0 to about 5.5, about 2.0 to about 5.0, about 2.0 to about 4.5, about 2.0 to about 4.5, about 2.0 to about 4.0, more preferably about 2.5 to about 3.5 or about 2.7 to about 3.1.

[0243] 17. The method according to any one of 11 to 16, wherein the iron binding efficiency of the at least one component is greater than about 10, about 10 to about 20, or about 10.5 to about 14.1, or about 11

[0244] To about 12.9.

[0245] 18. The method according to any one of 11 to 17, wherein the at least one component is present in an amount of greater than about 0% to about 10% by weight of the liquid detergent composition, or from about 0.5% to about 9.5% by weight, or from about 0.5% to about 9.5% by weight, or from about 1.0% to about 9.0% by weight, or from about 1.5% to about 8.5% by weight, or from about 2.0% to about 10% by weight of the liquid detergent composition.

[0246] 8.0% by weight, or about 2.5% to about 7.5% by weight, or about 3.0% to about 7.0% by weight, or about 3.5% to about 6.5% by weight, or about 4.0% to about 6.0% by weight, or about 4.5% to about 5.5% by weight, or about 4.0% to about 5.0% by weight.

[0247] 19. The method according to any one of 11 to 18, further comprising maintaining the pH of the wash liquor at less than about 10, about 7 to about 9.9, about 7.5 to about 9.0, about 7.5 to about 8.75, about 8.0 to about 9.0.

[0248] 20. The method according to any one of 11 to 19, wherein the liquid detergent composition is delivered to the wash liquor via a single unit dose of detergent comprising the liquid detergent composition.

[0249] 21. The method according to any one of 11 to 20, wherein the liquid detergent composition further comprises a surfactant, which comprises an anionic surfactant, a nonionic surfactant or a combination thereof, preferably an anionic surfactant comprises alkylbenzene sulfonate, methyl ester sulfonate, alkyl ether carboxylate, alkyl sulfate, alkyl alkoxylated sulfate or a combination thereof; more preferably alkylbenzene sulfonate.

[0250] 22. Use of a liquid detergent composition comprising at least one component of formula 7 to formula 12 for treating stains on fabrics and / or cleaning fabrics,

[0251]

[0252] in:

[0253] R1 is hydroxyl, C1-C6 carboxyl, straight or branched C1-C6 alkyl; straight or branched C2-C6 alkenyl; or straight or branched C2-C6 alkynyl;

[0254] a is 0 to 5;

[0255] R2 is a fused C1-C6 cycloalkyl, a fused C1-C6 cycloalkoxy or a fused C1-C6 cyclo

[0256] alkenyl;

[0257] b is 0 to 4;

[0258] R3 is oxygen or hydroxy; and

[0259] c is 0 to 4,

[0260] and combinations and salts thereof;

[0261]

[0262] 23. The use according to 22, wherein the at least one component according to formula 7 is tropolone or a salt thereof.

[0263] 24. The use according to any one of 22 to 23, wherein the at least one component according to formula 7 is hinokitiol or a salt thereof.

[0264] 25. The use according to any one of 22 to 24, wherein the pKa of the at least one component is

[0265] is about 8, preferably about 8 or less, more preferably about 7.5 or less, and even more preferably about 5

[0266] to about 8, even more preferably from about 5.0 to about 7.5, even more preferably from about 5.0 to about 7.25,

[0267] Or most preferably from about 5.0 to about 7.0.

[0268] 26. The use according to any one of 22 to 25, wherein the calcium binding efficiency of the at least one component is less than about 7, preferably from about 2 to about 7.0, from about 2 to about 6.8, from about 2.0 to about

[0269] 6.5, about 2.0 to about 6.0, about 2.0 to about 5.5, about 2.0 to about 5.0, about 2.0 to about

[0270] 4.5, about 2.0 to about 4.5, about 2.0 to about 4.0, more preferably about 2.5 to about 3.5 or about

[0271] 2.7 to about 3.1.

[0272] 27. The use according to any one of 22 to 26, wherein the iron binding efficiency of the at least one component is greater than about 10, about 10 to about 20, or about 10.5 to about 14.1, or about 11

[0273] To about 12.9.

[0274] 28. The use according to any one of 22 to 27, wherein the at least one component is present in an amount greater than about 0% to about 10% or about 0.5% to about 10% by weight of the liquid detergent composition.

[0275] 9.5%, or from about 0.5% to about 9.5% by weight, or from about 1.0% to about

[0276] 9.0%, or from about 1.5% to about 8.5% by weight, or from about 2.0% to about

[0277] 8.0%, or from about 2.5% to about 7.5% by weight, or from about 3.0% to about

[0278] 7.0%, or from about 3.5% to about 6.5% by weight, or from about 4.0% to about

[0279] 6.0%, or about 4.5% to about 5.5% by weight, or about 4.0% to about 5.0% by weight.

[0280] 29. The use according to any one of 22 to 28, wherein the liquid detergent composition further comprises a surfactant selected from the group consisting of anionic surfactants,

[0281] Nonionic surfactants and combinations thereof.

[0282] 30. The use according to 29, wherein the surfactant is an anionic surfactant, which comprises at least one selected from the group consisting of sodium dodecyl sulfate, linear alkylbenzene sulfonic acid, branched 2-alkyl primary alkyl alcohol sulfate, alkyl sulfate or a combination thereof, preferably alkylbenzene sulfonate.

[0283] 31. The use according to any one of 22 to 30, wherein the liquid detergent composition is contained in a single unit dose.

[0284] Example

[0285] The following examples are presented to provide a person of ordinary skill in the art with a complete disclosure and description of how to implement the method, how to prepare and how to use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some errors and deviations should be considered. The purpose of the following examples is not to limit the scope of the various embodiments, but rather to provide examples that illustrate specific embodiments only.

[0286] Decontamination Index Calculation Method

[0287] Image analysis can be used to compare each stain with an unstained fabric control. Software can be used to convert the captured images into standard chromaticity values, and these are compared with standards based on the commonly used Macbeth color reproduction chart, and chromaticity values ​​(stain levels) are assigned to each stain. The CIELAB color space, also known as L*a*b*, is a color space defined by the International Commission on Illumination (abbreviated as CIE) in 1976. It represents color as three values: L* for perceived brightness and a* and b* for four unique colors of human vision: red, green, blue and yellow. The brightness value L* defines black as 0 and white as 100. The a* axis is relative to the green-magenta opponent color, with negative values ​​toward green and positive values ​​toward magenta. The b* axis represents the blue-yellow opponent, with negative numbers toward blue and positive numbers toward yellow. In the following examples, the L*a*b* values ​​of various fabrics are analyzed using commercially available image analysis software. The SRI value is then calculated from the L*a*b* values ​​using the formula shown. The higher the SRI, the better the stain removal effect.

[0288]

[0289] in,

[0290]

[0291] Subscript "b" indicates the data of the stain before washing

[0292] Subscript "a" indicates the stain data after washing

[0293] Subscript "c" indicates data for undyed fabrics

[0294] Therefore, L*a*b* values ​​were obtained from undyed fabric, dyed fabric before washing and dyed fabric after washing.

[0295] Example 1: Single Unit Dose

[0296] Four detergent compositions suitable for use in unit dose detergents were prepared and tested as described in detail below. The composition of each is provided below. Table 2A provides the amount of a given active ingredient in the wash solution, expressed in ppm. Table 2B provides the amount in the composition in wt %.

[0297]

[0298]

[0299]

[0300] The following method was used to test the stain removal ability of the compositions during the washing process. Each composition was added individually to the tank of the oscillating detergent. The volume of each tank was 1 L. The washing temperature was set to 35°C. Throughout the process, 21 gpg of water was used. The product was stirred for 1 minute (400 rpm) and then fabrics (two internal replicates of each stain, 13×6 cm 2 SBL2004 (supplied by WFK) and another 6cm 2 knitted cotton ballast squares to bring the total fabric weight to 60 g). Once the fabric is added, the wash solution is stirred for 30 minutes (300 rpm). The wash solution is then drained and the fabric is subjected to two 5 minute rinse steps, then drained and spin dried. The process is repeated three more times, resulting in a total of four external repeats. After washing, the stained fabric is dried in a tumble dryer for 30 minutes.

[0301] A dose of detergent treatment as detailed in Table 3 below was added to the Oscillating Detergent and evaluated using the Wash Method.

[0302]

[0303] Table 4 summarizes the stain removal testing of HEDP on tropolone.

[0304]

[0305] As can be seen in Table 4, treatments at pH < 10.0 provided improved stain removal performance in the presence of tropolone compared to HEDP or no chelator.

[0306] Table 5 summarizes the stain removal testing of HEDP relative to hinokitiol.

[0307]

[0308] As can be seen from Table 5, the Examples with pH < 10.0 provide improved stain removal performance in the presence of hinokitiol.

[0309] Example 2: Stain Pretreatment

[0310] Four liquid detergent compositions were prepared and tested as detailed below. The composition of each is provided below. Table 6A provides the amount of a given active ingredient in the wash solution, expressed in ppm. Table 6B provides the amount in the composition in wt %.

[0311]

[0312]

[0313] The stain removal ability of the exemplary composition after treatment before the washing process was tested using the following method. Referring to Table 7, all detergent additives for treatment 2A-2D were added separately to the tank of the oscillating dirt-washing instrument. For treatment 2E-2H, each detergent composition of the pre-treatment dose was evenly applied to 4 stained fabrics via a syringe. After application, pressure was applied to each stain in a circular motion using the end of the syringe for 5 seconds. The pre-treated stain was then allowed to stand for 10 minutes, and then added to the tank of the oscillating dirt-washing instrument together with the remaining treatment detergent. The volume of each tank was 1L. The washing temperature was set to 35°C. Throughout the process, 21gpg water was used. The product was stirred for 1 minute (400rpm), and then fabrics (two internal repetitions of each stain, 13×6cm 2 SBL2004 (supplied by WFK) and another 6cm 2 knitted cotton ballast squares to bring the total fabric weight to 60 g). Once the fabric is added, the wash solution is stirred for 30 minutes (300 rpm). The wash solution is then drained and the fabric is subjected to two 5 minute rinse steps, then drained and spin dried. The process is repeated three more times, resulting in a total of four external repeats. After washing, the stained fabric is dried in a tumble dryer for 30 minutes.

[0314]

[0315] Table 8 summarizes the stain removal tests for each treatment.

[0316]

[0317] As can be seen in Table 8, when compared to DTPMP with pretreatment (Treatment 2F), the treatment compositions containing tropolone or hinokitiol (Treatment 2G and Treatment 2H) significantly improved the decontamination effect of the pretreatment.

[0318] Example 3: Composition for improving stain removal on synthetic garments

[0319] Four unit dose detergent compositions were prepared and tested as detailed below. The composition of each is provided below. Table 9A provides the amount of a given active ingredient in the wash solution, expressed in ppm. Table 9B provides the amount in the composition in wt %.

[0320]

[0321]

[0322]

[0323] As detailed in Table 10 below, the following method was used to test the stain removal ability of the exemplary treatment compositions in the washing process. Each composition was added individually to the tank of the oscillating detergent. The volume of each tank was 1 L. The washing temperature was set to 35°C. Throughout the process, 21 gpg of water was used. The product was stirred for 1 minute (400 rpm) and then fabrics (two internal replicates of each stain, 13×6 cm 2 SBL2004 (supplied by WFK) and another 6cm 2 knitted cotton ballast squares to bring the total fabric weight to 60 g). Once the fabric is added, the wash solution is stirred for 30 minutes (300 rpm). The wash solution is then drained and the fabric is subjected to two 5 minute rinse steps, then drained and spin dried. The process is repeated three more times, resulting in a total of four external repeats. After washing, the stained fabric is dried in a tumble dryer for 30 minutes.

[0324]

[0325] Table 11 summarizes the stain removal tests for each treatment.

[0326]

[0327] As can be seen from the above SRI values, formulations C and D of the present invention containing tropolone or hinokitiol significantly improved the stain removal effect on synthetic fabrics (polyester) relative to HEDP. As shown in Table 11, tropolone and hinokitiol showed better performance on synthetic fabrics than HEDP.

[0328] Example 4 and Example 5

[0329] Examples 4 and 5 are exemplary water-soluble unit dose formulations.The liquid detergent composition according to any embodiment described herein can be part of a single compartment water-soluble unit dose article, or can be separated over multiple compartments to obtain a full article composition that is less than an "across-compartment average."

[0330] Example 4: Single-chamber water-soluble unit dose product

[0331] The composition detailed in Table 12 below is encapsulated in a water-soluble film based on polyvinyl alcohol, more specifically, in a water-soluble film comprising a blend of polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer, alternatively in a water-soluble film comprising a carboxylated anionic polyvinyl alcohol copolymer (such as M8630 or M8310, available from MonoSol).

[0332]

[0333]

[0334] *Nuclease as claimed in co-pending European patent application 19219568.3 **Lutensol FP620-ethoxylated polyethyleneimine (PEI600 EO20) from BASF

[0335] ***Polyethylene glycol grafted polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, the polyethylene glycol grafted polymer comprising 40% polyethylene glycol backbone polymer by weight of the polymer system and 60% grafted vinyl acetate side chains by weight of the polymer system

[0336] ****Lutensit Z96 (zwitterionic polyamine available from BASF - zwitterionic hexamethylenediamine according to the formula:

[0337] 100% quaternized and about 40% of the polyethoxy (EO24) groups sulfonated).

[0338]

[0339] *****Texcare SRA300, purchased from Clariant

[0340] Example 5: Multi-compartment water-soluble unit dose product

[0341] This example presents a multi-compartment water-soluble unit dose laundry detergent product comprising a larger bottom compartment while having two smaller compartments stacked on top of the bottom compartment in a side-by-side configuration, according to the Ariel 3-in-1 Pods design as commercially available in the United Kingdom in January 2020. The composition detailed in Table 13 is encapsulated in a polyvinyl alcohol-based water-soluble outer film, more specifically, in a water-soluble film comprising a blend of polyvinyl alcohol homopolymers and carboxylated anionic polyvinyl alcohol copolymers and a water-soluble intermediate film comprising a blend of polyvinyl alcohol homopolymers, alternatively a blend of polyvinyl alcohol homopolymers and carboxylated anionic polyvinyl alcohol copolymers.

[0342]

[0343] *Nuclease as claimed in co-pending European patent application 19219568.3 **Lutensol FP620-ethoxylated polyethyleneimine (PEI600 EO20) from BASF

[0344] ***Polyethylene glycol grafted polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, the polyethylene glycol grafted polymer comprising 40% polyethylene glycol backbone polymer by weight of the polymer system and 60% grafted vinyl acetate side chains by weight of the polymer system

[0345] ****Lutensit Z96 (zwitterionic polyamine available from BASF - zwitterionic hexamethylenediamine according to the formula:

[0346] 100% quaternized and about 40% of the polyethoxy (EO24) groups sulfonated).

[0347]

[0348] *****Texcare SRA300, purchased from Clariant

[0349] Liquid Detergent Exemplary Formulations

[0350]

[0351]

[0352]

[0353]

[0354] 1C12-15EO2.5S alkyl ethoxy sulfate, wherein the alkyl portion of AES has a molecular weight of 211 to 218 Daltons, available from P&G Chemicals; 2 Branched Alkyl Sulfate Example Z; 3 High C12 (96%) linear alkylbenzene sulfonate from P&G Chemicals; 4 S sulfonic acid L24-9 commercially available from Huntsman; 5 C12 / C14 amine oxides from P&G Chemicals; 6 Citrosol 502 commercially available from Archer Daniels Midland; 7 Preferenz, commercially available from DuPont 8 Arctic, commercially available from Novozymes; 9 Disodium tetraborate pentahydrate commercially available from Univar Solutions; 10 PE-20 commercially available from BASF; 11 Sodium lauryl sulfate commercially available from P&G Chemicals

[0355] Composition Examples can be prepared by combining all raw materials to achieve Composition A, except that not all of the water is added to leave space (called pores) to add the branched alkyl sulfates and alkyl ethoxy sulfates of Compositions B to G and Compositions 1 to 3. To prepare Composition A, the following raw materials can be rapidly mixed with a mixing impeller for about 60 minutes to form a vortex: some water, solvent, surfactant (any surfactant other than branched alkyl sulfate or alkyl ethoxy sulfate), borax, stabilizer, neutralizer, builder, chelant, polymer, and enzyme to form a stable single-phase liquid.

[0356] To prepare Compositions B to G and Compositions 1 to 3, branched alkyl sulfates and alkyl ethoxy sulfates can be added to the top of Composition A (with holes) to achieve the desired levels. Caustic or sulfuric acid is added to achieve a consistent pH of 8.2-8.6 before adding the remaining water to balance the formula.

[0357] Compositions 4 to 9 can be prepared by rapidly mixing the following materials with a mixing impeller for about 60 minutes to form a vortex: some water, solvent, surfactant, borax, stabilizer, neutralizer, builder, chelant, polymer and enzyme to form a stable single phase liquid. Caustic or sulfuric acid is added to achieve a consistent pH of 8.2-8.6 before adding the remaining water to balance the formula.

[0358] Further definitions and cross references

[0359] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact numerical values ​​cited. Instead, unless otherwise indicated, each such dimension is intended to represent the stated value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0360] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art to any of the present invention disclosed or claimed herein, or an admission that it, by itself or in combination with any one or more of the references, proposes, suggests, or discloses any such invention. In addition, to the extent that any meaning or definition of a term in this invention 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 invention shall govern.

[0361] Although specific embodiments of the present disclosure have been illustrated and described, it will be apparent to those skilled in the art that many other changes and modifications may be made without departing from the spirit and scope of the invention. Therefore, it is intended that all such changes and modifications within the scope of the invention be covered in the appended claims.

Claims

1. A liquid detergent composition, comprising: At least one component according to one or more of Formula 7 to Formula 12: in: R1 is hydroxyl, C1-C6 carboxyl, straight or branched C1-C6 alkyl; straight or branched C2-C6 alkenyl; or straight or branched C2-C6 alkynyl; a is 0 to 5; R2 is a fused C1-C6 cycloalkyl group, a fused C1-C6 cycloalkoxy group or a fused C1-C6 cycloalkenyl group; b is 0 to 4; R3 is oxygen or hydroxy; and c is 0 to 4, and combinations and salts thereof; 2. The liquid detergent composition according to claim 1, wherein the at least one component according to Formula 7 is tropolone.

3. The liquid detergent composition according to claim 1, wherein the at least one component according to Formula 7 is hinokitiol.

4. A liquid detergent composition according to any preceding claim, wherein the pKa of the at least one component is less than 8.

5. A liquid detergent composition according to any preceding claim, wherein the at least one component has a calcium binding efficiency of less than 7.

6. A liquid detergent composition according to any preceding claim, wherein the at least one component has an iron binding efficiency of greater than 10.

7. A liquid detergent composition according to any preceding claim, wherein the at least one component is present in an amount from greater than 0% to 10% by weight of the liquid detergent composition.

8. A liquid detergent composition according to any preceding claim, further comprising a surfactant comprising an anionic surfactant, a nonionic surfactant or a combination thereof.

9. The liquid detergent composition according to claim 8, wherein the surfactant is an anionic surfactant comprising at least one of sodium lauryl sulfate, linear alkylbenzene sulfonic acid, branched 2-alkyl primary alkyl alcohol sulfate, alkyl sulfate or a combination thereof.

10. A single unit dose detergent comprising a liquid detergent composition according to any preceding claim.

11. A method for treating stains on fabric, the method comprising: The fabrics are washed in a wash liquor comprising a liquid detergent composition comprising at least one component according to any one of Formulae 7 to 12: in: R1 is hydroxyl, C1-C6 carboxyl, straight or branched C1-C6 alkyl; straight or branched C2-C6 alkenyl; or straight or branched C2-C6 alkynyl; a is 0 to 5; R2 is a fused C1-C6 cycloalkyl, a fused C1-C6 cycloalkoxy or a fused C1-C6 cycloalkenyl; b is 0 to 4; R3 is oxygen or hydroxy; and c is 0 to 4, and combinations and salts thereof; 12. The method of claim 11, wherein the at least one component according to formula 7 is tropolone.

13. The method of claim 11, wherein the at least one component according to Formula 7 is hinokitiol.

14. The method of claims 11 to 13, wherein the pKa of the at least one component is less than 8.

15. The method of claims 11 to 14, wherein the at least one component has a calcium binding efficiency of less than 7.

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