Biodegradable chelating agents and methods for fabric care

Abstract

Biodegradable chelating agents can be incorporated into various fabric care compositions and delivery forms. A fabric care composition may include at least one component according to formula (7), as well as combinations thereof and salts thereof, where R1 is a hydroxyl, C1-C6 carboxyl, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, or linear or branched C2-C6 alkynyl group, a is 0-5, R2 is a condensed C1-C6 cycloalkyl, condensed C1-C6 cycloalkoxy, or condensed C1-C6 cycloalkenyl, b is 0-4, R3 is oxygen or hydroxyl, and c is 0-4.

Description

[Technical Field]

[0001] This disclosure relates, in general terms, to chelating agents and methods for using chelating agents, and more specifically, to biodegradable chelating agents and methods. [Background technology]

[0002] Any consideration of shortcomings and necessities existing in the art prior to this disclosure does not in any way imply that such shortcomings and necessities were recognized by those skilled in the art prior to this disclosure.

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

[0004] [ka]

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

[0006] [ka]

[0007] Some phosphonate chelating agents are not readily biodegradable and can withstand some wastewater treatments. Such phosphonate chelating agents can have harmful effects on aquatic organisms. Therefore, there is a need to replace phosphonate chelating agents in various fabric care compositions with more biodegradable materials, preferably those that do not contain phosphorus.

[0008] Existing biodegradable substitutes for phosphonate chelating agents include amino acid derivative complexing agents, as well as stereoisomers and mixtures thereof. For example, as shown in Formula 3, methylglycine diacetic acid and its salts (MGDA) have been used to replace phosphonate chelating agents.

[0009] [ka]

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

[0011] [ka] [Overview of the Initiative] [Problems that the invention aims to solve]

[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, preferably those that do not contain phosphorus. [Means for solving the problem]

[0013] Various embodiments provide a biodegradable chelating agent that solves the above-mentioned problems and can be incorporated into various fabric care compositions and delivery forms, providing similar or improved results compared to conventional chelating agents.

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

[0015] [ka] R1 is a hydroxyl, C1-C6 carboxyl, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, or linear or branched C2-C6 alkynyl group. a is between 0 and 5. R2 is a condensed C1-C6 cycloalkyl, a condensed C1-C6 cycloalkoxy, or a condensed C1-C6 cycloalkenyl. b is between 0 and 4. R3 is oxygen or hydroxyl, c is between 0 and 4.

[0016] Various embodiments relate to single-unit-dose detergents comprising liquid detergent compositions. Various embodiments relate to methods for treating stains on fabrics, comprising washing the fabric in a cleaning solution comprising the liquid detergent composition. Various embodiments relate to the use of liquid detergent compositions for treating stains on fabrics.

[0017] These and other features, aspects, and advantages of various embodiments will be better understood by referring to the following specification, figures, and claims. [Brief explanation of the drawing]

[0018] Many aspects of this disclosure can be better understood by referring to the following figures. [Figure 1] This is a side cross-sectional view of a water-soluble pouch article containing a composition.

[0019] It should be understood that various embodiments are not limited to the examples illustrated in the figures. [Modes for carrying out the invention]

[0020] Introduction and Definitions This disclosure is provided to those skilled in the art to illustrate the invention, and those skilled in the art will understand that this disclosure is not limited to the specific examples or embodiments described. The examples and embodiments are single examples of the invention and will illustrate a broader scope to those skilled in the art. Unless otherwise defined herein, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. It should also be understood that the terms used herein are for illustrative purposes only and are not intended to limit the scope of the invention, as the scope of the invention is limited only by the appended claims.

[0021] All features disclosed herein (including the attached claims, abstract, and drawings) may be replaced by alternative features serving the same, equivalent, or similar purpose unless otherwise expressly stated. Therefore, unless otherwise expressly stated, each feature disclosed is merely an example of a comprehensive set of equivalent or similar features. The examples and embodiments described herein are for illustrative purposes only, and various modifications or changes will be suggested to those skilled in the art in light of them and will be included within the spirit and scope of this application. Many variations and modifications can be made to the embodiments of this disclosure without substantially departing from the spirit and principles of this disclosure. All such variations and modifications are included within the scope of this disclosure. For example, unless otherwise stated, this disclosure is not limited to, and is therefore subject to change, specific materials, reagents, reaction materials, manufacturing processes, etc. It will also be understood that the terminology used herein is intended solely to describe specific embodiments and is not intended to limit them. In this disclosure, steps may also be performed in different logically possible orders.

[0022] All numerical values ​​herein are assumed to be modified by the term “approximately,” whether expressly indicated or not. The term “approximately” generally refers to a range of numbers that a person skilled in the art would consider equivalent to (e.g., having the same function or result as) the listed values. In many cases, the term “approximately” may include numbers rounded to the nearest significant figure.

[0023] In everyday use, indefinite articles (such as "a" or "an") precede countable nouns, while uncountable nouns rarely take an indefinite article. Therefore, it should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" refer to multiple objects unless otherwise explicitly indicated by the context. Thus, for example, a reference to "a support" includes multiple supports. In particular, when a single countable noun is listed as an element of a claim, this specification generally uses phrases such as "single." For example, "single support."

[0024] Unless otherwise specified, all percentages indicating the amount of components in a composition represent weight percentages of the components based on the total weight of the composition. The terms "mol percent" or "mole percent" generally refer to the percentage of moles of a particular component that are equal to the total moles in the mixture. The sum of the mole fractions of each component in a solution is equal to 1.

[0025] Where a range of values ​​is provided, it is understood that each intermediate value between the upper and lower limits of that range (up to the tens digit of the lower limit, unless otherwise explicitly indicated by the context), and any other described value or intermediate value of the described range, are included within this disclosure. The upper and lower limits of these smaller ranges may independently be included within their smaller ranges and are included within the scope of this disclosure, excluding any specific limits of the described range. If the described range includes one or both limits, the range excluding one or both of those limits is also included within this disclosure.

[0026] In this specification and the following claims, numerous terms are used with reference to the following meanings, unless otherwise clearly intended.

[0027] "Standard temperature and pressure" generally refers to 25°C and 1 atmosphere. Standard temperature and pressure may also be called "ambient conditions." Unless otherwise specified, parts are by weight, temperature is in degrees Celsius, and pressure is atmospheric pressure or near atmospheric pressure. The term "high temperature" or "high temperature" generally refers to a temperature of at least 100°C.

[0028] "Average size" refers to particle diameter. The particle diameter of a spherical object can be clearly and quantitatively defined by its diameter. However, typical objects are likely to be irregular in shape and non-spherical. There are several ways to extend the above quantitative definition to apply to non-spherical particles. Existing definitions are based on replacing a given particle with a hypothetical sphere having one of the same properties as that particle. Volume-based particle diameter is equal to the diameter of a sphere having the same volume as the given particle. Area-based particle diameter is equal to the diameter of a sphere having the same surface area as the given particle. Weight-based particle diameter is equal to the diameter of a sphere having the same weight as the given particle. Hydrodynamic or aerodynamic particle diameter is equal to the diameter of a sphere having the same drag coefficient as the given particle.

[0029] "Mixing" refers to the manipulation of heterogeneous physical systems in industrial process engineering, which involves the manipulation of heterogeneous physical systems with the intention of making them more homogeneous. Mixing is performed in a way that allows heat and / or mass transfer to occur between one or more flows, components, or phases.

[0030] "To be positioned above" refers to a positional condition indicating that one object or material is positioned adjacent to the position of another object or material. This term does not require or excludes the presence of intervening objects, materials, or layers.

[0031] "Compositions" include compositions for hand washing, machine washing, and other purposes, including fabric care additive compositions and compositions suitable for use in immersion and / or pretreatment of fabrics. They may take the form of, for example, laundry detergents, fabric pretreatment agents, fabric conditioners, and / or other washing, rinsing, and drying additive products, and sprays. Compositions in liquid form may be in aqueous carriers. In other embodiments, fabric care compositions may take the form of granular detergents or fabric softener sheets added to dryers. Unless otherwise specified, the term includes: general-purpose or "strong" detergents in granular or powder form, especially cleaning detergents; general-purpose detergents in liquid, gel, or paste form, especially so-called strong liquid (HDL) type; liquid detergents for delicate fabrics; cleaning aids, e.g., bleaching additives and "stain sticks" or pretreatment types, products containing base materials, drying and wetting wipes and pads, nonwoven base materials, and sponges; and sprays and mists. Various dosage forms may be used. Compositions may be provided below. Single unit dose (SUD) packets or pouches, including foil or plastic pouches or water-soluble pouches, such as polyvinyl alcohol (PVA) pouches; dosing balls or containers; containers having an easily openable closure, such as a pull tab, screw cap, foil or plastic cover; or other containers known in the art. The composition may be a compact composition containing less than about 15%, less than about 10%, or less than 7% water.

[0032] "Unit dose" or "single unit dose" refers to an amount of fabric care composition suitable for processing a single load of laundry, such as approximately 0.05 to 100 g, 10 to 60 g, or 20 to 40 g.

[0033] "Liquid" includes free-flowing liquids, as well as pastes, gels, foams, and mousses. Non-limiting examples of liquids include light-duty and strong liquid detergent compositions, fabric strengtheners, detergent gels commonly used in laundry, bleaches, and laundry additives. Gases, such as suspended bubbles, or solids, such as particles, may also be included in the liquid.

[0034] As used herein, “solid” includes, but is not limited to, powders, granules, and mixtures thereof. Non-limiting examples of solids include granules, microcapsules, beads, noodles, and pearlescent balls. Solid compositions can offer technical advantages, including, but not limited to, advantages during cleaning, advantages in pretreatment, and / or aesthetic effects.

[0035] Tropolone and its derivatives, such as hinokitiol, were unexpectedly found to be able to match or exceed HEDP performance in stain removal for various fabric care applications, such as liquid laundry detergents and single unit dose (SUD) applications. Therefore, various embodiments satisfy the need to replace phosphonate chelating agents in fabric care compositions with phosphorus-free biodegradable materials.

[0036] Various embodiments relate to chelate compositions comprising tropolone, tropolone derivatives, and salts thereof. Tropolone is also known as 2-hydroxycyclohepta-2,4,6-trien-1-one and is shown in formula 5.

[0037] [ka]

[0038] Hinokitiol is a tropolone derivative also known as 2-hydroxy-6-(propan-2-yl)cyclohepta-2,4,6-trien-1-one, as shown in Formula 6.

[0039] [ka]

[0040] Various embodiments are shown in Equation 7

[0041] [ka] This relates to a chelate composition containing the component. Regarding Equation 7, R1 is a hydroxyl, C1-C6 carboxyl, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, or linear or branched C2-C6 alkynyl group. a can be anywhere from 0 to 5. R2 may be a condensed C1-C6 cycloalkyl, a condensed C1-C6 cycloalkoxy, or a condensed C1-C6 cycloalkenyl. b can be between 0 and 4. R3 may be oxygen or hydroxyl. c can be anywhere from 0 to 4.

[0042] It is understood that the component according to Formula 7 may be tropolone or hinokitiol. Formula 7 may represent tropolone when a, b, and c are 0. Formula 7 may represent hinokitiol when R1 is a branched C3 alkyl, a is 1, b is 0, and c is 0. The component according to Formula 7 may be various other compounds. For example, the component according to Formula 7 may be γ-thujaplisin, as shown in Formula 8.

[0043] [ka]

[0044] The component in formula 7 may be α-thujaplisin, as shown in formula 9.

[0045] [ka]

[0046] The component according to Formula 7 may be purpurogarin, as shown in Formula 10.

[0047] [ka]

[0048] The component in formula 7 may be puvellic acid, as shown in formula 11.

[0049] [ka]

[0050] The component in formula 7 may be puveronic acid, as shown in formula 12.

[0051] [ka]

[0052] Various embodiments include, but are not limited to, salts of tropolone or tropolone derivatives, and sodium salts and / or potassium salts of all components according to Formula 7.

[0053] Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a ligand and a metal atom. While not theoretically bound, the stain-removing effectiveness of a composition containing 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 can influence the ability of a chelating agent to bind to iron. These factors may include the pKa of the chelating agent compared to the wash pH, ​​and the affinity of the chelating agent for binding to other metals, materials, or compositions in the wash solution.

[0054] Various embodiments may provide or use compositions comprising one or more chelating agents having a pKa below the washing pH. For example, according to various embodiments, the chelating agents may have a pKa in the range of about 8, less than about 8, about 7, less than about 7, or about 5 to about 7.

[0055] Various embodiments may provide or use compositions comprising one or more chelating agents exhibiting specific binding efficiency with particular materials. Binding efficiency can be expressed as a binding constant. The binding constant (also called the formation constant or stability constant) is an equilibrium constant for the formation of a complex in solution. It is a measure of the strength of the interaction between reagents that together constitute the complex. As an example, various stains may include catechin, as shown in Equation 13.

[0056] [ka]

[0057] Such catechins may have a binding efficiency of approximately 3.5 with calcium and approximately 19.2 with iron, as shown in Table 1, and they compete with chelating agents to bind to these materials. Therefore, chelating agents according to various embodiments may be selected to ensure lower binding efficiency with calcium and higher binding efficiency with iron at the washing pH.

[0058] Various embodiments may provide or use compositions comprising one or more chelating agents 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 chelating agent is less likely to bind to calcium than HEDP, as shown in Table 1.

[0059] Various embodiments may provide or use compositions comprising one or more chelating agents 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, or greater than about 10, as shown in Table 1.

[0060] [Table 1]

[0061] In Table 1, the reaction between the metal and the ligand is logK(β 110This was described in [reference]. In this context, K is the equilibrium constant for the reaction between the ligand and the metal. The higher K, the more metal is bonded. This will be explained with the following example.

[0062] [ka]

[0063] β represents binding efficiency, and several subscripts (β) mlh This indicates how many metals (m), ligands (l), and protons (h) are involved in each case. Therefore, β 110 This indicates that one metal and one ligand are involved, and no protons are involved.

[0064] Liquid detergent composition Various embodiments relate to liquid detergent compositions comprising at least one component according to Formula 7, combinations thereof, and salts thereof. At least one component may be present in an amount greater than about 0% by weight 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.

[0065] It should be understood that a liquid detergent composition may contain a variety of other components in addition to at least one component according to Formula 7. For example, a liquid detergent composition may contain a surfactant. A liquid detergent composition may be a laundry detergent composition. A liquid "laundry detergent composition" may contain any composition intended for cleaning fabrics in a washing machine or hand washing setting. A liquid laundry detergent composition may be used in high-efficiency and standard washing machines, in addition to hand washing in a tub or basin, for example. It should be understood that a liquid detergent composition may include formulations that are considered to be heavy liquid (HDL) detergent compositions or stain pretreatment compositions, as used in the art.

[0066] The detergent composition may not contain a synthetic preservative. Examples of synthetic preservatives include methylisothiazolinone and benzisothiazolinone.

[0067] Surfactant The detergent composition may contain from about 5 wt% to about 75 wt%, or from about 5 wt% to about 70 wt%, or from about 5 wt% to about 65 wt%, or from about 5 wt% to about 55 wt%, or from about 5 wt% to about 50 wt%, or from about 10 wt% to about 45 wt%, or from about 10 wt% to about 40 wt% of a surfactant, based on the detergent composition. The surfactant can be anionic, nonionic, amphoteric, zwitterionic, or a combination thereof.

[0068] Examples of anionic surfactants can include, for example, alkylbenzene sulfonate, methyl ester sulfonate, alkyl ether carboxylate, alkyl sulfate, alkyl alkoxylated sulfate, or a combination thereof. The alkylbenzene sulfonate can include linear alkylbenzene sulfonate. The linear alkylbenzene sulfonate can have a small amount of branched alkylbenzene sulfonate as a byproduct of the manufacturing process, which is generally less than about 5%. The linear alkylbenzene sulfonate can be present, for example, at a level of from about 0.5 wt% to about 30 wt% of a liquid detergent composition. The linear alkylbenzene sulfonate can be selected, for example, from an alkali metal salt or an amine salt of alkylbenzene sulfonic acid, C 10 ~C 16 The linear alkylbenzene sulfonate surfactant can be selected from an alkali metal salt or an amine salt of alkylbenzene sulfonic acid, or C 10 ~C 16 In the alkali metal salt or amine salt of alkylbenzene sulfonic acid, or C 12 ~C 12 The linear alkylbenzene sulfonate surfactant can contain more than 50% of C 10 ~C 16 alkylbenzene sulfonate, more than 60%, more than 70% of C 11 ~C 14It may contain alkylbenzene sulfonates or mixtures thereof. The alkylbenzene sulfonates may be amine-neutralized alkylbenzene sulfonates, alkali metal-neutralized alkylbenzene sulfonates, or mixtures thereof. The amines include, for example, monoethanolamine, triethanolamine, monoisopropanolamine, or mixtures thereof. The alkali or alkaline earth metals include, for example, sodium, potassium, magnesium, or mixtures thereof.

[0069] Other acceptable anionic surfactants include alkyl sulfate anionic surfactants. Examples of alkyl sulfate anionic surfactants include alkyl sulfates, alkoxylated alkyl sulfates, or mixtures thereof. Alkyl sulfate anionic surfactants may be primary or secondary alkyl sulfate anionic surfactants, or mixtures thereof, for example, sodium lauryl sulfate. Alkoxylated alkyl sulfates may include ethoxylated alkyl sulfates, propoxylated alkyl sulfates, mixed ethoxylated / propoxylated alkyl sulfates, or mixtures thereof. Ethoxylated alkyl sulfates may have an average degree of ethoxylation of 0.1 to 5, or 0.5 to 3. Ethoxylated alkyl sulfates may have an average alkyl chain length of 8 to 18, more preferably 10 to 16, and most preferably 12 to 15. The alkyl moiety of ethoxylated alkyl sulfates may contain, on average, 13.7 to about 16 or 13.9 to 14.6 carbon atoms. At least about 50% or at least about 60% of AES molecules may contain an alkyl moiety having 14 or more carbon atoms, 14 to 18, 14 to 17, 14 to 16, or 14 to 15 carbon atoms.

[0070] Alkyl ether carboxylates can be linear or branched. They may have an average carbon chain length of about 10–26, about 10–20, or about 16–18. Alkyl ether carboxylates may have an average ethoxylation level of about 2–20, about 7–13, about 8–12, or about 9.5–10.5. They can be used in acid or salt form. The alkyl chain may contain one cis or trans double bond. Commercial alkyl ether carboxylates are available from Kao (Akypo®), Huntsman (Empicol®), and Clariant (Emulsogen®).

[0071] The alkyl chain of an alkyl sulfate anionic surfactant may be linear, branched, or a mixture thereof. A 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, where the branching is preferably at the 2-position, selectively located further down the alkyl chain, or polybranched, with the branching extending over the alkyl chain. The weight-average degree of polymerization of an alkyl sulfate anionic surfactant may be 0% to 100%, preferably 0% to 95%, more preferably 0% to 60%, and most preferably 0% to 20%. Alternatively, the weight-average degree of polymerization of an alkyl sulfate anionic surfactant may be 70% to 100%, preferably 80% to 90%. Preferably, the alkyl chain is selected from naturally derived materials, synthetic materials, or a mixture thereof. Preferably, the synthetic material includes oxo-synthetic materials, Ziegler-synthetic materials, Guerbet-synthetic materials, Fischer-Tropsch-synthetic materials, iso-alkyl-synthetic materials, or mixtures thereof, preferably oxo-synthetic materials.

[0072] Branched 2-alkyl primary alkyl alcohol sulfates and 2-alkyl primary alkyl alcohol ethoxysulfates having a specific alkyl chain length distribution may provide improved stain removal (particularly in cold water). 2-alkyl branched alcohols (and 2-alkyl branched alkyl sulfates and 2-alkyl branched alkyl ethoxysulfates, and other surfactants derived therefrom) are positional isomers with different positions of the hydroxymethyl group (consisting of a methylene crosslink (-CH2- unit) bonded to a hydroxy(-OH) group) in the carbon chain. Therefore, 2-alkyl branched alkyl alcohols generally consist of a mixture of positional isomers. Furthermore, it is well known that aliphatic alcohols such as 2-alkyl branched alcohols and surfactants are characterized by their chain length distribution. In other words, aliphatic alcohols and surfactants generally consist of a blend of molecules having different alkyl chain lengths (although it is possible to obtain single-chain-length pieces). In particular, the 2-alkyl primary alcohols described herein, which may have a specific alkyl chain length distribution and / or a specific proportion of certain positional isomers, cannot be obtained by simply blending commercially available materials. Specifically, a distribution of surfactants with m+n=11 in the range of approximately 50% to 100% by weight cannot be achieved by blending commercially available materials.

[0073] The detergent composition may include a mixture of surfactant isomers of formula 14 and a surfactant of formula 15:

[0074] [ka] Approximately 50% to 100% by weight of the first surfactant is an isomer having m+n=11, approximately 25% to 50% of the mixture is the surfactant isomer of formula 14 having n=0, and approximately 0.001% to 25% by weight of the first surfactant is the surfactant of formula 15, where X is the hydrophilic portion.

[0075] X can be neutralized with, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, calcium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diamine, polyamine, primary amine, secondary amine, tertiary amine, amine-containing surfactant, or a combination thereof.

[0076] X is sulfate, alkoxylated alkyl sulfate, sulfonate, amine oxide, polyalkoxylate, polyhydroxy moiety, phosphate ester, glycerol sulfonate, polygluconate, polyphosphate ester, phosphonate, sulfosuccinate, sulfosaccharinate, polyalkoxylated carboxylate, glucamide, taurinate, sarcosinate, glycinate, isethionate, dialkanolamide, monoalkanolamide, monoalkanolamide sulfate, diglycolamide, diglycolamide sulfate, glycerol ester, glycerol The following can be selected from ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonia alkanesulfonates, amidopropyl betaine, alkylated quaternary ammonium compounds, alkylated / polyhydroxyalkylated quaternary ammonium compounds, alkylated / polyhydroxylated oxypropyl quaternary ammonium compounds, imidazoline, 2-yl-succinate, sulfonated alkyl esters, sulfonated fatty acids, and mixtures thereof.

[0077] Anionic surfactants may also be biosurfactants. Examples of anionic biosurfactants include rhamnolipide, which may have one rhamnose sugar ring or two sugar rings.

[0078] The detergent composition may also contain a nonionic surfactant. The nonionic surfactant may include alcohol alkoxylates, oxo-synthetic alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, alkyl polyglucosides, or mixtures thereof. Preferably, nonionic surfactants 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 alkylalkoxylated nonionic surfactant, preferably an alkylalkoxylated nonionic surfactant, preferably an alkylethoxylated nonionic surfactant, and preferably contains an average of about 9 to about 15 carbon atoms, preferably about 10 to about 16, more preferably about 12 to about 15 carbon atoms in its alkyl chain, and 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 units of ethylene oxide per mole of alcohol. For example, nonionic surfactants may include ethoxylated nonionic surfactants, and ethoxylated nonionic surfactants having an average carbon chain length of about 10 to about 16 include ethoxylated nonionic surfactants having an average carbon chain length of about 12 to about 14 and an average degree of ethoxylation of about 9, and second ethoxylated nonionic surfactants having an average carbon chain length of about 14 to about 15 and an average degree of ethoxylation of about 7.

[0079] Nonionic surfactants have the formula R(OC2H4) n The formula may have an OH group, where R is selected from the group consisting of aliphatic hydrocarbon radicals containing about 8 to about 16 carbon atoms, and can be linear or branched, with an average value of n being about 5 to about 15. For example, additional nonionic surfactants may be selected from ethoxylated alcohols having an average of about 12 to 14 carbon atoms in the alcohol (alkyl) portion and an average degree of ethoxylation of about 7 to 9 moles of ethylene oxide per mole of alcohol.

[0080] An additional non-restrictive example is the formula R(OC2H4)n Ethoxylated alkylphenols of OH (wherein the formula R contains an alkylphenyl radical with an alkyl group containing approximately 8 to approximately 12 carbon atoms and an average n value of approximately 5 to approximately 15), NEODOL® nonionic surfactants manufactured by Shell, etc. 12 ~C 18 Alkyl ethoxylate; C 14 ~C 22 Medium-chain branched alcohol; C 14 ~C 22 Examples include medium-chain branched alkyl ethoxylates, such as BAEx (wherein x is 1 to 30). The nonionic ethoxylated alcohol surfactants herein may further contain residual alkoxylation catalysts, which can be considered residues or impurities from the reaction. They may further contain various impurities or by-products of the alkoxylation reaction. The impurities may vary depending on the catalyst used and the reaction conditions. Examples of impurities include alkyl ethers, such as dialkyl ethers such as didodecyl ethers, and glycols, such as diethylene glycol, triethylene glycol, pentaethylene glycol, and other polyethylene glycols.

[0081] Nonionic ethoxylated alcohols can be a narrow range of ethoxylated alcohols. The narrow range of ethoxylated alcohols is represented by the following general formula (I):

[0082] [ka] (In the formula, R is saturated or unsaturated, linear or branched C) 10 ~C 16 Selected from alkyl groups, more than 90% of n may have n=0 ≤ n ≤ 15. In addition, the average value of n can be about 4 to about 14, preferably about 6 to about 10, with less than about 10% by weight of the alcohol ethoxylate being ethoxylates having n<7, and 10% to about 20% by weight of the alcohol ethoxylate being ethoxylates having n=8.

[0083] The composition may contain approximately 10 average values ​​of n. The composition may have the following ranges for each of the following n: n=0 is up to 5%, n=1, 2, 3, 4, 5 are each up to 2%, n=6 is up to 4%, n=7 is up to 10%, n=8 is 12% to 20%, n=9 is 15% to 25%, n=10 is 15% to 30%, n=11 is 10% to 20%, n=12 is up to 10%, and n>12 is up to 10%. The composition may also have n between 9 and 10 at 30% to 70%. The composition may also have n between 8 and 11 at more than 50% of its composition.

[0084] R can be selected from saturated or unsaturated, linear or branched C10-C16 alkyl groups, with an average value of n being approximately 6-10. R can also be selected from saturated or unsaturated, linear or branched C8-C 16 It can be selected from alkyl groups, where more than 90% of n is 0 ≤ n ≤ 15, the mean value of n is about 5 to about 10, and less than about 20% by weight of alcohol ethoxylates are ethoxylates with n < 8. R can also be saturated or unsaturated, linear or branched C 10 ~C 16 Alkyl alkyl groups can be selected, and for over 90% of n, 0 ≤ n ≤ 15, with an average value of approximately 6 to 10. Less than approximately 10% by weight of alcohol ethoxylates are ethoxylates with n < 7, and 10% to approximately 20% by weight of alcohol ethoxylates are ethoxylates with n = 8.

[0085] The alcohol ethoxylates described herein are typically not single compounds as suggested by their general formula (I), but rather alcohol ethoxylates comprise mixtures of several congeners having varying polyalkylene oxide chain lengths and molecular weights. Among the congeners, those with a number of total alkylene oxide units per mole of alcohol that is close to the most dominant alkylene oxide adduct are desirable, while congeners with a number of total alkylene oxide units that is much less or much more than that of the most dominant alkylene oxide adduct are less desirable. In other words, “narrow range” or “peaked” alkoxylated alcohol compositions are desirable. “Narrow range” or “peaked” alkoxylated alcohol compositions refer to alkoxylated alcohol compositions with a narrow distribution of the number of alkylene oxide addition moles.

[0086] Alkoxylated alcohol compositions with a "narrow range" or "peaked" distribution may be desirable for selected applications. Congeners within the distribution range of the selected purpose may have an appropriate lipophilic-hydrophilic balance for the selected application. For example, in the case of an ethoxylated alcohol product containing an average ratio of 5 ethylene oxide (EO) units per molecule, congeners with the desired lipophilic-hydrophilic balance may be in the range of 2EO to 9EO. Congeners with shorter EO chain lengths (<2EO) or longer EO chain lengths (>9EO) may be too lipophilic or too hydrophilic for applications where surfactants with an α=5 EO / alcohol ratio are typically selected, thus being undesirable for applications where such longer or shorter congeners utilize this product. Therefore, it is advantageous to develop alkoxylated alcohols with a peaked distribution.

[0087] The narrow range of alkoxylated alcohol compositions of this disclosure may have an average ethoxylation degree in the range of about 0 to about 15, for example, about 4 to about 14, about 5 to 10, about 8 to 11, and about 6 to 9. The narrow range of alkoxylated alcohol compositions of this disclosure may have an average ethoxylation degree of 10. The narrow range of alkoxylated alcohol compositions of this disclosure may have an average ethoxylation degree of 9. The narrow range of alkoxylated alcohol compositions of this disclosure may have an average ethoxylation degree of 5.

[0088] Alkyl polyglucoside surfactants can be selected from C10-C16 alkyl polyglucoside surfactants. Alkyl polyglucoside surfactants can have a number average degree of polymerization of 0.1-3.0, preferably 1.0-2.0, and more preferably 1.2-1.6. Alkyl polyglucoside surfactants can include blends of short-chain alkyl polyglucoside surfactants having alkyl chains containing 10 or fewer carbon atoms and medium- to long-chain alkyl polyglucoside surfactants having alkyl chains containing more than 10 to 18 carbon atoms, preferably 12-14 carbon atoms.

[0089] Short-chain alkyl polyglucoside surfactants have a monomodal chain length distribution of C8-C10, medium-to-long-chain alkyl polyglucoside surfactants have a monomodal chain length distribution of C10-C18, while medium-chain alkyl polyglucoside surfactants have a monomodal chain length distribution of C12-C14. In contrast, C8-C18 alkyl polyglucoside surfactants typically have a monomodal distribution of alkyl chains of C8-C18, such as C8-C16. Therefore, combinations of short-chain alkyl polyglucoside surfactants with medium-to-long-chain or medium-chain alkyl polyglucoside surfactants have a broader chain length distribution, or even a bimodal distribution, than unblended C8-C18 alkyl polyglucoside surfactants. Preferably, the weight ratio of short-chain alkyl polyglucoside surfactant to long-chain alkyl polyglucoside surfactant is 1:1 to 10:1, preferably 1.5:1 to 5:1, and more preferably 2:1 to 4:1. Such blends of short-chain alkyl polyglucoside surfactants and long-chain alkyl polyglucoside surfactants have been found to result in faster dissolution and improved initial foaming of the detergent aqueous solution, combined with improved foaming stability.

[0090] C10-C16 alkyl polyglycosides are commercially available from several suppliers (e.g., Seppic's Simusol® surfactant, and BASF's Glucopon® 600 CSUP, Glucopon® 650 EC, Glucopon® 600 CSUP / MB, and Glucopon® 650 EC / MB). Glucopon® 215UP is a preferred short-chain APG surfactant. Glucopon® 600CSUP is a preferred medium-to-long-chain APG surfactant.

[0091] The detergent composition may also include amphoteric surfactants and / or zwitterionic surfactants. Suitable amphoteric or zwitterionic surfactants include amine oxides and / or betaines. Preferred amine oxides are alkyldimethylamine oxide or alkylamidopropyldimethylamine oxide, more preferably alkyldimethylamine oxide, and especially cocodimethylamine oxide. Amine oxides may have linear or medium-chain branched alkyl moieties. A typical linear amine oxide has one R4C8~C 18 Examples include water-soluble amine oxides containing an alkyl moiety and two R5 and R6 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide is of the following formula 16: R4-N(R5)(R6)O (16) Characterized by, in the formula, R4 is C8~C 18 The alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. Linear amine oxide surfactants are particularly linear C 10 ~C 18 Alkyldimethylamine oxide and linear C8-C 12 It may also contain alkoxyethyl dihydroxyethylamine oxide.

[0092] Other suitable surfactants include betaines such as alkylbetaine, alkylamidebetaine, amideazolinium betaine, sulfobetaine (sultaine), and phosphobetaine, or combinations thereof.

[0093] fragrance The detergent composition may further contain a fragrance. The fragrance may be present at levels such as, for example, about 0.2% to about 6.0%, or about 0.2% to about 5.0%, or about 0.2% to about 4%, or about 0.2% to about 3%, or about 0.2% to about 2.0%.

[0094] water The detergent composition also contains water. Water may be present at a level of about 5% to about 95% by weight of the composition.

[0095] pH The detergent composition may have a pH of about 5.0 to about 12, preferably 6.0 to 10.0, and more preferably 8.0 to 10, and the pH of the detergent composition is measured as a 10% dilution in desalinated water at 20°C.

[0096] auxiliary ingredients Compositions according to various embodiments may contain one or more auxiliary components. The non-limiting list of auxiliary agents provided below is suitable for use in the composition and can preferably be incorporated into specific embodiments for, for example, to assist or enhance performance, for treatment of substrates to be washed, or to modify the aesthetics of the composition, such as when using colorants, dyes, etc. Suitable auxiliary materials include, but are not limited to, polymers such as cationic polymers, surfactants, builders, color transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalysts, bleach activators, polymer dispersants, clay stain removers / anti-re-adhesion agents, whitening agents, foam inhibitors, dyes, additional fragrances and fragrance delivery systems, structural elastomates, fabric softeners, carriers, hydrotropes, processing aids, and / or pigments.

[0097] Liquid detergent compositions may contain one or more auxiliary components. These auxiliary components may include, for example, color care agents; organic solvents; cosmetic dyes; color dyes; leuco dyes; opacifying agents such as those marketed under the Acusol brand name; glossing agents 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; fragrance capsules; preservatives; antioxidants such as potassium sulfite or potassium bisulfite, and those marketed under the brand name Ralox; and Tinosan, available from BASF. Antibacterial and antiviral agents including 4,4'-dichloro-2-hydroxydiphenyl ether such as HP100; anti-mite active substances such as benzyl benzoate; structuring agents including hydrogenated castor oil; silicone-based defoaming materials; inorganic electrolytes such as sodium chloride, potassium chloride, magnesium chloride, and calcium chloride, and related sodium sulfate, potassium sulfate, magnesium sulfate, and calcium sulfate salts; and organic electrolytes such as sodium, potassium, magnesium, and calcium salts of carbonates, bicarbonates, and carboxylates such as formate, citrate, and acetate; sodium hydroxide, hydrogen chloride, Furthermore, examples include pH adjusters containing alkanolamines, including monoethanolamine, diethanolamine, triethanolamine, and monoisopropanolamine; probiotics; sanitizing agents; quaternary ammonium salts such as zinc ricinoleate, thymol, and Bardac®; polyethyleneimine (such as Lupasol® from BASF) and its zinc complexes; silver and silver compounds; cationic biocides containing octyldecyldimethylammonium chloride; dioctyldimethylammonium chloride; didecyldimethylammonium chloride; dispersants; cleaning polymers; glucans; or mixtures thereof.

[0098] Organic solvents may include alcohols and / or polyols. For example, organic solvents may include ethanol, propanol, isopropanol, sugar alcohols, glycols, glycol ethers, or combinations thereof. Organic solvents may include polyethylene glycol, particularly low molecular weight polyethylene glycols such as PEG200 and PEG400; diethylene glycol; glycerol; 1,2-propanediol; polypropylene glycols including dipropylene glycol and tripropylene glycol, and low molecular weight polypropylene glycols such as PPG400; or mixtures thereof.

[0099] The enzymes may include, for example, proteases, amylases, cellulases, mannanases, lipases, xyloglucanases, pectin lyases, nuclease enzymes, or mixtures thereof.

[0100] The composition may contain one or more polymers. Examples include optionally modified carboxymethylcellulose, modified polyglucans, polycarboxylates such as poly(vinylpyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polyacrylate, maleic acid / acrylic acid copolymers, and lauryl methacrylate / acrylic acid copolymers.

[0101] The composition may comprise one or more amphiphilic cleansing polymers. Such polymers have a balanced combination of hydrophilic and hydrophobic properties to remove grease particles from fabrics and surfaces. Suitable amphiphilic alkoxylated grease cleansing polymers comprise a core structure and a plurality of alkoxylate groups bonded to the core structure. These may comprise alkoxylated polyalkyleneimines, particularly ethoxylated polyethyleneimines, or polyethyleneimines having an inner polyethylene oxide block and an outer polypropylene oxide block. Typically, these can be incorporated into the composition of the present invention in amounts of 0.005% to 10% by weight, generally 0.5% to 8% by weight.

[0102] The composition may contain a zwitterionic polyamine which is a modified hexamethylenediamine. Modifications of hexamethylenediamine include: (1) Alkylation modification of one or two alkoxylation groups per nitrogen atom of hexamethylenediamine. Alkylation modification consists of substituting the hydrogen atom on the nitrogen of hexamethylenediamine with a (poly)alkoxylene chain having an average of about 1 to about 40 alkoxy moieties per modification, and the terminal alkoxy moieties of the alkoxylene chain are protected with hydrogen, C1-C4 alkyl, sulfate, carbonate, or a mixture thereof. (2) Substitution of one C1-C4 alkyl moiety per nitrogen atom of hexamethylenediamine and one or two alkoxylation modifications. Alkylation modification consists of substituting the hydrogen atom with a (poly)alkoxylene chain having an average of about 1 to about 40 alkoxy moieties per modification, and the terminal alkoxy moieties of the alkoxylene chain are protected with hydrogen, C1-C4 alkyl, or a mixture thereof. Or, (3) a combination of these.

[0103] Other suitable polymers include amphiphilic graft copolymers. Preferred amphiphilic graft copolymers comprise (i) a polyethylene glycol backbone and (ii) at least one pendant 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, the weight ratio of polyethylene oxide to polyvinyl acetate is about 40-60, and the graft sites are 1 or less per 50 ethylene oxide units. Typically, these are incorporated into the composition of the present invention in amounts of 0.005-10% by weight, more usually 0.05-8% by weight.

[0104] The composition may contain one or more fouling-releasing polymers. Examples include fouling-releasing polymers having a structure defined by one of the following formulas (17), (18), or (19): (17) -[(OCHR7-CHR8) g -O-OC- Ar-CO-] d (18) -[(OCHR9-CHR 10 ) h -O-OC-s Ar-CO-] e (19) -[(OCHR 11 -CHR 12 ) i -OR 13 ] f d, e, and f are between 1 and 50. g, h, and i are between 1 and 200. Ar is a 1,4-substituted phenylene, sAr is a 1,3-substituted phenylene with SO3Me substituted at position 5. Me is a compound of Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri-, or tetra-alkylammonium (alkyl groups are C1-C 18 Alkyl or C2-C 10 It is a hydroxyalkyl group, or a mixture thereof. R7, R8, R9, R 10 , R 11 , and R 12 These are independently H or C1~C 18 Selected from n- or iso-alkyl, R 13 This refers to a linear or branched chain C1-C 18 Alkyl, or linear or branched C2-C 30 Alkenyl, or cycloalkyl group having 5-9 carbon atoms, or C8-C 30 Aryl group, or C6~C 30 It is an arylalkyl group.

[0105] Suitable fouling-releasing polymers are polyester fouling-releasing polymers such as Repel-o-tex polymers, including Repel-o-tex SF, SF-2, and SRP6 supplied by Rhodia. Other suitable fouling-releasing polymers include Texcare polymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN260, SRN300, and SRN325 supplied by Clariant. Another suitable fouling-releasing polymer is Marloquest polymer, e.g., Marloquest SL, supplied by Sasol.

[0106] Known polymer stain-removing agents, hereinafter referred to as "SRAs (single or multiple)", may be optionally used in this detergent composition. If used, the SRAs generally constitute 0.01% to 10.0% by weight of the composition, typically 0.1% to 5% by weight, and preferably 0.2% to 3.0% by weight.

[0107] SRA can include, for example, various charged monomer units, such as anionic or cationic (see U.S. Patent No. 4,956,447), as well as uncharged monomer units, and the structure may be linear, branched, or even star-shaped. Examples of SRAs are listed in U.S. Patent Nos. 4,968,451, 4,711,730, 4,721,580, 4,702,857, 4,877,896, 3,959,230, 3,893,929, 4,000,093, 5,415,807, 4,201,824, 4,240,918, 4,525,524, 4,201,824, 4,579,681, and 4,787,989.

[0108] The composition may contain carboxylate polymers such as maleate / acrylate random copolymers or polyacrylate homopolymers. Suitable carboxylate polymers include polyacrylate homopolymers having a molecular weight of 4,000 Da to 9,000 Da, and maleate / acrylate random copolymers having a molecular weight of 50,000 Da to 100,000 Da, or 60,000 Da to 80,000 Da.

[0109] Alternatively, these materials may include polyacrylates having one ethoxy side chain for every 7-8 acrylate units. The side chain is of the formula -(CH2CH2O) m (CH2) n The compound is CH3 [wherein m is 2 to 3 and n is 6 to 12]. The side chains are ester-bonded to the polyacrylate "backbone" to provide a "comb-shaped" polymer structure. The molecular weight can vary, but is typically in the range of about 2,000 to about 50,000. Such alkoxylated polycarboxylates may constitute about 0.05% to about 10% by weight of the compositions herein.

[0110] Such carboxylate polymers can be advantageously used in the compositions herein at concentrations of about 0.1% to about 7% by weight. Suitable polymer 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 graft polymers may be prepared from polyalkylene glycol compounds and monomer materials, the monomer materials comprising carboxyl group-containing monomers and optional additional monomers. Any 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, vinylaryl monomers, isobutylene monomers, vinyl acetate monomers, salts of any of these, derivatives of any of these, and mixtures thereof.

[0111] The composition may contain alkoxylated polyamines. Such substances include, but are not limited to, ethoxylated polyethyleneimines, ethoxylated hexamethylenediamines, and their sulfated derivatives. Polypropoxylated derivatives are also included. A wide variety of amines and polyacryeneimines may be alkoxylated to varying degrees and optionally further modified to provide the aforementioned advantages. A useful example is a 600 g / mol polyethyleneimine core ethoxylated to 20 EO groups per NH group. A preferred ethoxylated polyethyleneimine is PE-20, available from BASF.

[0112] A useful alkoxylated polyamine polymer is the alkoxylated polyethyleneimine type, which has a polyalkyleneimine core having one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, and the alkoxylated polyalkyleneimine is represented by empirical formula (20): (20) (PEI) j -(EO) k -R 14 It has, In the formula, j is the average number-average molecular weight (MW) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine. PEI ) is in the range of 100 to 100,000 daltons, k is the average degree of ethoxylation in the one or more side chains of the alkoxylated polyalkylene imine, in the range of 5 to 40, R 14 These are independently selected from the group consisting of hydrogen, C1-C4 alkyl groups, and combinations thereof.

[0113] Other suitable alkoxylated polyalkyleneimines include those having a polyalkyleneimine core having one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, and the alkoxylated polyalkyleneimine having empirical formula (21): (21) (PEI) o -(EO) m (PO) n -R 15 or (PEI) o -(PO) n (EO) m -R 15 It has, In the formula, o is the average number-average molecular weight (MW) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine. PEI) is in the range of 100 to 100,000 daltons, m is the average degree of ethoxylation in one or more side chains of the alkoxylated polyalkylene imine in the range of 10 to 50, n is the average degree of propoxylation in one or more side chains of the alkoxylated polyalkylene imine in the range of 1 to 50, R 15 These are independently selected from the group consisting of hydrogen, C1-C4 alkyl groups, and combinations thereof.

[0114] Cellulose polymers can be used in accordance with the present invention. Preferred cellulose polymers are selected from alkylcellulose, alkylalkoxyalkylcellulose, carboxyalkylcellulose, alkylcarboxyalkylcellulose, sulfoalkylcellulose, and more preferably from carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, and mixtures thereof. Preferred carboxymethylcellulose has a carboxymethyl substitution degree of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da. Preferred carboxymethylcellulose has a substitution degree greater than 0.65 and a blocking degree greater than 0.45, as described, for example, in International Publication No. 09 / 154933.

[0115] The consumer products of the present invention may also comprise one or more cellulosic polymers, including those selected from alkylcellulose, alkylalkoxyalkylcellulose, carboxyalkylcellulose, and alkylcarboxyalkylcellulose. In one embodiment, the cellulose polymer is selected from the group including carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, and mixtures thereof. In one embodiment, the carboxymethylcellulose has a carboxymethyl substitution degree of 0.5-0.9 and a molecular weight of 100,000 Da-300,000 Da. Examples of carboxymethylcellulose polymers include carboxymethylcellulose, commercially available from CPKelco as Finnfix® GDA, hydrophobic modified carboxymethylcellulose, for example, alkyl ketene dimer derivatives of carboxymethylcellulose, commercially available from CPKelco as Finnfix® SH1, or block carboxymethylcellulose, commercially available from CPKelco as Finnfix® V.

[0116] Cationic polymers can also be used in accordance with the present invention. Preferred cationic polymers have a cation 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 yet another embodiment, and at least 1.5 meq / gm in yet another embodiment, at the pH of the intended use of the composition (generally pH 3 to pH 9, and in one embodiment, pH 4 to pH 8), but less than 7 meq / gm in one embodiment and less than 5 meq / gm in another embodiment. In this specification, “cation 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 preferred cationic polymers is generally 10,000 to 10,000,000, at least 50,000 to 5,000,000 in one embodiment, and 100,000 to 3,000,000 in another embodiment.

[0117] Cationic polymers suitable for use in the compositions of this specification may contain a cationic nitrogen-containing moiety, such as a quaternary ammonium compound, or a protonated cationic amino compound. Any anionic counterion may be used in combination with the cationic polymer, provided that the polymer remains soluble in water, in the composition, or in the coacervate phase of the composition, and that the counterion is physically and chemically compatible with the essential components of the composition, or otherwise does not excessively impair the performance, stability, or aesthetics of the product. Non-limiting examples of such counterions include halides (e.g., chlorides, fluorides, bromides, iodides), sulfates, and methyl sulfates.

[0118] Non-exclusive examples of such polymers are listed in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes (The Cosmetic, Toiletry, and Fragrance Association, Inc. (Washington, DC) (1982)).

[0119] Particularly useful cationic polymers that can be used include cationic cellulose, cationic guar, poly(acrylamide-co-diallyldimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide-co-methacryloamidopropyl-pentamethyl-1,3-propylene-2-ol-ammonium dichloride), poly(acrylamide-co-N,N-dimethylaminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethylaminoethyl methacrylate) and its quaternary derivatives, poly(acrylamide-methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethylammonium chloride-co-acrylic acid), poly(diallyldimethylammonium chloride), poly(diallyldimethylammonium chloride-co-acrylic acid), poly(ethyl methacrylate-co-oleyl methacrylate-co-diethylaminoethyl methacrylate) and its quaternary derivatives, poly(ethyl methacrylate-co-dimethylaminoethyl methacrylate) and its quaternary derivatives, poly(hydroxypropyl acrylate-co-methacrylamidopropyltrimethylammonium chloride) and its quaternary derivatives, poly(hydroxyethyl acrylate-co-dimethylaminoethyl methacrylate) and its quaternary derivatives, poly(methyl acrylate Examples of cationic polymers include polymers selected from the group consisting of poly(vinylpyrrolidone-co-dimethylaminoethyl acrylate) and its quaternary derivatives, poly(methacrylate-co-methacrylamidopropyltrimethylammonium chloride), poly(vinylformamide-co-acrylic acid-co-diallyldimethylammonium chloride), poly(vinylformamide-co-diallyldimethylammonium chloride), poly(vinylpyrrolidone-co-acrylamide-co-vinylimidazole) and its quaternary derivatives, poly(vinylpyrrolidone-co-dimethylaminoethyl methacrylate) and its quaternary derivatives, poly(vinylpyrrolidone-co-methacrylamide-co-vinylimidazole) and its quaternary derivatives, poly(vinylpyrrolidone-co-vinylimidazole) and its quaternary derivatives, polyethyleneimine (including its quaternary derivatives), and mixtures thereof.

[0120] Other cationic polymers suitable for use in this composition include polysaccharide polymers, cationic guar gum derivatives, quaternary nitrogen-containing cellulose ethers, synthetic polymers, etherified cellulose, and copolymers of guar and starch. When used, the cationic polymers herein are soluble in the composition or soluble in the composite coacervate phase in the composition formed by the cationic polymers described above, as well as anionic, amphoteric, and / or bipolar surfactant components. The composite coacervate of the cationic polymer may also be formed together with other charged materials in the composition.

[0121] Suitable cationic polymers are described in U.S. Patent No. 3,962,418, U.S. Patent No. 3,958,581, and U.S. Patent Application Publication No. 2007 / 0207109(A1).

[0122] The composition may contain one or more anti-transfer agents. In one embodiment of the present invention, the inventors have surprisingly found that a composition containing a polymer anti-transfer agent in addition to a specific dye exhibits improved performance. This is because, surprisingly, the polymer anti-transfer agent prevents the dye from adhering. Suitable anti-transfer agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone and polyvinylimidazole, or mixtures thereof. Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and Chromabond S-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, Sokalan HP53, Sokalan HP59, Sokalan® HP56K and Sokalan® HP66 from BASF. The dye control agent may be selected from the group consisting of (i) sulfonated phenol / formaldehyde polymers, (ii) urea derivatives, (iii) polymers of ethylenically unsaturated monomers molecularly imprinted with dyes, (iv) fibers made of water-insoluble polyamides having an average diameter of about 2 μm or less, (v) polymers that can be obtained from the polymerization of benzoxazine monomer compounds, and (vi) combinations thereof. Other suitable DTIs are described in International Publication No. 2012 / 004134. If present in the composition of interest, the anti-dye agent may be present in a concentration of about 0.0001% to about 10% by weight, about 0.01% to about 5% by weight, or even about 0.1% to about 3% by weight of the composition.

[0123] Examples of water-soluble polymers include, but are not limited to, polyvinyl alcohol (PVA), modified PVA, polyvinylpyrrolidone; PVA copolymers such as PVA / polyvinylpyrrolidone and PVA / polyvinylamine; partially hydrolyzed polyvinyl acetate; polyalkylene oxides such as polyethylene oxide; polyethylene glycol; acrylamide; acrylic acid; alkylcellulose materials such as cellulose, e.g., methylcellulose, ethylcellulose, and propylcellulose; cellulose ethers; cellulose esters; celluloseamides; polyvinyl acetate; polycarbonate Carrier materials may include: rubonates and salts; polyamino acids or peptides; polyamides; polyacrylamides; maleic acid / acrylic acid copolymers; polysaccharides including starch and modified starch; gelatin; alginates; other hemicellulose polysaccharides including xyloglucan, xylan, glucuronoxylan, arabinoxylan, mannan, glucomannan, and galactoglucomannan; and natural gums such as pectin, xanthan gum, and carrageenan, locus bean, arabic, and tragacanth; and combinations thereof.

[0124] The composition may contain a fabric shading agent. Suitable fabric shading agents include dyes, dye-clay conjugates, and pigments. Suitable dyes include small molecule dyes and high molecule dyes. Suitable low molecule dyes include low molecule dyes selected from the group consisting of dyes classified by Color Index (CI) as direct blue, direct red, direct violet, acid blue, acid red, acid violet, basic blue, basic violet, and basic red, or mixtures thereof. Suitable dyes include alkoxylated azothiophene, solvent violet 13, acid violet 50, and direct violet 9.

[0125] Encapsulating agent The composition may contain an encapsulating agent. For example, the composition may contain an encapsulating agent in an amount of about 0.05% to about 5% by weight of the composition, or about 0.05% to about 5% by weight, or about 0.1% to about 5% by weight, or about 0.2% to about 2% by weight. The composition may contain an amount of encapsulating agent sufficient to provide the composition with about 0.05% to about 10% by weight, or about 0.1% to about 5% by weight, or about 0.1% to about 2% by weight of fragrance. The inclusion body may include a shell and a core. The core may be surrounded by the shell.

[0126] In this specification, the amount or weight percentage of the inclusion means the sum of the shell material and the core material.

[0127] The encapsulating agent may have a median volume weight size of about 0.5 micrometers to about 100 micrometers, or more preferably 10 to 100 micrometers, more preferably about 1 micrometer to about 60 micrometers, or more preferably 10 to 50 micrometers, or more preferably 20 to 45 micrometers, or alternatively 20 to 60 micrometers.

[0128] Single Unit Dose (SUD) Detergent Compositions According to various embodiments, any of the compositions described herein may be disposed in a water-soluble single unit dose (SUD) pouch as described in U.S. Patent No. 10,513,588(B2) by Friedrich et al., titled "Water-Soluble Polyvinyl Alcohol Film With Plasticizer Blend, Related Methods, and Related Articles," which is incorporated by reference in whole.

[0129] SUD packets and pouches may include at least one sealed compartment that can be filled with an active ingredient such as a detergent to produce a measuring dose pouch. The pouch may include one or more compartments. Figure 1 shows an article of a water-soluble pouch 100 formed from water-soluble polymer films 10, 20 sealed at an interface 30. One or both of the films 10, 20 contain a PVOH polymer and first, second, and third plasticizers. The films 10, 20 define an internal pouch container volume 40 for containing any desired composition 50 to be released into an aqueous environment. The composition 50 is not particularly limited and includes, for example, any of the various cleaning compositions described below. In embodiments having multiple compartments (not shown), each compartment may contain the same and / or different compositions. Furthermore, the composition may take any preferred form, such as liquid, solid, and combinations thereof (e.g., solid suspended in liquid), but is not limited thereto. In some embodiments, the pouch comprises first, second, and third compartments, each compartment containing a different first, second, and third composition.

[0130] SUD packets and pouches may be made from a water-soluble film containing a combination of polyvinyl alcohol (PVOH) polymer and plasticizers. The water-soluble film may contain a combination of polyvinyl alcohol (PVOH) polymer and at least three plasticizers.

[0131] Polyvinyl alcohol (PVOH) polymers may include one or more PVOH homopolymers, one or more PVOH copolymers, and combinations thereof. The PVOH polymer in a water-soluble film is not particularly limited and may include a single PVOH homopolymer, a single PVOH copolymer, or a blend of PVOH homopolymers, copolymers, or combinations thereof. In some embodiments, the water-soluble film may include water-soluble polymers other than PVOH polymers. In one class of embodiments, the PVOH polymer is a partially or completely hydrolyzed PVOH homopolymer comprising vinyl alcohol monomer units and optionally vinyl acetate monomer units. In another type of embodiment, the PVOH polymer is a partially or completely hydrolyzed PVOH copolymer comprising anionic monomer units, vinyl alcohol monomer units, and optionally vinyl acetate monomer units. In various embodiments, the anionic monomers include one or more vinylacetic acid, maleic acid, monoalkyl maleic acid, dialkyl maleic acid, monomethyl maleic acid, dimethyl maleic acid, maleic anhydride, fumaric acid, monoalkyl fumaric acid, dialkyl fumaric acid, monomethyl fumaric acid, dimethyl fumaric acid, fumaric anhydride, itaconic acid, monomethyl itaconic acid, dimethyl itaconic acid, itaconic anhydride, vinylsulfonic acid, allylsulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the above (e.g., sodium salt, potassium salt, or other alkali metal salts), esters of the above (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, this anionic monomer may include one or more acrylamide-methylpropanesulfonic acid (e.g., 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid) and their alkali metal salts (e.g., sodium salts).Similarly, anionic monomers may include monomethyl maleate and one or more alkali metal salts thereof (e.g., sodium salts). Examples of non-PVOH water-soluble polymers include polyethyleneimines, polyvinylpyrrolidone, polyalkylene oxides, polyacrylamides, cellulose ethers, cellulose esters, celluloseamides, polyvinyl acetate, polyamides, gelatin, methylcellulose, carboxymethylcellulose and their salts, dextrins, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrins, starches, modified starches, guar gums, acacia gums, xanthan gum, carrageenan, and polyacrylates and their salts.

[0132] The combination of plasticizers may include dipropylene glycol as the first plasticizer, a sugar alcohol (e.g., sorbitol) as the second plasticizer, and a polyol (e.g., glycerin) as the third plasticizer. The sugar alcohol plasticizer may be, for example, isomalt, maltitol, sorbitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol, or mannitol. In certain embodiments, the sugar alcohol plasticizer may be a sorbitol-containing plasticizer such as sorbitol or isomalt. The polyol plasticizer may be, for example, glycerin, diglycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol up to 400 MW, neopentyl glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, trimethylolpropane, or polyether polyol. In certain embodiments, the polyol plasticizer may be glycerin, propylene glycol, or 1,3-propanediol, for example, glycerin. In one class of embodiments, the water-soluble film comprises a polyvinyl alcohol (PVOH) polymer and a plasticizer blend comprising dipropylene glycol as a first plasticizer, sorbitol as a second plasticizer, and glycerin as a third plasticizer.

[0133] In some embodiments, the water-soluble film may include at least one plasticizer (e.g., a second plasticizer, a third plasticizer, or others) that is substantially solid at room temperature and / or typical use, storage, or transport temperatures, 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 such a range (e.g., lower than the typical film-forming process temperature such as casting, but higher than the typical use, storage, or transport temperature). Examples of such solid plasticizers include sorbitol (melting point 95°C) and trimethylolpropane (melting point 58°C). Additionally or selectively, the water-soluble film may contain at least one plasticizer (e.g., a second plasticizer, a third plasticizer, or otherwise) which is generally liquid at room temperature and / or typical use, storage, or transport temperatures, for example, 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 below such a range.

[0134] In some examples, a water-soluble unit-dose article includes at least one water-soluble film oriented to create at least one unit-dose internal compartment, the at least one unit-dose internal compartment containing a detergent composition. The water-soluble film and the detergent composition are described in more detail below.

[0135] In some examples, the consumer product comprises a container and at least one water-soluble unit-dose article, possibly at least two water-soluble unit-dose articles, possibly at least 20 water-soluble unit-dose articles, and possibly at least 30 water-soluble unit-dose articles. In some examples, the water-soluble unit-dose article is in the form of a pouch. In some examples, the water-soluble unit-dose article contains a unit dose of the composition in a volume sufficient to provide a benefit in the end use. In some examples, the water-soluble unit-dose article comprises one water-soluble film molded to include at least one internal compartment surrounded by the water-soluble film. At least one compartment contains the cleaning composition. The water-soluble film is sealed to prevent the cleaning composition from leaking out of the compartment during storage. However, when the water-soluble unit-dose article is added to water, the water-soluble film dissolves, releasing the contents of the internal compartment into the cleaning solution.

[0136] A unit dose article may contain two or more compartments, 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 an overlapping orientation, i.e., one on top of the other. Alternatively, the compartments may be arranged in a side-by-side orientation, i.e., one adjacent to the other. The compartments may be oriented in a "tire and rim" configuration, i.e., the first compartment is positioned adjacent to the second compartment, but the first compartment at least partially surrounds the second compartment, but does not completely enclose it. Alternatively, one compartment may be completely enclosed within another compartment. In some examples, a unit dose article contains at least two compartments, one of which is smaller than the other. In some examples, if a unit dose article contains at least three compartments, two of the compartments may be smaller than a third compartment, and in some examples, the smaller compartments are superimposed on the larger compartments. In some examples, the superimposed compartments are oriented side-by-side. In some examples, each individual unit-dose article may have a weight of 10g-40g, or even 15g-35g. The water-soluble film may be soluble or dispersible in water. Before being formed into unit-dose articles, the water-soluble film has a thickness of 20-150 micrometers in some examples, 35-125 micrometers in other examples, 50-110 micrometers in further examples, and about 76 micrometers in even further examples. Examples of water-soluble film materials include polymer materials. Film materials can be obtained, for example, by casting, blow molding, extrusion, or blow-extrusion of polymer materials.In some examples, the water-soluble film comprises a polyvinyl alcohol homopolymer or polyvinyl alcohol copolymer, for example, a blend of a polyvinyl alcohol homopolymer and / or a polyvinyl alcohol copolymer, the polyvinyl alcohol copolymer preferably selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, particularly carboxylated anionic polyvinyl alcohol copolymers, for example, a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer, or a blend of two or more, preferably two polyvinyl alcohol homopolymers. In another example, the water-soluble film comprises a single polyvinyl alcohol polymer, more preferably a carboxylated anionic polyvinyl alcohol copolymer. In some examples, the water-soluble film is supplied by Monosol as commodity reference numbers M8630, M8900, M8779, and M8310. In some examples, the film may be opaque, transparent, or translucent. The film may include printed areas. The printed areas can be obtained using techniques such as flexographic printing or inkjet printing. The film may contain aversive agents, for example, bittering agents. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate, or mixtures thereof. Exemplary concentrations of the aversive agent include, but are not limited to, 1-5000 ppm, 100-2500 ppm, or 250-2000 ppm. The water-soluble film or 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 mixtures thereof.

[0137] In some embodiments, the detergent product comprises a detergent composition. The detergent composition may be a laundry detergent composition, an automatic dishwashing composition, a hard surface cleaning composition, or a combination thereof. The detergent composition may comprise a solid, a liquid, or a mixture thereof. The term liquid includes gels, solutions, dispersions, pastes, or mixtures thereof. The solid may be a powder. In this specification, powder means that the detergent composition may comprise solid particles or a single homogeneous solid. In some embodiments, the powder detergent composition comprises particles. In this case, the powder detergent composition comprises individual solid particles, in contrast to the solid being a single homogeneous solid. The particles may be free-flowing or compressed. The laundry detergent composition may be used in a hand-washing operation of fabrics or in an automatic machine-washing operation of fabrics, for example, in an automatic machine-washing operation of fabrics. An exemplary laundry detergent composition comprises a non-soap surfactant, which comprises anionic non-soap surfactants and nonionic surfactants. In some embodiments, the laundry detergent composition comprises 10% to 60% by weight, or 20% to 55% by weight, of the non-soap surfactant of the laundry detergent composition. Exemplary weight ratios of non-soap anionic surfactants to nonionic surfactants are 1:1–20:1, 1.5:1–17.5:1, 2:1–15:1, or 2.5:1–13:1. Exemplary non-soap anionic surfactants include linear alkylbenzene sulfonates, alkyl sulfate anionic surfactants, or mixtures thereof. Examples of weight ratios of linear alkylbenzene sulfonates to alkyl sulfate anionic surfactants are 1:2–9:1, 1:1–7:1, 1:1–5:1, or 1:1–4:1. Exemplary linear alkylbenzene sulfonates are C 10 ~C 16 Alkylbenzenesulfonic acid or C 11 ~C 14It is an alkylbenzene sulfonic acid. "Linear" in this specification means that the alkyl group is linear. An exemplary alkyl sulfate anionic surfactant may include an alkoxylated alkyl sulfate, a non-alkoxylated alkyl sulfate, or a mixture thereof. An exemplary alkoxylated alkyl sulfate anionic surfactant includes an ethoxylated alkyl sulfate anionic surfactant. An exemplary alkyl sulfate anionic surfactant may include an ethoxylated alkyl sulfate anionic surfactant having a molar average degree of ethoxylation of 1-5, 1-3, or 2-3. An exemplary alkyl sulfate anionic surfactant may include a non-ethoxylated alkyl sulfate and an ethoxylated alkyl sulfate, and the molar average degree of ethoxylation of the alkyl sulfate anionic surfactant is 1-5, 1-3, or 2-3. The exemplary alkyl fraction of the alkyl sulfate anionic surfactant is derived from an aliphatic alcohol, an oxo-synthetic alcohol, a Guerbet alcohol, or a mixture thereof. In some examples, the laundry detergent composition contains 10%-50% by weight, 15%-45% by weight, 20%-40% by weight, or 30%-40% by weight of a non-soap anionic surfactant. In some examples, the nonionic surfactant is selected from alcohol alkoxylates, oxo-synthetic alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, or mixtures thereof. In some examples, the laundry detergent composition contains 0.01%-10% by weight, 0.01%-8% by weight, 0.1%-6% by weight, or 0.15%-5% by weight of a nonionic surfactant. In some embodiments, the laundry detergent composition comprises 1.5% to 20% by weight, 2% to 15% by weight, 3% to 10% by weight, or 4% to 8% by weight of soap, in some embodiments, a fatty acid salt, in some embodiments, an amine-neutralized fatty acid salt, in some embodiments, the amine is selected from alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, or mixtures thereof, and in some embodiments, monoethanolamine.In some examples, the laundry detergent composition is a liquid laundry detergent composition. In some examples, the liquid laundry detergent composition contains less than 15% by weight or less than 12% by weight of water. In some examples, the laundry detergent composition is a liquid laundry detergent composition comprising a non-aqueous solvent selected from 1,2-propanediol, dipropylene glycol, tripropylene glycol, glycerol, sorbitol, polyethylene glycol, or mixtures thereof. In some examples, the liquid laundry detergent composition contains 10%-40% by weight or 15%-30% by weight of the non-aqueous solvent. In some examples, the laundry detergent composition contains a fragrance. In some embodiments, the laundry detergent composition includes auxiliary components that can be selected from the group including citrate-containing builders, proteases, amylases, lipases, cellulases, mannanases, xyloglucanases, DNA, and mixtures thereof (encapsulated) enzymes, bleaches, bleach catalysts, aesthetic dyes, color dyes, whitening agents, cleaning polymers including alkoxylated polyamines and polyethyleneimines, stain-removing polymers, fabric conditioning polymers including polyquaternium-10 (CathEC), further surfactants including amine oxides and solvents, chelating agents including aminocarboxylates and aminophosphonate chelating agents, color transfer inhibitors, encapsulated fragrances, polycarboxylates, structuring agents, pH adjusters, antioxidants, preservatives, antimicrobial agents including Tinosan HP100, probiotics, and mixtures thereof. In some embodiments, the laundry detergent composition has a pH of 6-10, 6.5-8.9, or 7-8, and the pH of the laundry detergent composition is measured as the 10% product concentration in desalinated water at 20°C. In the case of liquids, laundry detergent compositions may be Newtonian or non-Newtonian. In some examples, liquid laundry detergent compositions are non-Newtonian. While we do not wish to be bound by theory, non-Newtonian liquids have different properties than Newtonian liquids; more specifically, the viscosity of non-Newtonian liquids depends on the shear rate, while Newtonian liquids have a constant viscosity regardless of the shear rate applied. The decrease in viscosity of non-Newtonian liquids when shear is applied is thought to further promote the dissolution of liquid detergents.The liquid laundry detergent compositions described herein may have any suitable viscosity, depending on factors such as the ingredients used and the purpose of the composition.

[0138] combination Various embodiments relate to the following: 1. A liquid detergent composition, At least one component according to one or more of the formulas 7-12:

[0139] [ka] R1 is a hydroxyl, C1-C6 carboxyl, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, or linear or branched C2-C6 alkynyl group. a is between 0 and 5. R2 is a condensed C1-C6 cycloalkyl, a condensed C1-C6 cycloalkoxy, or a condensed C1-C6 cycloalkenyl. b is between 0 and 4. R3 is oxygen or hydroxyl, c is between 0 and 4.

[0140] [ka] A liquid detergent composition comprising these combinations and salts. 2. The liquid detergent composition according to claim 1, wherein at least one component according to formula 7 is tropolone or a salt thereof. 3. A liquid detergent composition according to either 1 or 2, wherein at least one component according to Formula 7 is hinokitiol or a salt thereof. 4. A liquid detergent composition according to any one of 1 to 3, wherein at least one component has a pKa of about 8, preferably about 8 or less, more preferably about 7.5 or less, even more preferably about 5 to about 8, even more preferably about 5.0 to about 7.5, even more preferably about 5.0 to about 7.25, or most preferably about 5.0 to about 7.0. 5. A liquid detergent composition according to any one of 1 to 4, wherein 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, more preferably about 2.5 to about 3.5, or about 2.7 to about 3.1. 6. A liquid detergent composition according to any one of claims 1 to 5, wherein at least one component has an iron binding efficiency of more than about 10, about 10 to about 20, about 10.5 to about 14.1, or about 11 to about 12.9. 7. A liquid detergent composition according to any one of 1 to 6, wherein at least one component is present in an amount greater than about 0% by weight 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. 8. A liquid detergent composition according to any one of 1 to 7, further comprising a surfactant including an anionic surfactant, a nonionic surfactant, or a combination thereof. 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, more preferably alkylbenzene sulfonate. A single-unit-dose detergent comprising the liquid detergent composition described in any of sections 10.1 to 10.9. 11. A method for treating stains on fabric, At least one component from one or more of formulas 7-12:

[0141] [ka] R1 is a hydroxyl, C1-C6 carboxyl, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, or linear or branched C2-C6 alkynyl group. a is between 0 and 5. R2 is a condensed C1-C6 cycloalkyl, a condensed C1-C6 cycloalkoxy, or a condensed C1-C6 cycloalkenyl. b is between 0 and 4. R3 is oxygen or hydroxyl, c is between 0 and 4.

[0142] [ka] A method comprising washing fabrics in a cleaning solution comprising a liquid detergent composition containing these combinations and salts. 12. A method for pre-treating stains on fabric, A step of applying a liquid detergent composition to a fabric, wherein the liquid detergent composition comprises at least one component of one or more formulas 7 to 12:

[0143] [ka] R1 is a hydroxyl, C1-C6 carboxyl, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, or linear or branched C2-C6 alkynyl group. a is between 0 and 5. R2 is a condensed C1-C6 cycloalkyl, a condensed C1-C6 cycloalkoxy, or a condensed C1-C6 cycloalkenyl. b is between 0 and 4. R3 is oxygen or hydroxyl, c is between 0 and 4.

[0144] [ka] Methods including combinations thereof and salts. 13. The method according to any one of 11 to 12, wherein at least one component according to formula 7 is tropolone or a salt thereof. 14. The method according to any one of 11 to 13, wherein at least one component according to Formula 7 is hinokitiol or a salt thereof. 15. The method according to any one of 11 to 14, wherein at least one component has a pKa of about 8, preferably about 8 or less, more preferably about 7.5 or less, even more preferably about 5 to about 8, even more preferably about 5.0 to about 7.5, even more preferably about 5.0 to about 7.25, or most preferably about 5.0 to about 7.0. 16. The method according to any one of 11 to 15, wherein 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, more preferably about 2.5 to about 3.5, or about 2.7 to about 3.1. 17. The method according to any one of 11 to 16, wherein at least one component has an iron binding efficiency of more than about 10, about 10 to about 20, about 10.5 to about 14.1, or about 11 to about 12.9. 18. The method according to any one of 11 to 17, wherein at least one component is present in an amount 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. 19. The method according to any one of 11 to 18, further comprising maintaining the pH of the washing solution to less than approximately 10, approximately 7 to approximately 9.9, approximately 7.5 to approximately 9.0, approximately 7.5 to approximately 8.75, or approximately 8.0 to approximately 9.0. 20. The method according to any one of 11 to 19, wherein the liquid detergent composition is delivered to the cleaning solution via a single unit dose detergent containing the liquid detergent composition. 21. The method according to any one of 11 to 20, wherein the liquid detergent composition further comprises an anionic surfactant, a nonionic surfactant, or a combination thereof, preferably an anionic surfactant comprising alkylbenzene sulfonate, methyl ester sulfonate, alkyl ether carboxylate, alkyl sulfate, alkyl alkoxylated sulfate, or a combination thereof, more preferably alkylbenzene sulfonate. 22. At least one component of formulas 7-12 for treating stains on fabrics and / or washing fabrics.

[0145] [ka] R1 is a hydroxyl, C1-C6 carboxyl, linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, or linear or branched C2-C6 alkynyl group. a is between 0 and 5. R2 is a condensed C1-C6 cycloalkyl, a condensed C1-C6 cycloalkoxy, or a condensed C1-C6 cycloalkenyl. b is between 0 and 4. R3 is oxygen or hydroxyl, c is between 0 and 4.

[0146] [ka] The use of liquid detergent compositions containing these combinations and salts. 23. The use according to 22, wherein at least one component according to Formula 7 is tropolone or a salt thereof. 24. The use according to any one of 22 to 23, wherein at least one component according to Formula 7 is hinokitiol or a salt thereof. 25. Use according to any one of 22 to 24, wherein at least one component has a pKa of about 8, preferably about 8 or less, more preferably about 7.5 or less, even more preferably about 5 to about 8, even more preferably about 5.0 to about 7.5, even more preferably about 5.0 to about 7.25, or most preferably about 5.0 to about 7.0. 26. Use according to any one of 22 to 25, wherein 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, more preferably about 2.5 to about 3.5, or about 2.7 to about 3.1. 27. Use according to any one of 22 to 26, wherein at least one component has an iron binding efficiency of more than about 10, about 10 to about 20, about 10.5 to about 14.1, or about 11 to about 12.9. 28. The use according to any one of 22 to 27, wherein at least one component is present in an amount 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. 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, nonionic surfactants, and combinations thereof. 30. The use according to 29, wherein the surfactant is an anionic surfactant, preferably an alkylbenzene sulfonate, comprising at least one selected from the group consisting of sodium lauryl sulfate, linear alkylbenzene sulfonic acid, branched 2-alkyl primary alkyl alcohol sulfate, alkyl sulfate, or a combination thereof. 31. The use according to any one of 22 to 30, wherein the liquid detergent composition is contained in a single unit dose. [Examples]

[0147] The following examples are presented to provide a complete disclosure and explanation of how to carry out the methods disclosed and claimed herein, how to prepare the compositions and compounds, and how to use them, to those skilled in the art. While every effort has been made to ensure accuracy with respect to the figures (e.g., quantities, temperatures, etc.), some errors and deviations should be taken into consideration. The purpose of the following examples is not to limit the scope of various embodiments, but simply to provide examples illustrating specific embodiments.

[0148] Stain Removal Index Calculation Method Image analysis can be used to compare each stain to a control example of stain-free fabric. The software can convert the resulting images to standard color values, compare them to the standard based on a commonly used Macbeth color retention chart, and assign a color value (stain level) to each stain. The CIELAB color space is L * a * b * Also known as the color space, it is a color space defined in 1976 by the International Commission on Illumination (CIE). [a] It defines color as three values, namely the L of perceived lightness. * And the four inherent colors of human vision, namely red, green, blue, and yellow * and b * It is expressed as follows: Brightness value L * Here, 0 defines black and 100 defines white. * The axis is relative to the opposite colors green and magenta, with negative values ​​pointing towards green and positive values ​​pointing towards magenta. * The axis represents the opposite colors of blue and yellow, with negative numbers for blue and positive numbers for yellow. In the following examples, commercially available image analysis software is used to analyze various fabrics. * a * b * The values ​​were analyzed. Next, the SRI value was calculated using the given formula L * a * b *Calculated from the value. The higher the SRI, the better the stain removal.

[0149]

Number

[0150]

Number

[0151] Example 1: Single unit dose Four detergent compositions suitable for unit dose detergents were prepared and tested as detailed below in this specification. Each composition is shown below. Table 2A provides the amount of a given active ingredient in the wash solution in ppm. Table 2B provides the amount by weight % in the composition.

[0152]

Table 2

[0153]

Table 3

[0154] The following method was used to test the ability of the compositions to remove dirt in the washing process. Each composition was separately added to the pots of the Tergotometer. The volume of each pot was 1 L. The washing temperature was set at 35 °C. Throughout the procedure, 21 gpg of water was used. After stirring the product for 1 minute (400 rpm), the fabric was added (two internal replicas of each stain, 13 × 6 cm 2SBL2004 (supplied by WFK) and an additional 6cm 2 (A knitted cotton ballast square was added to bring the total weight of the fabric to 60g.) After adding the fabric, the washing solution was agitated for 30 minutes (300 rpm). The washing solution was then drained, the fabric was subjected to two 5-minute rinsing steps, drained, and tumble-dried. This procedure was repeated three more times to obtain a total of four external replicas. After washing, the stained fabrics were dried in a tumble dryer for 30 minutes.

[0155] As detailed in Table 3 below, one detergent treatment was applied to a turgotometer and evaluated using the washing method.

[0156] [Table 4]

[0157] Table 4 summarizes the stain removal tests between HEDP and troporon.

[0158] [Table 5]

[0159] As can be seen from Table 4, treatment at pH < 10.0 resulted in improved stain removal performance in the presence of tropolone compared to treatment without HEDP or a chelating agent.

[0160] Table 5 summarizes the stain removal tests for HEDP versus hinokitiol.

[0161] [Table 6]

[0162] As can be seen from Table 5, the examples with pH < 10.0 yielded improved stain removal performance in the presence of hinokitiol.

[0163] Example 2: Stain pretreatment Four liquid detergent compositions were prepared and tested as detailed below in this specification. Their respective compositions are shown below. Table 6A provides the amount of a given active ingredient in the cleaning solution in ppm. Table 6B provides the amount in weight % of the composition.

[0164] [Table 7]

[0165] [Table 8]

[0166] The ability of exemplary compositions to remove stains after pre-treatment before the washing process was tested using the following method. Referring to Table 7, the complete detergent additives for treatments 2A-2D were added separately to the pots of the turgotometer. For treatments 2E-2H, the pre-treatment dose of each detergent composition was applied equally to four stained fabrics via syringe. After application, pressure was applied to each stain using the end of the syringe in a circular motion for 5 seconds. The pre-treated stains were then left for 10 minutes before being added to the pots of the turgotometer along with the remaining treatment detergent. The capacity of each pot was 1 L. The washing temperature was set to 35°C. 21 gpg of water was used throughout the procedure. After stirring the product for 1 minute (400 rpm), the fabrics were added (two internal replicas of each stain, 13 × 6 cm). 2 SBL2004 (supplied by WFK) and an additional 6cm 2 (A knitted cotton ballast square was added to bring the total weight of the fabric to 60g.) After adding the fabric, the washing solution was agitated for 30 minutes (300 rpm). The washing solution was then drained, the fabric was subjected to two 5-minute rinsing steps, drained, and tumble-dried. This procedure was repeated three more times to obtain a total of four external replicas. After washing, the stained fabrics were dried in a tumble dryer for 30 minutes.

[0167] [Table 9]

[0168] Table 8 summarizes the stain removal tests for each treatment.

[0169]

Table 10

[0170] As can be seen from Table 8, the treatment compositions containing tropolone or hinokitiol promote a significant improvement in stain removal with pretreatment (Treatments 2G and 2H) compared to DTPMP with pretreatment (Treatment 2F).

[0171] Example 3: Compositions for Improving Stain Removal from Synthetic Clothing Four unit-dose detergent compositions were prepared and tested as detailed below in this specification. Each composition is shown below. Table 9A provides the amount of a given active ingredient in the cleaning solution in ppm. Table 9B provides the amount by weight % in the composition.

[0172] <o000901>

Table 11

[0173]

Table 12

[0174] Using the following method, as detailed in Table 10 below, the ability of exemplary treatment compositions to remove stains during the cleaning process was tested. Each composition was separately added to the pots of a Tergotometer. The volume of each pot was 1 L. The cleaning temperature was set at 35 °C. Throughout the procedure, 21 gpg of water was used. After stirring the product for 1 minute (400 rpm), the fabric was added (two internal replicas of each stain, 13 × 6 cm 2 of SBL2004 (supplied by WFK) and an additional 6 cm 2 It should be noted that there seems to be an error in the original text where "<o000901>" is likely a misspelling and should probably be " ". This has been maintained as is in the translation for the sake of following the instructions precisely.(A knitted cotton ballast square was added to bring the total weight of the fabric to 60g.) After adding the fabric, the washing solution was agitated for 30 minutes (300 rpm). The washing solution was then drained, the fabric was subjected to two 5-minute rinsing steps, drained, and tumble-dried. This procedure was repeated three more times to obtain a total of four external replicas. After washing, the stained fabrics were dried in a tumble dryer for 30 minutes.

[0175] [Table 13]

[0176] Table 11 summarizes the stain removal tests for each treatment.

[0177] [Table 14]

[0178] As can be seen from the above SRI values, formulas C and D of the present invention, which contain tropolone or hinokitiol, significantly improve stain removal on synthetic fabrics (polyester) compared to HEDP. As shown in Table 11, tropolone and hinokitiol showed better performance than HEDP on synthetic fabrics.

[0179] Examples 4 and 5 Examples 4 and 5 are exemplary water-soluble unit-dose formulations. The liquid detergent composition may be part of a single-chamber water-soluble unit-dose article or may be divided across multiple compartments to result in the following “compartment-averaged” whole article composition.

[0180] Example 4: Single-chamber water-soluble unit dose article The compositions detailed in Table 12 are encapsulated in polyvinyl alcohol-based water-soluble films, more specifically, water-soluble films containing a blend of polyvinyl alcohol homopolymer and carboxylated anionic polyvinyl alcohol copolymer, or water-soluble films containing selectively MonoSol carboxylated anionic polyvinyl alcohol copolymers such as M8630 or M8310.

[0181] [Table 15] * The nuclease enzyme is as claimed in concurrently pending European Patent Application No. 19219568.3. ** Lutensol FP620 - Ethoxylated Polyethyleneimine (PEI600 EO20) manufactured by BASF *** A polyethylene glycol graft polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, wherein the polymer system comprises 40% by weight of the polyethylene glycol backbone polymer and 60% by weight of the grafted vinyl acetate side chains. **** Lutensit Z96 (a zwitterionic polyamine manufactured by BASF - a zwitterionic hexamethylenediamine with the following formula: 100% quaternized, and approximately 40% of the polyethoxy (EO24) groups are sulfonated).

[0182] [ka] ***** Clariant Texcare SRA300

[0183] Example 5: Multi-compartment water-soluble unit dose article The following is a multi-compartment water-soluble single-dose laundry article having a larger bottom compartment with two smaller compartments arranged in an overlapping configuration on top of the bottom compartment, following the design of the Ariel 3-in-1 pod as commercially available in the UK in January 2020. The composition detailed in Table 13 is encapsulated in a water-soluble outer film of polyvinyl alcohol-based, more specifically, a water-soluble film comprising a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer, and a blend of polyvinyl alcohol homopolymers, optionally a water-soluble intermediate film comprising a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer.

[0184]

Table 16

[0185]

Chem.

[0186] [Table 17]

[0187] [Table 18]

[0188] [Table 19] 1 C12-15EO2.5S alkylethoxysulfates, available from P&G Chemicals, with the alkyl portion of AES having a molecular weight of 211-218 Daltons; 2 Branched alkyl sulfate example Z; 3 High C12 (96%) linear alkylbenzene sulfonate supplied by P&G Chemicals; 4 The Surfonic L24-9, commercially available from Huntsman; 5 C12 / C14 amine oxide supplied by P&G Chemicals; 6 Citrosol 502, commercially available from Archer Daniels Midland; 7 Preferenz, a commercially available product from DuPont; 8 Arctic, commercially available from Novozymes; 9 Disodium tetraborate pentahydrate, commercially available from Univar Solutions; 10 BASF's commercially available PE-20; 11 Sodium lauryl sulfate, available from P&G Chemicals.

[0189] Comparative examples can be prepared by combining all the raw materials to obtain composition A, except that not all of the water is added to compositions B-G and compositions 1-3 in order to leave space (referred to as holes) for addition to the branched alkyl sulfate and alkyl ethoxy sulfate. To prepare composition A, the following raw materials can be rapidly mixed in a mixing impeller for about 60 minutes to achieve a vortex: some water, solvent, surfactant (any surfactant other than branched alkyl sulfate or alkyl ethoxy sulfate), borax, stabilizer, neutralizer, builder, chelating agent, polymer, and enzyme to yield a stable one-phase liquid.

[0190] To prepare compositions B-G and compositions 1-3, branched alkyl sulfates and alkyl ethoxysulfates can be added to the top of composition A (which has holes) to achieve the desired level. Before adding the remaining water to balance the formulation, caustic substances or sulfur can be added to achieve a consistent pH of 8.2-8.6.

[0191] Compositions 4-9 can be prepared by rapidly mixing the following materials in a mixing impeller for about 60 minutes to achieve a vortex: some water, solvent, surfactant, borax, stabilizer, neutralizer, builder, chelating agent, polymer, and enzyme to yield a stable one-phase liquid. Caustic substances or sulfur are added to achieve a consistent pH of 8.2-8.6 before adding the remaining water to balance the formulation.

[0192] Further definitions and cross-references The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise specified, each such dimension is intended to mean both the listed value and the functionally equivalent range encompassing that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm."

[0193] All documents referenced herein, including any patents or patent applications that are cross-referenced or related, and any patent applications or patents on which this application claims priority or benefit thereof, are incorporated herein by reference in their entirety, unless expressly excluded or otherwise limited. No reference to any document shall be deemed prior art to any invention disclosed or claimed herein, nor shall any such invention be taught, suggested, or disclosed, either alone or in combination with any one or more other references. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in any document incorporated by reference, the meaning or definition given to that term in this document shall prevail.

[0194] While specific embodiments of this disclosure have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, 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, At least one component according to one or more of formulas 7 to 12: 【Chemistry 1】 R １ is a hydroxyl, C １ to C ６ carboxyl, straight-chain or branched-chain C １ to C ６ alkyl, straight-chain or branched-chain C ２ to C ６ alkenyl, or straight-chain or branched-chain C ２ to C ６ alkynyl group, a is between 0 and 5. R ２ is condensation C １ ~C ６ Cycloalkyl, condensed C １ ~C ６ Cycloalkoxy or condensed C １ ~C ６ It is a cycloalkenyl, b is between 0 and 4. R ３ is oxygen or hydroxyl, and c is between 0 and 4. 【Chemistry 2】 A liquid detergent composition comprising these combinations and salts.

2. The liquid detergent composition according to claim 1, wherein at least one component according to formula 7 is tropolone.

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

4. The liquid detergent composition according to any one of claims 1 to 3, wherein at least one of the components has a pKa of less than 8.

5. The liquid detergent composition according to any one of claims 1 to 4, wherein at least one of the components has a calcium binding efficiency of less than 7.

6. The liquid detergent composition according to any one of claims 1 to 5, wherein at least one of the components has an iron bonding efficiency of more than 10.

7. The liquid detergent composition according to any one of claims 1 to 6, wherein the at least one component is present in an amount of more than 0% to 10% by weight of the liquid detergent composition.

8. A liquid detergent composition according to any one of claims 1 to 7, further comprising a surfactant including 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 the liquid detergent composition according to any one of claims 1 to 9.

11. A method for treating stains on fabric, At least one component according to any of formulas 7 to 12: 【Transformation 3】 R １ is hydroxyl, C １ ~C ６ Carboxyl, linear, or branched C chain １ ~C ６ Alkyl, linear, or branched C ２ ~C ６ Alkenyl, or linear or branched C ２ ~C ６ It is an alkynyl group, a is between 0 and 5. R ２ is condensation C １ ~C ６ Cycloalkyl, condensed C １ ~C ６ Cycloalkoxy or condensed C １ ~C ６ It is a cycloalkenyl, b is between 0 and 4. R ３ is oxygen or hydroxyl, c is between 0 and 4. 【Chemistry 4】 A method comprising washing the fabric in a cleaning solution comprising a liquid detergent composition containing a combination of these and salts.

12. The method according to claim 11, wherein the at least one component according to formula 7 is tropolone.

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

14. The method according to any one of claims 11 to 13, wherein at least one of the components has a pKa of less than 8.

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

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