Biodegradable chelating agents and methods for fabric care

Abstract

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

Description

Technical Field

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

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

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

[0004]

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

[0006]

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

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

[0009]

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

[0011]

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

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

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

[0015]

[0016] in:

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

[0018] a is 0 to 5;

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

[0020] b is 0 to 4;

[0021] R3 is oxygen or hydroxy; and

[0022] c is 0 to 4.

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

[0024]

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

[0025] Introduction and Definitions

[0026] The present disclosure is written to describe the present invention to those of ordinary skill in the art, and those of ordinary skill in the art will understand that the present disclosure is not limited to the specific examples or embodiments described. Examples and embodiments are single instances of the present invention, which will make the larger scope obvious to those of ordinary skill in the art. Unless otherwise defined, all technical terms and scientific terms used herein have the same meaning as those commonly understood by those of ordinary skill in the art. It should also be understood that the terms used herein are not only for the purpose of describing examples and embodiments, and are not intended to be limiting, because the scope of the present disclosure will be limited only by the appended claims.

[0027] Unless otherwise expressly stated, all features disclosed in this specification (including any attached claims, abstracts and drawings) may be replaced by alternative features for the same, equivalent or similar purposes. Therefore, unless otherwise expressly stated, each feature disclosed is only an example of a general series of equivalent or similar features. The examples and embodiments described herein are only for illustrative purposes, and those of ordinary skill in the art will propose various modifications or changes according to these examples and embodiments, and these modifications or changes will be included in the spirit and scope of this application. Without substantially departing from the spirit and principles of the present disclosure, many changes and modifications may be made to the embodiments of the present disclosure. All such modifications and changes are intended to be included in the scope of the present disclosure herein. For example, unless otherwise specified, the present disclosure is not limited to specific materials, reagents, reaction materials, manufacturing processes, etc., because they may vary. It should also be understood that the terms used herein are only used for the purpose of describing specific embodiments and are not intended to be limited. It is also possible in the present disclosure that steps may be performed in different orders that are logically possible.

[0028] All numerical values ​​herein are assumed to be modified by the term "about", whether or not explicitly stated. The term "about" generally refers to a numerical range that one skilled in the art considers equivalent to the value (e.g., having the same function or result). In many cases, the term "about" may include numerical values ​​that are rounded to the nearest significant figure.

[0029] In everyday usage, indefinite articles (such as "a") precede countable nouns, and uncountable nouns almost never take indefinite articles. Thus, it must be noted that, as used in this specification and the claims that follow, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a carrier" includes a plurality of carriers. In particular, when a singular countable noun is listed as an element in a claim, this specification will generally use phrases such as "single." For example, "a single carrier."

[0030] Unless otherwise indicated, all percentages indicating the amount of a component in a composition represent the percentage by weight of the component based on the total weight of the composition. The term "mole percent" generally refers to the percentage of the number of moles of a particular component to the total number of moles in a mixture. The sum of the mole fractions of each component in a solution is equal to 1.

[0031] Where a numerical range is provided, it is understood that every intervening value (to one-tenth of the unit of the lower limit unless the context clearly dictates otherwise) between the upper and lower limits of that range, as well as any other stated or intervening values ​​in the stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the disclosure, subject to any explicitly excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding one or both of those included limits are also encompassed within the disclosure.

[0032] Throughout this specification and the claims that follow, reference will be made to a number of terms that are defined to have the following meanings, unless a contrary intention is apparent.

[0033] "Standard temperature and pressure" generally refers to 25°C and 1 atmosphere. Standard temperature and pressure may also be referred to as "ambient conditions". Unless otherwise indicated, parts are by weight, temperatures are in °C, and pressures are at or near atmospheric pressure. The terms "elevated temperature" or "elevated temperature" generally refer to temperatures of at least 100°C.

[0034] "Average size" refers to particle size. The particle size of a spherical object can be clearly and quantitatively defined by its diameter. However, typical material objects may be irregularly shaped and non-spherical. There are several ways to extend the above quantitative definitions to apply to non-spherical particles. Existing definitions are based on replacing a given particle with an imaginary sphere having one of the same properties as the particle. Volume-based particle size is equal to the diameter of a sphere with the same volume as the given particle. Area-based particle size is equal to the diameter of a sphere with the same surface area as the given particle. Weight-based particle size is equal to the diameter of a sphere with the same weight as the given particle. Hydrodynamic or aerodynamic particle size is equal to the diameter of a sphere with the same drag coefficient as the given particle.

[0035] "Mixing" refers to a unit operation in industrial process engineering that involves the manipulation of a heterogeneous physical system with the goal of making it more homogeneous. Mixing is performed to allow heat and / or mass transfer between one or more streams, components, or phases.

[0036] "Disposed on" refers to a positional state indicating that one object or material is arranged in a position adjacent to that of another object or material. The term does not require or exclude the presence of intervening objects, materials, or layers.

[0037] "Compositions" include fabric care compositions for hand washing, machine washing and other purposes, and include fabric care additive compositions and compositions suitable for soaking and / or pre-treating fabrics. They can take the form of, for example, laundry detergents, fabric pretreaters, fabric conditioners and / or other washing, rinsing, dryer added products and sprays. Compositions in liquid form can be in an aqueous carrier. Compositions in liquid form can be in an aqueous carrier. In other aspects, fabric care compositions are in the form of granular detergents or dryer added fabric softener tablets. Unless otherwise specified, the term includes multi-purpose or "heavy duty" detergents in granular or powder form, especially cleaning detergents; multi-purpose detergents in liquid, gel or paste form, especially the so-called heavy duty liquid (HDL) type; liquid delicate fabric detergents; cleaning adjuvants, such as bleach additives and "stain removal bars" or pre-treatment products loaded with substrates, dry and wet wipes and pads, nonwoven substrates and sponges; and sprays and fine mists. Various dosage forms can be used. The composition can be provided in a single unit dose (SUD) package or pouch, including a foil or plastic pouch or a water-soluble pouch, such as a polyvinyl alcohol (PVA) pouch; a metering ball or container; a container with an easy-to-open closure (such as a pull tab, a screw cap, a foil or plastic cap, etc.); or other containers known in the art. The composition can be a compact composition containing less than about 15%, or less than about 10%, or less than about 7% water.

[0038] "Unit dose" or "single unit dose" means an amount of the fabric care composition suitable for treating one load of laundry, such as from about 0.05 g to about 100 g, or from 10 g to about 60 g, or from about 20 g to about 40 g.

[0039] "Liquids" include free-flowing liquids as well as pastes, gels, foams and mousses. Non-limiting examples of liquids include light-duty and heavy-duty liquid detergent compositions, fabric enhancers, detergent gels typically used for laundry, bleaching agents and laundry additives. Gases (e.g., suspended bubbles) or solids (e.g., particles) may be contained in the liquid.

[0040] As used herein, "solid" includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include: granules, microcapsules, beads, pellets, and pearlescent beads. Solid compositions can provide technical benefits, including, but not limited to, whole wash process benefits, pre-treatment benefits, and / or aesthetic benefits.

[0041] Unexpectedly, it was found that tropolone and its derivatives such as hinokitiol can match or exceed the performance of HEDP in stain removal for single unit dose (SUD) applications. Thus, various embodiments meet the need to replace phosphonate chelating agents in fabric care compositions with phosphorus-free biodegradable materials.

[0042] Various embodiments are directed to chelating compositions comprising tropolone, tropolone derivatives, and salts thereof. Tropolone is also known as 2-hydroxycyclohepta-2,4,6-trien-1-one and is

[0043] As shown in formula 5.

[0044]

[0045] Hinokitiol is a tropol derivative, also known as 2-hydroxy-6-(propan-2-yl)cyclohepta-2,4,6-trien-1-one, as shown in Formula 6.

[0046]

[0047] Various embodiments relate to chelating compositions comprising components according to Formula 7

[0048]

[0049] Regarding formula 7,

[0050] R1 can be hydroxyl, C1-C6 carboxyl, straight chain or branched C1-C6 alkyl; straight chain or branched C2-

[0051] C6 alkenyl; or a straight or branched C2-C6 alkynyl group;

[0052] a can be 0 to 5;

[0053] R2 may be a fused C1-C6 cycloalkyl, a fused C1-C6 cycloalkoxy or a fused C1-C6 cycloalkenyl;

[0054] b can be 0 to 4;

[0055] R3 may be oxygen or hydroxyl; and

[0056] c can be 0 to 4.

[0057] It should be understood that the component according to Formula 7 can be tropolone or hinokitiol. When a, b and c are 0, Formula 7 can represent tropolone. When R1 is a branched C3 alkyl, a is 1, b is 0 and c is 0, Formula 7 can represent hinokitiol. The component according to Formula 7 can also be a variety of other compounds.

[0058] For example, the component according to Formula 7 can be γ-thujacetin as shown in Formula 8.

[0059]

[0060] The component according to Formula 7 may be α-thujasuline as shown in Formula 9.

[0061]

[0062] The component according to Formula 7 may be red phenol as shown in Formula 10.

[0063]

[0064] The component according to Formula 7 may be penicillic acid as shown in Formula 11.

[0065]

[0066] The component according to Formula 7 may be penicillanic acid as shown in Formula 12.

[0067]

[0068] Various embodiments relate to salts of tropolone or tropolone derivatives and all components according to Formula 7, including but not limited to sodium salts, potassium salts.

[0069] Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordination bonds between a ligand and a metal atom. Without being bound by theory, the decontamination efficacy of a composition comprising one or more chelating agents may depend at least in part on the ability of the chelating agent to bind to iron, which may be present in some stains (such as fruit or beverage stains). Several factors may affect the ability of a chelating agent to bind iron. These factors may include the pKa of the chelating agent compared to the wash pH, ​​and the affinity of the chelating agent to bind to other metals, materials or compositions in the wash.

[0070] Various embodiments can provide or employ compositions comprising one or more chelating agents having a pKa less than the wash pH. For example, the chelating agent can have a pKa of about 8, less than about 8, about 7, less than about 7, or in the range of about 5 to about 7, according to various embodiments.

[0071] Various embodiments may provide or employ compositions comprising one or more chelating agents that exhibit specific binding efficiency with a particular material. The binding efficiency may be expressed as a binding constant. The binding constant (also referred to as a formation constant or stability constant) is the equilibrium constant for complex formation in solution. It is a measure of the strength of interaction between agents that form a complex together. As an example, various stains may comprise catechins as shown in Formula 13.

[0072]

[0073] As shown in Table 1, this catechin may have a binding efficiency of about 3.5 with calcium and about 19.2 with iron, and competes with chelating agents for binding to these substances. Therefore, chelating agents according to various embodiments may be selected to ensure a lower binding efficiency with calcium and a higher binding efficiency with iron at wash pH.

[0074] Various embodiments can provide or employ compositions comprising one or more chelators having a calcium binding efficiency of about 2.0 to about 7.0, or about 2.2 to about 6.8, or about 2.5 to about 3.5, or about 2.7 to about 3.1, or less than about 6.8. A calcium binding efficiency of less than about 6.8 indicates that the chelator is less likely to bind calcium than HEDP, as shown in Table 1.

[0075] Various embodiments may provide or employ compositions comprising one or more chelators having an iron binding efficiency of about 10 to about 20, or about 10.5 to about 14.1, or about 11 to about 12.9, greater than about 10, as shown in Table 1.

[0076]

[0077] In Table 1, the reaction between metal and ligand is expressed as logK(β 110 ) description. In this context, K is the equilibrium constant for the reaction between the ligand and the metal. The higher the K, the more metal is bound. This is illustrated in the following examples.

[0078]

[0079] β represents the binding efficiency and accepts some subscripts (β mlh ) to indicate how much metal (m), ligand (l), and proton (h) are involved. 110 Indications involve one metal, one ligand, and no protons.

[0080] Solid detergent composition

[0081] Various embodiments relate to solid detergent compositions comprising at least one component according to Formula 7, combinations thereof, and salts. The at least one component may be present in an amount of greater than about 0% to about 10% by weight, or about 0.5% to about 9.5% by weight, or about 0.5% to about 9.5% by weight, or about 1.0% to about 9.0% by weight, or about 1.5% to about 8.5% by weight, or about 2.0% to about 8.0% by weight, or about 2.5% to about 7.5% by weight, or about 3.0% to about 7.0% by weight, or about 3.5% to about 6.5% by weight, or about 4.0% to about 6.0% by weight, or about 4.5% to about 5.5% by weight, or about 4.0% to about 5.0% by weight of the solid detergent composition.

[0082] It should be understood that, in addition to at least one component according to Formula 7, the solid detergent composition may also include a variety of other components. For example, the solid detergent composition may include a surfactant. The solid detergent composition may be a laundry detergent composition. A solid "laundry detergent composition" may include any composition intended to clean fabrics in a washing machine or hand-washing environment. In addition to hand-washing in a bucket or basin, for example, the solid laundry detergent composition can be used in high-efficiency and standard washing machines.

[0083] The detergent composition may be free of synthetic preservatives. Examples of synthetic preservatives include methylisothiazolinone and benzisothiazolinone.

[0084] Free-flowing solid granular laundry detergent composition

[0085] Typically, the free-flowing solid particulate laundry detergent composition is a fully formulated laundry detergent composition rather than a portion thereof such as a spray-dried, extruded or agglomerated particle forming only part of the laundry detergent composition. Typically, the solid composition comprises a plurality of chemically distinct particles, such as spray-dried base detergent particles and / or agglomerated base detergent particles and / or extruded base detergent particles; one or more, typically two or more, or five or more, or even ten or more particles are combined, the particles being selected from: surfactant particles, including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant strips, surfactant flakes; phosphate particles; zeolite particles; silicate particles, especially sodium silicate particles; carbonate particles, especially sodium carbonate particles; polymer particles, such as carboxylate polymer particles, cellulose polymer particles, starch particles, polyester particles, polyamine particles, terephthalic acid polymer particles, polyethylene glycol particles; aesthetic particles, such as colored strips, needles, lamellar particles and ring particles; enzyme particles, such as protease particles, amylase particles, lipase particles, cellulase particles, mannanase particles, pectate lyase particles, xyloglucanase particles, bleaching enzyme particles and any of these enzymes co-granules of at least one enzyme, preferably the enzyme granules comprise sodium sulfate; bleaching agent granules, such as percarbonate granules, especially coated percarbonate granules, such as percarbonate coated with carbonate, sulfate, silicate, borosilicate, or any combination thereof, perborate granules, bleach activator granules such as tetraacetylethylenediamine granules and / or alkyloxybenzenesulfonate granules, bleach catalyst granules such as transition metal catalyst granules, and / or isoquinolinium bleach catalyst granules, preformed peracid granules, especially coated preformed peracid granules particles; filler particles, such as sulfate particles and chloride particles; clay particles, such as montmorillonite particles and clay and silicone particles; flocculant particles, such as polyethylene oxide particles; wax particles, such as wax agglomerates; silicone particles, brightener particles; dye transfer inhibitor particles; dye fixative particles; perfume particles, such as perfume microcapsules and starch-encapsulated perfume accord particles, and pro-perfume particles, such as Schiff base reaction product particles; hueing dye particles; chelant particles, such as chelant agglomerates; and any combination thereof.

[0086] Suitable laundry detergent compositions comprise detergent ingredients selected from the group consisting of detersive surfactants, such as anionic detersive surfactants, nonionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants and amphoteric detersive surfactants; polymers, such as carboxylate polymers, soil release polymers, anti-redeposition polymers, cellulosic polymers and care polymers; bleaches, such as hydrogen peroxide sources, bleach activators, bleach catalysts and preformed peracids; photobleaches, such as sulfonated zinc phthalocyanine and / or sulfonated aluminum phthalocyanine; enzymes, such as proteases, amylases, cellulases, lipases; zeolite builders; phosphate builders; auxiliary builders, such as citric acid and citrates; carbonates, such as sodium carbonate and sodium bicarbonate; sulfates, such as sodium sulfate; silicates, such as sodium silicate; chloride salts, such as sodium chloride; brighteners; chelating agents; hueing agents; dye transfer inhibitors; dye fixatives; perfumes; silicones; fabric softeners, such as clays; flocculants, such as polyethylene oxides; suds suppressors; and any combination thereof.

[0087] Suitable laundry detergent compositions may have a low buffering capacity. Such laundry detergent compositions typically have a reserve alkalinity to pH 9.5 of less than 5.0 g NaOH / 100 g. These low buffered laundry detergent compositions typically contain low levels of carbonates.

[0088] Surfactants

[0089] The detergent composition may contain from about 5% to about 75%, or from about 5% to about 70%, or from about 5% to about 65%, or from about 5% to about 55%, or from about 5% to about 50%, or from about 10% to about 45%, or from about 10% to about 40% of a surfactant, by weight of the detergent composition. The surfactant may be an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant, or a combination thereof.

[0090] Anionic surfactants may include, for example, alkylbenzene sulfonates, methyl ester sulfonates, alkyl ether carboxylates, alkyl sulfates, alkyl alkoxylated sulfates, or combinations thereof. The alkylbenzene sulfonates may include linear alkylbenzene sulfonates. The linear alkylbenzene sulfonates may contain a small amount of branched alkylbenzene sulfonates as a byproduct of the manufacturing process, but this is generally less than about 5%. The linear alkylbenzene sulfonates may be present, for example, at a level of 0.5% to about 30% by weight of the liquid detergent composition. The linear alkylbenzene sulfonates may be selected from, for example, alkylbenzene sulfonic acid, C 10 To C 16 Alkylbenzenesulfonic acid alkali metal salt or amine salt. 10 To C 16 The linear alkylbenzene sulfonate surfactant may contain more than 50% C12 , greater than 60%, greater than 70% C 12 , more preferably greater than 75%. The linear alkylbenzene sulfonate may contain C 10 -C 16 Alkylbenzene sulfonate, C 11 -C 14 Alkylbenzene sulfonate or a mixture thereof. The alkylbenzene sulfonate may be an amine-neutralized alkylbenzene sulfonate, an alkali metal-neutralized alkylbenzene sulfonate or a mixture thereof. The amine includes, for example, monoethanolamine, triethanolamine, monoisopropanolamine or a mixture thereof. The alkali metal or alkaline earth metal includes, for example, sodium, potassium, magnesium or a mixture thereof.

[0091] Another acceptable anionic surfactant comprises an alkyl sulfate anionic surfactant. The alkyl sulfate anionic surfactant may include, for example, alkyl sulfate, alkoxylated alkyl sulfate or a mixture thereof. The alkyl sulfate anionic surfactant may be a primary alkyl sulfate anionic surfactant or a secondary alkyl sulfate anionic surfactant or a mixture thereof, such as sodium lauryl sulfate. Alkoxylated alkyl sulfate may include ethoxylated alkyl sulfate, propoxylated alkyl sulfate, mixed ethoxylated / propoxylated alkyl sulfate or a mixture thereof. The ethoxylated alkyl sulfate may have an average ethoxylation degree between 0.1 and 5 or between 0.5 and 3. The ethoxylated alkyl sulfate may have an average alkyl chain length between 8 and 18, more preferably between 10 and 16, and most preferably between 12 and 15. The alkyl portion of the ethoxylated alkyl sulfate may include, on average, 13.7 to about 16 or 13.9 to 14.6 carbon atoms. At least about 50% or at least about 60% of the AES molecules may include alkyl moieties having 14 or more carbon atoms, 14 to 18 or 14 to 17 or 14 to 16 or 14 to 15 carbon atoms.

[0092] The alkyl ether carboxylates may be straight chain or branched. They may have an average carbon chain length of from about 10 to about 26, from about 10 to about 20, or from about 16 to about 18. The alkyl ether carboxylates may have an average ethoxylation level of from about 2 to about 20, from about 7 to about 13, from about 8 to about 12, or from about 9.5 to about 10.5. The acid form or the salt form may be used. The alkyl chain may contain one cis or trans double bond. Commercial alkyl ether carboxylates are available from, for example, Kao Huntsman and Clariant

[0093] The alkyl chain of the alkyl sulfate anionic surfactant may be linear, branched or a mixture thereof. The branched alkyl sulfate anionic surfactant may be a branched primary alkyl sulfate, a branched secondary alkyl sulfate or a mixture thereof, preferably a branched primary alkyl sulfate, wherein the branch is preferably at the 2-position, or alternatively may be further present under the alkyl chain, or may be multi-branched, wherein the branch is distributed over the alkyl chain. The weight average degree of branching of the alkyl sulfate anionic surfactant may be from 0% to 100%, preferably from 0% to 95%, more preferably from 0% to 60%, most preferably from 0% to 20%. Alternatively, the weight average degree of branching of the alkyl sulfate anionic surfactant may be from 70% to 100%, preferably from 80% to 90%. Preferably, the alkyl chain is selected from materials of natural origin, materials of synthetic origin or mixtures thereof. Preferably, the material of synthetic origin comprises oxo-synthesized material, Ziegler-synthesized material, Guerbet-synthesized material, Fischer-Tropsch-synthesized material, isoalkyl-synthesized material or mixtures thereof, preferably oxo-synthesized material.

[0094] Branched 2-alkyl primary alkyl alcohol sulfates and 2-alkyl primary alkyl alcohol ethoxy sulfates with specific alkyl chain length distribution can provide increased detergency (especially in cold water). 2-alkyl branched alcohols (and 2-alkyl branched alkyl sulfates and 2-alkyl branched alkyl ethoxy sulfates and other surfactants derived from them) are positional isomers, wherein the position of the hydroxymethyl group (composed of a methylene bridge (-CH2-unit) connected to a hydroxyl (-OH) group) on the carbon chain is different. Therefore, 2-alkyl branched alkyl alcohols are generally composed of a mixture of positional isomers. In addition, it is well known that fatty alcohols (such as 2-alkyl branched alcohols) and surfactants are characterized by chain length distribution. In other words, fatty alcohols and surfactants are generally composed of a blend of molecules with different alkyl chain lengths (although a single chain length intercept can be obtained). It is noteworthy that the 2-alkyl primary alcohols described herein cannot be obtained by simply blending commercially available materials, and it can have a specific alkyl chain length distribution and / or a specific fraction of certain positional isomers. Specifically, a distribution of about 50% to about 100% by weight of surfactant having m+n=11 is not achievable by blending commercially available materials.

[0095] The detergent composition may comprise a mixture of surfactant isomers of Formula 14 and a surfactant of Formula 15:

[0096] (14)

[0097] (15)CH3-(CH2) m+n+3 -X

[0098] wherein about 50% to about 100% by weight of the first surfactant is an isomer having m+n=11; wherein about 25% to about 50% of the mixture of surfactant isomers of formula 14 has n=0; wherein about 0.001% to about 25% by weight of the first surfactant is a surfactant of formula 15; and wherein X is a hydrophilic moiety.

[0099] X can be neutralized, for example, with sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, calcium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diamines, polyamines, primary amines, secondary amines, tertiary amines, amine-containing surfactants, or combinations thereof.

[0100] X can be selected from sulfates, alkoxylated alkyl sulfates, sulfonates, amine oxides, polyalkoxylates, polyhydroxy moieties, phosphates, glycerol sulfonates, polyglucose salts, polyphosphates, phosphonates, sulfosuccinates, sulfosuccinamates, polyalkoxylated carboxylates, glucamides, taurates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerides, glyceride sulfates, glycerol ethers, glycerol ether sulfates, polyglyceryl ethers, polyglyceryl ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkane sulfonates, amidopropyl betaines, alkylated quaternary ammonium salts, alkylated / polyhydroxylated alkylated quaternary ammonium salts, alkylated / polyhydroxylated oxypropyl quaternary ammonium salts, imidazolines, 2-hydroxy-succinates, sulfonated alkyl esters, sulfonated fatty acids, and mixtures thereof.

[0101] Anionic surfactants may also be biosurfactants. Anionic biosurfactants may include, for example, rhamnolipids. Rhamnolipids may have a single rhamnose sugar ring or two sugar rings.

[0102] The detergent composition may also contain a nonionic surfactant. The nonionic surfactant may include alcohol alkoxylates, oxy alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, alkyl polyglucosides or mixtures thereof. Preferably, the nonionic surfactant may include, for example, alkoxylated alcohol nonionic surfactants, alkyl polyglucosides nonionic surfactants and mixtures thereof. Preferably, the alkoxylated alcohol nonionic surfactant is a linear or branched primary or secondary alkyl alkoxylated nonionic surfactant, preferably an alkyl alkoxylated nonionic surfactant, preferably an alkyl ethoxylated nonionic surfactant, preferably containing an average of about 9 to about 15 carbon atoms in its alkyl chain, preferably about 10 to about 16 carbon atoms, more preferably about 12 to about 15 carbon atoms; and having an average of about 5 to about 12, preferably about 6 to about 10, most preferably about 7 to about 8 or about 9 to about 10 ethylene oxide units per mole of alcohol. For example, the nonionic surfactant may include an ethoxylated nonionic surfactant, wherein the ethoxylated nonionic surfactant having an average carbon chain length of about 10 to about 16 includes an ethoxylated nonionic surfactant having an average carbon chain length of about 12 to about 14 and an average ethoxylation level of about 9 and a second ethoxylated nonionic surfactant having an average carbon chain length of about 14 to about 15 and an average ethoxylation level of about 7.

[0103] The nonionic surfactant may have the formula R(OC2H4) n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon groups containing from about 8 to about 16 carbon atoms and may be linear or branched, and n has an average value of from about 5 to about 15. For example, the additional nonionic surfactant may be selected from ethoxylated alcohols having an average of from about 12 to 14 carbon atoms in the alcohol (alkyl) portion and an average degree of ethoxylation of from about 7 to 9 moles of ethylene oxide per mole of alcohol.

[0104] Additional non-limiting examples include the formula R(OC2H4) n OH, wherein R comprises an alkylphenyl group, wherein the alkyl group comprises from about 8 to about 12 carbon atoms, and n has an average value of from about 5 to about 15, C 12 -C 18 Alkyl ethoxylates, such as those from Shell Nonionic surfactant; C 14 -C 22 Mid-chain branched alcohol; C 14 -C 22 Medium Chain Branched Alkyl Ethoxylate, BAE x, wherein x is 1 to 30. The nonionic ethoxylated alcohol surfactants herein may also contain residual alkoxylation catalysts, which may be considered as residues or impurities of the reaction. It may also contain various impurities or by-products of the alkoxylation reaction. The impurities may vary depending on the catalyst used and the reaction conditions. Impurities include alkyl ethers, such as dialkyl ethers, such as didodecyl ether; glycols, such as diethylene glycol, triethylene glycol, pentaethylene glycol, other polyethylene glycols.

[0105] The nonionic ethoxylated alcohol may be a narrow range ethoxylated alcohol. The narrow range ethoxylated alcohol may have the following general formula (I):

[0106]

[0107] Wherein R is selected from saturated or unsaturated, linear or branched C 10 -C 16 alkyl groups, and wherein greater than 90% of n is 0≤n≤15. In addition, the average value of n may be between about 4 and about 14, preferably between about 6 and about 10, wherein less than about 10% by weight of the alcohol ethoxylates are ethoxylates with n<7, and between 10% by weight and about 20% by weight of the alcohol ethoxylates are ethoxylates with n=8.

[0108] The composition may comprise an average value of n of about 10. The composition may have the following ranges for each of the following n: n=0 is up to 5%, each of n=1, 2, 3, 4, 5 is up to 2%, n=6 is up to 4%, n=7 is up to 10%, n=8 is between 12% and 20%, n=9 is between 15% and 25%, n=10 is between 15% and 30%, n=11 is between 10% and 20%, n=12 is up to 10%, and n>12 is up to 10%. The composition may have between 30% and 70% of n=9 to 10. The composition may have greater than 50% of its composition consisting of n=8 to 11.

[0109] R is selected from saturated or unsaturated, linear or branched C10-C16 alkyl groups, wherein the average value of n is between about 6 and about 10. R may also be selected from saturated or unsaturated, linear or branched C8-C 16 Alkyl groups, wherein more than 90% of n is 0≤n≤15, and wherein the average value of n is between about 5 and about 10, wherein less than about 20% by weight of the alcohol ethoxylates are ethoxylates with n<8. R may also be selected from saturated or unsaturated, linear or branched C 10 -C 16Alkyl groups wherein greater than 90% of n is 0≤n≤15, and wherein the average value of n is between about 6 and about 10, wherein less than about 10% by weight of the alcohol ethoxylates are ethoxylates with n<7, and between 10% by weight and about 20% by weight of the alcohol ethoxylates are ethoxylates with n=8.

[0110] The alcohol ethoxylates described herein are generally not a single compound as shown in their general formula (I), but rather they comprise a mixture of several homologs having different polyalkylene oxide chain lengths and molecular weights. Among the homologs, those having a total number of alkylene oxide units per mole of alcohol that is closer to the most common alkylene oxide adducts are ideal; homologs having a total number of alkylene oxide units that is much lower or much higher than the most common alkylene oxide adducts are less ideal. In other words, a "narrow range" or "peaked" alkoxylated alcohol composition is ideal. A "narrow range" or "peaked" alkoxylated alcohol composition refers to an alkoxylated alcohol composition having a narrow distribution of mole numbers of alkylene oxide additions.

[0111] A "narrow range" or "peaked" alkoxylated alcohol composition may be ideal for a selected application. Homologs within a selected target distribution range may have an appropriate lipophilic-hydrophilic balance for a selected application. For example, in the case of an ethoxylated alcohol product comprising an average ratio of 5 ethylene oxide (EO) units per molecule, homologs having a desired lipophilic-hydrophilic balance may be in the range of 2EO to 9EO. Homologs having shorter EO chain lengths (<2EO) or longer EO chain lengths (>9EO) may be undesirable for applications where surfactants with an EO / alcohol ratio of 5 are typically selected because such longer and shorter homologs are too lipophilic or too hydrophilic for the application utilizing the product. Therefore, it is advantageous to develop alkoxylated alcohols having a peaked distribution.

[0112] The narrow range alkoxylated alcohol compositions of the present disclosure may have an average degree of ethoxylation of from about 0 to about 15, e.g., from about 4 to about 14, from about 5-10, from about 8-11, and from about 6-9. The narrow range alkoxylated alcohol compositions of the present disclosure may have an average degree of ethoxylation of 10. The narrow range alkoxylated alcohol compositions of the present disclosure may have an average degree of ethoxylation of 9. The narrow range alkoxylated alcohol compositions of the present disclosure may have an average degree of ethoxylation of 5.

[0113] The alkyl polyglucoside surfactant may be selected from C10-C16 alkyl polyglucoside surfactants. The alkyl polyglucoside surfactant may have a number average degree of polymerization of 0.1 to 3.0, preferably 1.0 to 2.0, more preferably 1.2 to 1.6. The alkyl polyglucoside surfactant may comprise a blend of a short chain alkyl polyglucoside surfactant and a medium chain to long chain alkyl polyglucoside surfactant, wherein the short chain alkyl polyglucoside surfactant has an alkyl chain containing 10 or less carbon atoms, and the medium chain to long chain alkyl polyglucoside surfactant has an alkyl chain containing greater than 10 carbon atoms to 18 carbon atoms, preferably 12 to 14 carbon atoms.

[0114] Short-chain alkyl polyglucoside surfactants have a unimodal chain length distribution between C8-C10, medium-chain to long-chain alkyl polyglucoside surfactants have a unimodal chain length distribution between C10-C18, and medium-chain alkyl polyglucoside surfactants have a unimodal chain length distribution between C12-C14. In contrast, C8 to C18 alkyl polyglucoside surfactants generally have a unimodal distribution of alkyl chains between C8 and C18, such as C8 to C16, etc. Therefore, the combination of short-chain alkyl polyglucoside surfactants and medium-chain to long-chain or medium-chain alkyl polyglucoside surfactants has a wider chain length distribution than non-blended C8 to C18 alkyl polyglucoside surfactants, or even a bimodal distribution. Preferably, the weight ratio of short-chain alkyl polyglucoside surfactants to long-chain alkyl polyglucoside surfactants is 1: 1 to 10: 1, preferably 1.5: 1 to 5: 1, more preferably 2: 1 to 4: 1. It has been found that blends of such short chain alkyl polyglucoside surfactants and long chain alkyl polyglucoside surfactants result in faster dissolution of the detergent solution in water and improved initial foaming, while also improving foam stability.

[0115] C10-C16 alkyl polyglucosides are commercially available from several suppliers (e.g., surfactants; and 600CSUP, 650EC, 600CSUP / MB and 650EC / MB). 215UP is the preferred short chain APG surfactant. 600CSUP is the preferred medium to long chain APG surfactant.

[0116] The detergent composition may also contain amphoteric and / or zwitterionic surfactants. Suitable amphoteric or zwitterionic surfactants include amine oxides and / or betaines. Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amidopropyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides, and especially coconut dimethyl amine oxide. The amine oxide may have a straight chain or intermediate branched alkyl portion. Typical straight chain amine oxides include water-soluble amine oxides containing one R4C8 to C 18 An alkyl moiety and two R5 and R6 moieties selected from the group consisting of a C1 to C3 alkyl group and a C1 to C3 hydroxyalkyl group. Preferably, the amine oxide is characterized by formula 16

[0117] R4-N(R5)(R6)O(16)

[0118] Where R4 is C8 to C 18 alkyl, and R5 and R6 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl. Specifically, the linear amine oxide surfactant may include a linear C 10 -C 18 Alkyl dimethyl amine oxide and linear C8-C 12 Alkoxyethyl dihydroxyethyl amine oxide.

[0119] Other suitable ionic surfactants include betaines, such as alkyl betaines, alkyl amido betaines, amidazolinium betaines, sulfobetaines (sulfobetaines), and phosphobetaines, or combinations thereof.

[0120] polymer

[0121] Suitable polymers include carboxylate polymers, soil release polymers, anti-redeposition polymers, cellulosic polymers, conditioning polymers, and any combination thereof.

[0122] Carboxylate polymers

[0123] The composition may comprise a carboxylate polymer such as a maleate / acrylate random copolymer or a polyacrylate homopolymer. Suitable carboxylate polymers include: polyacrylate homopolymers having a molecular weight of 4,000 to 9,000 Da; maleate / acrylate random copolymers having a molecular weight of 50,000 to 100,000 Da, or 60,000 to 80,000 Da.

[0124] Another suitable carboxylate polymer is a copolymer comprising: (i) 50 wt% to less than 98 wt% of structural units derived from one or more monomers containing carboxyl groups; (ii) 1 wt% to less than 49 wt% of structural units derived from one or more monomers containing sulfonate moieties; and (iii) 1 wt% to 49 wt% of structural units derived from one or more types of monomers selected from monomers containing ether bonds represented by formula (I) and (II):

[0125] Formula (I) :

[0126]

[0127] Wherein in formula (I), R0 represents a hydrogen atom or a CH3 group, R represents a CH2 group, a CH2CH2 group or a single bond, and X represents a number from 0 to 5, provided that when R is a single bond, X represents a number from 1 to 5, and R1 is a hydrogen atom or a C1 to C 20 Organic groups;

[0128] Formula (II)

[0129]

[0130] In formula (II), R0 represents a hydrogen atom or a CH3 group, R represents a CH2 group, a CH2CH2 group or a single bond, X represents a number from 0 to 5, and R1 is a hydrogen atom or a C1 to C 20 Organic group.

[0131] It may be preferred that the polymer has a weight average molecular weight of at least 50 kDa or even at least 70 kDa.

[0132] Detergent polymers

[0133] The composition may comprise a soil release polymer. Suitable soil release polymers have a structure as defined by one of the following structures (I), (II) or (III):

[0134] (I)-[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d

[0135] (II)-[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e

[0136] (III)-[(OCHR5 -CHR 6 ) c -OR 7 ] f

[0137] in:

[0138] a, b and c are 1 to 200;

[0139] d, e and f are 1 to 50;

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

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

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

[0143] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Independently selected from H or C1-C 18 n-alkyl or C1-C 18 isoalkyl; and

[0144] R 7 A straight or branched C1-C 18 Alkyl, or straight or branched C2-C 30 alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or a C8-C 30 Aryl group, or C6-C 30 Arylalkyl group.

[0145] Suitable soil release polymers are available from Clariant as A series of polymers are sold, e.g. SRN240 and SRA300. Other suitable soil release polymers are available from Solvay as A series of polymers are sold, e.g. SF2 and Crystal.

[0146] Anti-redeposition polymers

[0147] Suitable anti-redeposition polymers include polyethylene glycol polymers and / or polyethylene imine polymers.

[0148] Suitable polyethylene glycol polymers include random graft copolymers comprising: (i) a hydrophilic backbone comprising polyethylene glycol; and (ii) one or more hydrophobic side chains selected from the group consisting of: C4-C 25 Alkyl groups, polypropylene, polybutylene, vinyl esters of saturated C1-C6 monocarboxylic acids, C1-C6 alkyl esters of acrylic or methacrylic acid, and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone having randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone may be in the range of 2,000Da to 20,000Da, or 4,000Da to 8,000Da. The molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains may be in the range of 1:1 to 1:5, or 1:1.2 to 1:2. The average number of grafting sites per ethylene oxide unit may be less than 0.02, or less than 0.016, the average number of grafting sites per ethylene oxide unit may be in the range of 0.010 to 0.018, or the average number of grafting sites per ethylene oxide unit may be less than 0.010, or in the range of 0.004 to 0.008.

[0149] Suitable polyethylene glycol polymers are described in WO08 / 007320.

[0150] A suitable polyethylene glycol polymer is Sokalan HP22.

[0151] Cellulose polymer

[0152] Suitable cellulosic polymers are selected from alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, alkyl carboxyalkyl celluloses, sulfonate alkyl celluloses, more preferably selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

[0153] Suitable carboxymethyl celluloses have a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.

[0154] Suitable carboxymethyl celluloses have a degree of substitution greater than 0.65 and a degree of blockiness greater than 0.45, for example as described in WO 09 / 154933.

[0155] Care polymers

[0156] Suitable care polymers include cationically modified or hydrophobically modified cellulosic polymers. Such modified cellulosic polymers can provide anti-abrasion benefits and dye lock benefits to fabrics during the wash cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose.

[0157] Other suitable care polymers include dye lock polymers, such as condensation oligomers produced by condensation of imidazole and epichlorohydrin, preferably in a 1:4:1 ratio. Suitable commercially available dye lock polymers are FDI (Cognis).

[0158] Other suitable care polymers include amino-silicones, which can provide fabric feel benefits and fabric form retention benefits.

[0159] Bleach

[0160] Suitable bleaching agents include a hydrogen peroxide source, a bleach activator, a bleach catalyst, a preformed peracid, and any combination thereof. Particularly suitable bleaching agents include a hydrogen peroxide source in combination with a bleach activator and / or a bleach catalyst.

[0161] Hydrogen peroxide source

[0162] Suitable sources of hydrogen peroxide include sodium perborate and / or sodium percarbonate.

[0163] Bleach Activator

[0164] Suitable bleach activators include tetraacetylethylenediamine and / or alkylphenol sulfonates.

[0165] Bleach Catalyst

[0166] The composition may contain a bleaching catalyst. Suitable bleaching catalysts include oxaziridinium bleaching catalysts, transition metal bleaching catalysts, especially manganese and iron bleaching catalysts. Suitable bleaching catalysts have a structure that conforms to the following general formula:

[0167]

[0168] Where R 13 Selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, isononyl, isodecyl, isotridecyl and isopentadecyl.

[0169] Preformed peracid

[0170] Suitable preformed peracids include phthalimidyl-peroxycaproic acid.

[0171] Enzymes

[0172] Suitable enzymes include lipases, proteases, cellulases, amylases, and any combination thereof.

[0173] Protease

[0174] Suitable proteases include metalloproteases and / or serine proteases. Examples of suitable neutral or alkaline proteases include: subtilisin (EC 3.4.21.62); trypsin-type or chymotrypsin-type proteases; and metalloproteases. Suitable proteases include chemically modified or genetically modified mutants of the aforementioned suitable proteases.

[0175] Suitable commercially available proteases include those sold under the trade names Liquanase Savinase and Those sold by Novozymes A / S (Denmark); under the trade name Prefer A series of proteases, including P280, P281, P2018-C, P2081-WE, P2082-EE and P2083-A / J, Purafect Purafect and Purafect Those sold by DuPont; under the trade name and Those sold by Solvay Enzymes; those purchased from Henkel / Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604, with the following mutations: S99D+S101 R+S103A+V104I+G159S, hereinafter referred to as BLAP); BLAP R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I) and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D), all from Henkel / Kemira; and KAP (alkalophilic Bacillus subtilisin with mutations A230V+S256G+S259N) from Kao.

[0176] Suitable proteases are described in WO11 / 140316 and WO11 / 072117.

[0177] Amylase

[0178] Suitable amylases are derived from the AA560 alpha amylase endogenous to Bacillus sp. DSM 12649, preferably with the following mutations: R118K, D183*, G184*, N195F, R320K and / or R458K. Suitable commercially available amylases include Plus, Natalase, Ultra, SZ, (both from Novozymes) and AA, Preferenz Series of amylase, and Ox Am, HT Plus (both from Du Pont).

[0179] Suitable amylases are described in WO06 / 002643.

[0180] Cellulase

[0181] Suitable cellulases include those derived from bacteria or fungi. Chemically modified or protein engineered mutants are also suitable. Suitable cellulases include cellulases from Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, such as fungal cellulases produced by Humicola insolens, Myceliophthorathermophila and Fusarium oxysporum.

[0182] Commercially available cellulases include and Premium, and (Novozymes A / S), Series enzymes (DuPont), and Series enzymes (AB Enzymes). Suitable commercially available cellulases include Premium, Classic. Suitable proteases are described in WO07 / 144857 and WO10 / 056652.

[0183] Lipase

[0184] Suitable lipases include those of bacterial, fungal or synthetic origin, and their variants. Chemically modified or protein engineered mutants are also suitable. The example of a suitable lipase includes a lipase from Humicola (synonym Thermomyces), for example from H. lanuginosa (T. lanuginosus).

[0185] The lipase may be a "first cycle lipase", e.g., such as those described in WO06 / 090335 and WO13 / 116261. In one aspect, the lipase is a first wash lipase, preferably a variant of the wild-type lipase from Thermomyces lanuginosus comprising a T231R and / or N233R mutation. Preferred lipases include those sold under the trade name and Those sold by Novozymes (Bagsvaerd, Denmark).

[0186] Other suitable lipases include: Liprl 139, e.g., as described in WO2013 / 171241; and TfuLip2, e.g., as described in WO2011 / 084412 and WO2013 / 033318.

[0187] Other enzymes

[0188] Other suitable enzymes are bleaching enzymes such as peroxidases / oxidases, including those of plant, bacterial or fungal origin and variants thereof. Commercially available peroxidases include (Novozymes A / S). Other suitable enzymes include choline oxidase and perhydrolase, such as those used in Gentle Power Bleach TM Those in .

[0189] Other suitable enzymes include those sold under the trade name (from Novozymes A / S, Bagsvaerd, Denmark) and Pectate lyase sold under the trade name (Novozymes A / S, Bagsvaerd, Denmark) and Mannanase sold by Du Pont.

[0190] Zeolite Builder

[0191] The composition may comprise a zeolite builder. The composition may comprise from 0% to 5% by weight of a zeolite builder, or 3% by weight of a zeolite builder. The composition may even be substantially free of zeolite builder; substantially free means "no intentional addition". Typical zeolite builders include zeolite A, zeolite P and zeolite MAP.

[0192] Phosphate Builder

[0193] The composition may comprise a phosphate builder. The composition may comprise from 0% to 5% by weight of a phosphate builder, or to 3% by weight of a phosphate builder. The composition may even be substantially free of phosphate builder; substantially free means "no intentionally added". A typical phosphate builder is sodium tripolyphosphate.

[0194] Carbonate

[0195] The composition may comprise carbonates. The composition may comprise 0% to 10% by weight of carbonates, or 0% to 5% by weight of carbonates. The composition may even be substantially free of carbonates; substantially free means "no intentional addition". Suitable carbonates include sodium carbonate and sodium bicarbonate.

[0196] Silicate

[0197] The composition may comprise a silicate. The composition may comprise 0 to 10 wt% silicate, or 0 to 5 wt% silicate. A preferred silicate is sodium silicate, particularly preferred is sodium silicate having a Na2O:SiO2 ratio of 1.0 to 2.8, preferably 1.6 to 2.0.

[0198] Sulfate

[0199] A suitable sulfate salt is sodium sulfate.

[0200] Brightener

[0201] Suitable fluorescent brighteners include: distyrylbiphenyl compounds, such as CBS-X, diaminostilbene disulfonic acid compounds, such as DMS pure Xtra and HRH, and pyrazoline compounds, e.g. SN and coumarin compounds, e.g. SWN.

[0202] Preferred brighteners are: sodium 2(4-phenylvinyl-3-sulfophenyl)-2H-naphtho[1,2-d]triazole, disodium 4,4'-bis{[(4-phenylamino-6-(N-methyl-N-2-hydroxyethyl)amino1,3,5-triazine-2-yl)];amino}stilbene-2-2'disulfonate, disodium 4,4'-bis{[(4-phenylamino-6-morpholino-1,3,5-triazine-2-yl)]amino}stilbene-2-2'disulfonate and disodium 4,4'-bis(2-sulfonostyryl)biphenyl. A suitable fluorescent brightener is CI. Fluorescent brightener 260, which can be used in the form of its β or α crystalline form or a mixture of these crystalline forms.

[0203] Other chelating agents

[0204] The composition may also include one or more additional chelating agents, i.e., not a chelating compound according to formula 7, the chelating agent being selected from: diethylenetriamine pentaacetate, diethylenetriamine penta(methylphosphonic acid), ethylenediamine-N'N'-disuccinic acid, ethylenediamine tetraacetate, ethylenediamine tetra(methylenephosphonic acid) and hydroxyethane di(methylenephosphonic acid). Preferred chelating agents are ethylenediamine-N'N'-disuccinic acid (EDDS) and / or hydroxyethane diphosphonic acid (HEDP). The composition preferably includes ethylenediamine-N'N'-disuccinic acid or a salt thereof. Preferably, ethylenediamine-N'N'-disuccinic acid is in the form of the S, S enantiomer. Preferably, the composition includes 4,5-dihydroxy-isobenzene disulfonic acid disodium salt. Preferred chelating agents may also act as calcium carbonate crystal growth inhibitors, such as: 1-hydroxyethane diphosphonic acid (HEDP) and its salts; N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and its salts; 2-phosphonobutane-1,2,4-tricarboxylic acid and its salts; and combinations thereof.

[0205] Toner

[0206] Suitable tinting agents include small molecule dyes, typically belonging to the Color Index (CI) classification of acid, direct, basic, reactive (including their hydrolyzed forms) or solvent or disperse dyes, such as dyes classified as blue, violet, red, green or black, and providing the desired hue, either alone or in combination. Preferred such tinting agents include acid violet 50, direct violet 9, 66 and 99, solvent violet 13, and any combination thereof.

[0207] Many hueing agents that may be suitable for use in the present invention are known and described in the art, such as the hueing agents described in WO2014 / 089386.

[0208] Suitable hueing agents include phthalocyanine and azo dye conjugates such as described in WO2009 / 069077.

[0209] Suitable toners can be alkoxylated. Such alkoxylated compounds can be prepared by organic synthesis, which can produce a mixture of molecules with different degrees of alkoxylation. Such mixtures can be used directly to provide toners, or can undergo purification steps to increase the ratio of the target molecule. Suitable toners include alkoxylated disazo dyes, such as those described in WO2012 / 054835, and / or alkoxylated thiophene azo dyes, such as those described in WO2008 / 087497 and WO2012 / 166768.

[0210] Toner can be incorporated in the detergent composition as a part for reaction mixture, and this reaction mixture is the result of organic synthesis dye molecules by one or more optional purification steps.This type of reaction mixture generally comprises dye molecules themselves, and can also comprise the by product of unreacted starting material and / or organic synthesis pathway in addition.Suitable toner can be incorporated in the hueing dye particles, such as described in WO 2009 / 069077.

[0211] Dye transfer inhibitors

[0212] Suitable dye transfer inhibitors include polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinyl pyrrolidone, polyvinyl oxazolidones, polyvinyl imidazoles and mixtures thereof. Preferred are poly(vinyl pyrrolidone), poly(vinyl pyridine betaine), poly(vinyl pyridine N-oxide), poly(vinyl pyrrolidone-vinylimidazole) and mixtures thereof. Suitable commercially available dye transfer inhibitors include PVP-K15 and K30 (Ashland), HP165, HP50, HP53, HP59, HP56K, HP56, HP66 (BASF), S-400, S403E and S-100 (Ashland).

[0213] spices

[0214] Suitable fragrances include fragrance materials selected from the following groups: (a) fragrance materials having a ClogP of less than 3.0 and a boiling point of less than 250°C (quadrant 1 fragrance materials); (b) fragrance materials having a ClogP of less than 3.0 and a boiling point of 250°C or greater (quadrant 2 fragrance materials); (c) fragrance materials having a ClogP of 3.0 or greater and a boiling point of less than 250°C (quadrant 3 fragrance materials); (d) fragrance materials having a ClogP of 3.0 or greater and a boiling point of 250°C or greater (quadrant 4 fragrance materials); and (e) mixtures thereof.

[0215] For perfume, it is preferably in the form of perfume delivery technology. Such delivery technology also stabilizes and enhances the release of deposition and perfume materials from washed fabrics. Such perfume delivery technology can also be used to further increase the persistence of perfume released from washed fabrics. Suitable perfume delivery technology includes: perfume microcapsules, former perfumes, polymer-assisted delivery, molecule-assisted delivery, fiber-assisted delivery, amine-assisted delivery, cyclodextrin, starch-encapsulated accords, zeolites and other inorganic carriers and any mixture thereof. Suitable perfume microcapsules are described in WO2009 / 101593.

[0216] Siloxane

[0217] Suitable silicones include polydimethylsiloxanes and aminosilicones. Suitable silicones are described in WO05075616.

[0218] Method for preparing solid composition

[0219] Generally, the particles of the composition can be prepared by any suitable method, such as spray drying, agglomeration, extrusion, and any combination thereof.

[0220] Typically, a suitable spray drying process comprises the steps of forming an aqueous slurry mixture, transferring it to a pressure nozzle by at least one pump, preferably two pumps. Atomizing the aqueous slurry mixture into a spray drying tower and drying the aqueous slurry mixture to form spray-dried particles. Preferably, the spray drying tower is a countercurrent spray drying tower, although a cocurrent spray drying tower may also be suitable.

[0221] Typically, the spray-dried powder is subjected to cooling, such as air stripping. Typically, the spray-dried powder is subjected to particle size classification, such as sieving, to obtain a desired particle size distribution. Preferably, the spray-dried powder has a particle size distribution such that the weight average particle size is in the range of 300 microns to 500 microns, and less than 10% by weight of the spray-dried particles have a particle size greater than 2360 microns.

[0222] It may be preferred to heat the aqueous slurry mixture to raise the temperature prior to atomization into a spray drying tower, such as described in WO2009 / 158162.

[0223] For anionic surfactants, such as linear alkylbenzene sulfonates it may be preferred that they are introduced into the spray drying process after the step of forming the aqueous slurry mixture: for example, the acid precursor is introduced into the aqueous slurry mixture after pumping, such as described in WO 09 / 158449.

[0224] It may be preferred for a gas such as air to be introduced into the spray drying process after the step of forming the aqueous slurry, such as described in WO2013 / 181205.

[0225] It may be preferred for any inorganic ingredients, such as sodium sulphate and sodium carbonate, if present in the aqueous slurry mixture, that the sodium sulphate and sodium carbonate are micronised to a small particle size, such as described in WO2012 / 134969.

[0226] Typically, suitable agglomeration processes include the step of contacting a detersive ingredient, such as a detersive surfactant, e.g. linear alkylbenzene sulfonate (LAS) and / or an alkyl alkoxylated sulfate, with an inorganic material, such as sodium carbonate and / or silica in a mixer. The agglomeration process may also be an in-situ neutralization agglomeration process, wherein an acid precursor of a detersive surfactant, such as LAS, is contacted with an alkaline material, such as carbonate and / or sodium hydroxide in a mixer, and wherein the acid precursor of the detersive surfactant is neutralized by the alkaline material during the agglomeration process to form a detersive surfactant.

[0227] Other suitable detergent ingredients that may be agglomerated include polymers, chelating agents, bleach activators, silicones, and any combination thereof.

[0228] Agglomeration process can be high, medium or low shear agglomeration process, wherein high shear, medium shear or low shear mixer is used accordingly. Agglomeration process can be multi-step agglomeration process, wherein two or more mixers are used, such as high shear mixer combined with medium or low shear mixer. Agglomeration process can be continuous process or batch process.

[0229] It may be preferred for the agglomerates to be subjected to a drying step, for example to a fluidized bed drying step. It may also be preferred for the agglomerates to be subjected to a cooling step, for example to a fluidized bed cooling step.

[0230] Typically, the agglomerates are subjected to particle size classification, such as fluidized bed elution and / or sieving, to obtain a desired particle size distribution. Preferably, the agglomerates have a particle size distribution such that the weight average particle size is in the range of 300 microns to 800 microns, and less than 10% by weight of the agglomerates have a particle size of less than 150 microns, and less than 10% by weight of the agglomerates have a particle size greater than 1200 microns.

[0231] It may be preferred for fine and oversized agglomerates to be recycled back into the agglomeration process. Typically, oversized particles are subjected to a comminution step, such as grinding, and recycled back to a suitable location in the agglomeration process, such as a mixer. Typically, fines are recycled back to a suitable location in the agglomeration process, such as a mixer.

[0232] For ingredients, such as polymers and / or nonionic detersive surfactants and / or perfumes, it may be preferred to spray onto base detergent particles, such as spray-dried base detergent particles and / or agglomerated base detergent particles. Typically, the spraying step is carried out in a tumble drum mixer.

[0233] Additives

[0234] Compositions according to various embodiments may include one or more adjunct ingredients. The non-limiting list of adjuncts provided below is suitable for use in the compositions of the present invention and may be desirably incorporated in certain embodiments, for example to aid or enhance the performance of treating the substrate to be cleaned, or to alter the aesthetics of the composition, as in the case of perfumes, colorants, dyes, and the like. Suitable adjunct materials include, but are not limited to, polymers such as cationic polymers, surfactants, builders, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersants, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structural elasticizers, fabric softeners, carriers, hydrotropes, processing aids, and / or pigments.

[0235] Methods of washing fabrics

[0236] The method for washing fabrics comprises contacting a solid composition with water to form a wash liquor, and a step of washing fabrics in the wash liquor. Typically, the wash liquor has a temperature higher than 0°C to 90°C, or to 60°C, or to 40°C, or to 30°C, or to 20°C. Before, after, or while contacting the solid composition with water, the fabric may be contacted with water. Typically, the wash liquor is formed by contacting a laundry detergent with water so that the concentration of the laundry detergent composition in the wash liquor is 0.2g / L to 20g / L, or 0.5g / L to 10g / L, or to 5.0g / L. The method for washing fabrics can be carried out in a front loading automatic washing machine, a top loading automatic washing machine, including a high efficiency automatic washing machine, or a suitable hand washing container. Typically, the wash liquor comprises 90 liters or less, or 60 liters or less, or 15 liters or less, or 10 liters or less of water. Typically, 200 g or less, alternatively 150 g or less, alternatively 100 g or less, alternatively 50 g or less of the laundry detergent composition is contacted with water to form the wash liquor.

[0237] Fibrous water-soluble products

[0238] The composition according to any embodiment described herein can be delivered via or in the form of a fibrous water-soluble product. The fibrous water-soluble product can include one or more layers. These layers can be stacked on top of each other. These layers can be placed directly on top of each other, with particles between these layers, or a combination thereof.

[0239] The fibrous water-soluble unit dose product may contain 50% or more bio-based materials, such as, for example, 50% to 95% bio-based materials. Some of the individual components of the fibrous water-soluble unit dose product may be completely bio-based to produce a product with a total bio-based content greater than 50%.

[0240] These fibrous water-soluble unit dose articles can dissolve under a variety of wash conditions, such as low temperature, low water and / or one or more short wash cycles, where consumers have overloaded the machine, especially with items with high water absorbency, while providing sufficient active agent delivery to achieve the desired effect on the target consumer matrix (with similar performance to today's liquid products).

[0241] The surface of the fibrous water-soluble unit dose product may include a printed area. The printed area may cover about 10% to about 100% of the surface of the product. The printed area may include ink, pigment, dye, bluing agent or a mixture thereof. The printed area may be opaque, translucent or transparent. The printed area may include monochrome or polychromatic. The printed area may be on more than one side of the product and include instruction text, graphics, etc. The surface of the water-soluble unit dose product may include an aversive agent, such as a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate or a mixture thereof. Any suitable amount of an aversive agent may be used. Suitable content includes, but is not limited to, 1ppm to 5000ppm, or even 100ppm to 2500ppm, or even 250rpm to 2000ppm.

[0242] The fibrous water-soluble unit dose article may exhibit a thickness of greater than 0.01 mm and / or greater than 0.05 mm and / or greater than 0.1 mm and / or to about 100 mm and / or to about 50 mm and / or to about 20 mm and / or to about 10 mm and / or to about 5 mm and / or to about 2 mm and / or to about 0.5 mm and / or to about 0.3 mm.

[0243] The fibrous water-soluble unit dose product may have a density of about 500 g / m 2 Up to about 5,000g / m 2 , or about 1,000g / m 2 Up to about 4,000g / m 2 , or about 1,500g / m 2 About 3,500g / m 2 , or about 2,000g / m 2 About 3,000g / m 2 or a combination thereof.

[0244] The fibrous water-soluble unit dose product may exhibit different regions, such as different regions of basis weight, density, thickness and / or wetting properties. The fibrous water-soluble unit dose product may be compressed at the edge seal. The fibrous water-soluble unit dose product may include texture on one or more surfaces of its surface. The surface of the fibrous water-soluble unit dose product may include a pattern, such as a non-random repeating pattern. The fibrous water-soluble unit dose product may include holes. The fibrous water-soluble unit dose product may include a fibrous structure having discrete fiber element regions that are different from other regions of the fiber elements in the structure. The fibrous water-soluble unit dose product may be used as is, or may be coated with one or more active agents.

[0245] The fibrous water-soluble unit dose product may include one or more plies. The fibrous water-soluble unit dose product may include at least two and / or at least three and / or at least four and / or at least five plies. The fiber plies may be a fiber structure. Each ply may include one or more layers, such as one or more fiber element layers, one or more particle layers, and / or one or more fiber element / particle mixture layers. The layer may be sealed. Specifically, the particle layer and the fiber element / particle mixture layer may be sealed so that the particles do not leak. The water-soluble unit dose product may include a plurality of plies, wherein each ply includes two layers, wherein one layer is a fiber element layer, one layer is a fiber element / particle mixture layer, and a plurality of plies are sealed (e.g., at the edge) together. Sealing may inhibit the leakage of particles and help the unit dose product to maintain its original structure. However, after the water-soluble unit dose product is added to water, the unit dose product dissolves and releases the particles into the washing liquid.

[0246] The fibrous water-soluble unit dose can be in the form of any three-dimensional structure. The fibrous water-soluble unit dose product can be perforated. The product can also be cut or formed into various sizes for different intended uses. For example, the water-soluble unit dose can be square, rounded square, kite-shaped, rectangular, triangular, circular, oval, and mixed forms thereof.

[0247] The fibrous water-soluble unit dose may contain less than 10 ingredients. The water-soluble unit dose may contain 3 to 9 ingredients, such as 4 ingredients, 5 ingredients, 6 ingredients, 7 ingredients or 8 ingredients.

[0248] The fibrous water-soluble unit dose products disclosed herein include water-soluble fiber structures and one or more particles. The fibrous water-soluble fiber structure may include multiple fiber elements, such as multiple filaments. One or more particles, such as one or more particles containing active agents, may be distributed throughout the structure. The fibrous water-soluble unit dose products may include multiple two or more and / or three or more fiber elements, which are entangled or otherwise associated with each other to form a fiber structure and one or more particles, which may be distributed throughout the fiber structure.

[0249] The fibrous water-soluble unit dose product may include a water-soluble fiber structure. The water-soluble fiber structure may include two or more different fiber elements. Non-limiting examples of the differences in fiber elements may be physical differences, such as differences in diameter, length, texture, shape, rigidity, elasticity, etc.; chemical differences such as cross-linking level, solubility, melting point, Tg, active agent, filament forming material, color, active agent content, basis weight, filament forming material content, whether there is any coating on the fiber element, whether it can be biodegraded, whether it is hydrophobic, contact angle, etc.; whether the fiber element loses its physical structure when it is exposed to the expected use conditions; whether the fiber element changes morphology when the fiber element is exposed to the expected use conditions; and the difference in the rate of releasing one or more of its active agents when the fiber element is exposed to the expected use conditions. Two or more fiber elements in the fiber structure may contain different active agents. This may be a situation where different active agents may be incompatible with each other, such as anionic surfactants and cationic polymers. When different fiber elements are used, the resulting structure may show different wetting, absorption and dissolution characteristics.

[0250] Fiber structure

[0251] The fibrous structure includes one or more fibrous elements. The fibrous elements may be associated with each other to form a structure. The fibrous structure may include particles within and / or on the structure. The fibrous structure may be uniform, layered, integral, partitioned, or, if desired, have different active agents defining the various parts described above.

[0252] The fibrous structure may comprise one or more layers, the layers together forming a ply.

[0253] Fiber components

[0254] The fibrous element may be water soluble. The fibrous element may contain one or more filament-forming materials and / or one or more active agents, such as the above-mentioned surfactants. The one or more active agents can be released from the fibrous element, such as when the fibrous element and / or the fibrous structure including the fibrous element is exposed to the conditions of the intended use.

[0255] The fibrous elements may be spun from a filament-forming composition (also referred to as a fibrous element-forming composition) via a suitable spinning process operation, such as meltblowing, spunbonding, electrospinning, and / or spin spinning.

[0256] As used herein, "filament forming composition" and / or "fiber element forming composition" means a composition suitable for preparing fiber elements such as by meltblowing and / or spunbonding. The filament forming composition comprises one or more filament forming materials, which exhibit properties that make them suitable for spinning into fiber elements. The filament forming material may comprise a polymer. In addition to one or more filament forming materials, the filament forming composition may also comprise one or more active agents, such as surfactants. In addition, the filament forming composition may comprise one or more polar solvents (such as water), and before spinning fiber elements (such as filaments from the filament forming composition), one or more filament forming materials (e.g., all) and / or one or more active agents (e.g., all) in the filament forming material and / or the active agent are dissolved and / or dispersed therein.

[0257] The filament formation composition may include two or more different filament formation materials.Therefore, fiber element may be a single component (a kind of filament formation material) and / or a multicomponent, such as a bicomponent.Two or more different filament formation materials are randomly combined to form a fiber element.For purposes of the present disclosure, two or more different filament formation materials may be orderly combined to form a fiber element such as a core-shell bicomponent fiber element, which is considered not to be a random mixture of different filament formation materials.Bicomponent fiber element may be in any form, such as side-by-side, core-shell, island-in-the-sea, etc.

[0258] The fibrous elements may be substantially free of alkyl alkoxylated sulfates. Each fibrous element may contain from about 0%, or about 0.1%, or about 5%, or about 10%, or about 15%, or about 20%, or about 25%, or about 30%, or about 35%, or about 40% to about 0.2%, or to about 1%, or to about 5%, or to about 10%, or to about 15%, or to about 20%, or to about 25%, or to about 30%, or to about 35%, or to about 40%, or to about 50% alkyl alkoxylated sulfates, based on the weight of the dry fibrous element. The amount of alkyl alkoxylated sulfates in each fibrous element is sufficiently small so as not to affect its processing stability and film dissolution. Alkyl alkoxylated sulfates, when dissolved in water, may experience a highly viscous hexagonal phase at a certain concentration range (e.g., 30% to 60% by weight), producing a gel-like substance. Thus, if incorporated in significant amounts into fibrous elements, alkyl alkoxylated sulfates can significantly slow the dissolution of a water-soluble unit dose preparation in water, or worse, result in undissolved solids. Accordingly, most such surfactants are formulated as granules.

[0259] The fiber elements may each comprise at least one filament-forming material and an active agent, preferably a surfactant. The surfactant may have a relatively low hydrophilicity because such surfactants are less likely to form a viscous, gel-like hexagonal phase upon dilution. By using such surfactants in forming the filaments, gel formation during washing may be effectively reduced, which in turn may result in faster dissolution and low or no residue in washing. The surfactant may be selected from, for example, unalkoxylated C6-C 20 Linear or branched alkyl sulfate (AS), C6-C 20 Linear alkylbenzene sulfonate (LAS), and combinations thereof. The surfactant may be C6-C 20 Linear alkylbenzene sulfonate (LAS). LAS surfactants are well known in the art and can be readily obtained by sulfonating commercially available linear alkylbenzenes. Exemplary C6-C 20 Linear alkylbenzene sulfonates include alkali metal, alkaline earth metal or C6-C 20 Ammonium salts of linear alkylbenzenesulfonic acids, such as C 11 -C 18 Linear alkylbenzene sulfonic acid or C 11 -C 14 Sodium, potassium, magnesium and / or ammonium linear alkylbenzene sulfonic acid. 12 Sodium or potassium linear alkylbenzene sulfonic acid, such as C 12 The sodium salt of linear alkylbenzene sulfonic acid, ie, sodium dodecylbenzene sulfonate, can be used as the first surfactant.

[0260] The fibrous element may comprise at least about 5 weight %, and / or at least about 10 weight %, and / or at least about 15 weight %, and / or at least about 20 weight %, and / or less than about 80 weight %, and / or less than about 75 weight %, and / or less than about 65 weight %, and / or less than about 60 weight %, and / or less than about 55 weight %, and / or less than about 50 weight %, and / or less than about 45 weight %, and / or less than about 40 weight %, and / or less than about 35 weight %, and / or less than about 30 weight %, and / or less than about 25 weight % of the long fibers, based on the dry fibrous element and / or dry fibrous structure. The filament forming material and greater than about 20% by weight, and / or at least about 35% by weight, and / or at least about 40% by weight, and / or at least about 45% by weight, and / or at least about 50% by weight, and / or at least about 55% by weight, and / or at least about 60% by weight, and / or at least about 65% by weight, and / or at least about 70% by weight, and / or less than about 95% by weight, and / or less than about 90% by weight, and / or less than about 85% by weight, and / or less than about 80% by weight, and / or less than about 75% by weight of an active agent, preferably a surfactant, based on the weight of the dry fibrous element and / or dry fibrous structure. The fibrous element may contain greater than about 80% of a surfactant based on the weight of the dry fibrous element and / or dry fibrous structure.

[0261] Preferably, each fibrous element can be characterized by a sufficiently high total surfactant content, such as at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70% of the first surfactant based on the weight of the dry fibrous element and / or dry fibrous structure.

[0262] The total content of filament-forming materials present in the fiber elements may be from about 5% to less than about 80% by weight based on the dry fiber elements and / or dry fiber structure, and the total content of surfactants present in the fiber elements may be from greater than about 20% to about 95% by weight based on the dry fiber elements and / or dry fiber structure.

[0263] Typically, a fibrous element is an elongated particle having a length that greatly exceeds an average diameter, such as a length-to-average diameter ratio of at least about 10. The fibrous element may be a filament or a fiber. A filament is relatively longer than a fiber. A filament may have a length greater than or equal to about 5.08 cm (2 inches), and / or greater than or equal to about 7.62 cm (3 inches), and / or greater than or equal to about 10.16 cm (4 inches, and / or greater than or equal to about 15.24 cm (6 inches). A fiber may have a length less than about 5.08 cm (2 inches), and / or less than about 3.81 cm (1.5 inches), and / or less than about 2.54 cm (1 inch).

[0264] One or more long filaments form that material and activating agent can form the weight ratio of the total content of material and activating agent with long filament for about 2.0 or less, and / or about 1.85 or less, and / or less than about 1.7, and / or less than about 1.6, and / or less than about 1.5, and / or less than about 1.3, and / or less than about 1.2, and / or less than about 1, and / or less than about 0.7, and / or less than about 0.5, and / or less than about 0.4, and / or less than about 0.3, and / or greater than about 0.1, and / or greater than about 0.15, and / or greater than about 0.2 amount is present in fiber element. One or more long filaments form that material and activating agent can form the weight ratio of the total content of material and activating agent with long filament for about 0.2 to about 0.7 present in fiber element.

[0265] The fiber element may include about 10% to less than about 80% of filament-forming materials, such as polyvinyl alcohol polymers, starch polymers and / or carboxymethyl cellulose polymers, based on the weight of dry fiber elements and / or dry fiber structures, and active agents such as surfactants greater than about 20% to about 90% based on the weight of dry fiber elements and / or dry fiber structures. The fiber element may also include a plasticizer such as glycerol and / or an additional pH regulator such as citric acid. The fiber element may have a weight ratio of about 2.0 or less of filament-forming materials to active agents. The filament-forming material may be selected from the group consisting of: polyvinyl alcohol, starch, carboxymethyl cellulose, polyethylene oxide and other suitable polymers, especially hydroxyl-containing polymers and derivatives thereof. The weight average molecular weight range of the filament-forming material may be about 100,000 g / mol to about 3,000,000 g / mol. It is believed that within this range, the filament-forming material can provide tensile rheology without elasticity, thereby inhibiting fiber attenuation during fiber manufacturing.

[0266] The one or more active agents may be releasable and / or release when the fibrous elements and / or fibrous structures comprising the fibrous elements are exposed to conditions of intended use.The one or more active agents in the fibrous elements may be selected from the group consisting of surfactants, organic polymeric compounds, and mixtures thereof.

[0267] The fibrous elements may exhibit a diameter of less than about 300 μm, and / or less than about 75 μm, and / or less than about 50 μm, and / or less than about 25 μm, and / or less than about 10 μm, and / or less than about 5 μm, and / or less than about 1 μm. The fibrous elements may exhibit a diameter greater than about 1 μm as measured according to the Diameter Test Method described herein. The diameter of the fibrous elements can be used to control the release rate of one or more active agents present in the fibrous elements and / or the rate of loss and / or change of the physical structure of the fibrous elements.

[0268] The particles may be incorporated into the fibrous water-soluble product as discussed above at a level of about 0.1 g to about 15 g. The type of particles used may be any type compatible with the manufacturing system. One parameter that may contribute to the successful deposition of particles according to this method is the flowability of the particles. The flowability (f p ) can be defined as the ratio of the consolidation stress (cs) to the unrestrained yield strength (ys). p The larger the value, the better the particle flow. p <1 is non-flowing, f p >1 but less than 2 is very cohesive, f p 2 to less than 4 is considered cohesive, f p 4 to less than 10 is considered easy to flow, and f p A value of 10 or greater is considered free flowing. For the above method, f p Particles having values ​​of about 4 or greater are preferred. The flowability of particles can be measured and calculated as discussed below in the Flowability Method.

[0269] The particles can be powders, particles, agglomerates, encapsulates, microcapsules and / or pellets. Many well-known methods in the art can be used to prepare particles, such as spray drying, agglomeration, extrusion, granulation, encapsulation, tableting and combinations thereof. The shape of the particles can be in the following forms: spherical, rod-shaped, plate-shaped, tubular, square, rectangular, disc-shaped, star-shaped, fiber, or have regular or irregular random shapes. The particles can have a D50 particle size of about 100 μm to about 1600 μm.

[0270] The particles may include mixtures of chemically different particles, such as: surfactant particles, including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant strips, surfactant flakes; phosphate particles; zeolite particles; silicate particles, especially sodium silicate particles; carbonate particles, especially sodium carbonate particles; polymer particles, such as carboxylate polymer particles, cellulose polymer particles, starch particles, polyester particles, polyamine particles, terephthalic acid polymer particles, polyethylene glycol particles; aesthetic particles, such as colored strips, needles, lamellar particles and ring particles; enzyme particles, such as protease particles, amylase particles, lipase particles, cellulase particles, mannanase particles, pectate lyase particles, xyloglucanase particles, bleaching enzyme particles and co-particles of any of these enzymes, which enzyme particles may contain sodium sulfate; bleaching agent particles, such as percarbonate particles, especially coated percarbonate particles. Salt particles, such as percarbonate coated with carbonate, sulfate, silicate, borosilicate, or any combination thereof, perborate particles, bleach activator particles such as tetraacetylethylenediamine particles and / or alkyloxybenzenesulfonate particles, bleach catalyst particles such as transition metal catalyst particles, and / or isoquinolinium bleach catalyst particles, preformed peracid particles, especially coated preformed peracid particles; filler particles, such as sulfate particles and chloride particles; clay particles, such as montmorillonite particles and clay and silicone particles; flocculant particles, such as polyethylene oxide particles; wax particles, such as wax agglomerates; silicone particles, brightener particles; dye transfer inhibitor particles; dye fixative particles; perfume particles, such as perfume microcapsules and starch-encapsulated perfume accord particles, and pro-perfume particles, such as Schiff base reaction product particles; hueing dye particles; chelant particles, such as chelant agglomerates; and any combination thereof.

[0271] combination

[0272] Various embodiments relate to:

[0273] 1. A solid detergent composition, comprising:

[0274] At least one component according to one or more of Formula 7 to Formula 12:

[0275]

[0276] in:

[0277] R1 is hydroxyl, C1-C6 carboxyl, straight chain or branched C1-C6 alkyl; straight chain or branched

[0278] a linear C2-C6 alkenyl group; or a linear or branched C2-C6 alkynyl group;

[0279] a is 0 to 5;

[0280] R2 is a fused C1-C6 cycloalkyl, a fused C1-C6 cycloalkoxy or a fused C1-C6

[0281] Cycloalkenyl;

[0282] b is 0 to 4;

[0283] R3 is oxygen or hydroxy; and

[0284] c is 0 to 4,

[0285] and combinations and salts thereof;

[0286]

[0287]

[0288] 2. The solid detergent composition according to 1, wherein at least one component according to Formula 7 is tropolone.

[0289] 3. The solid detergent composition according to any one of 1 or 2, wherein the at least one component according to Formula 7 is hinokitiol.

[0290] 4. A solid detergent composition according to any one of 1 to 3, wherein the pKa of the at least one component is about 8, preferably about 8 or less, more preferably about 7.5 or less, even more preferably from about 5 to about 8, even more preferably from about 5.0 to about 7.5, even more preferably from about 5.0 to about 7.25, or most preferably from about 5.0 to about 7.0.

[0291] 5. A solid detergent composition according to any one of 1 to 4, wherein the calcium binding efficiency of at least one component is less than about 7, preferably from about 2 to about 7.0, from about 2 to about 6.8, from about

[0292] 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

[0293] 2.0 to about 4.5, about 2.0 to about 4.5, about 2.0 to about 4.0, more preferably about 2.5 to about

[0294] 3.5 or about 2.7 to about 3.1.

[0295] 6. A solid detergent composition according to any one of 1 to 5, wherein the iron binding efficiency of the at least one component is greater than about 10.

[0296] 7. A solid detergent composition according to any one of 1 to 6, wherein at least one of the components

[0297] The component is present in an amount from greater than about 0% to about 10% by weight of the solid detergent composition.

[0298] 8. A solid detergent composition according to any one of 1 to 7, further comprising a surfactant, wherein the surfactant comprises an anionic surfactant, a nonionic surfactant or a combination thereof, preferably an anionic surfactant comprises alkylbenzene sulfonate, methyl ester sulfonate, alkyl ether carboxylate, alkyl sulfate, alkyl alkoxylated sulfate or a combination thereof; more preferably alkylbenzene sulfonate.

[0299] 9. The solid detergent composition according to any one of 1 to 8, wherein the solid detergent composition is in the form of granules, beads or fibers.

[0300] 10. A single unit dose detergent comprising the solid detergent composition according to any one of 1 to 9.

[0301] 11. A method for treating stains on fabric, the method comprising:

[0302] The fabric is washed in a wash liquor comprising a solid detergent composition comprising at least one component according to one or more of Formulae 7 to 12:

[0303]

[0304] in:

[0305] R1 is hydroxyl, C1-C6 carboxyl, straight chain or branched C1-C6 alkyl; straight chain or branched

[0306] C2-C6 alkenyl; or a straight-chain or branched C2-C6 alkynyl group;

[0307] a is 0 to 5;

[0308] R2 is a fused C1-C6 cycloalkyl group, a fused C1-C6 cycloalkoxy group or a fused C1-C6 cycloalkenyl group;

[0309] b is 0 to 4;

[0310] R3 is oxygen or hydroxyl; and c is 0 to 4, and combinations and salts thereof;

[0311]

[0312]

[0313] 12. The method according to 11, wherein the at least one component according to formula 7 is tropolone.

[0314] 13. The method according to any one of 11 or 12, wherein the at least one component according to formula 7 is hinokitiol.

[0315] 14. The method according to any one of 11 to 13, wherein the pKa of the at least one component is

[0316] is about 8, preferably about 8 or less, more preferably about 7.5 or less, and even more preferably about 5

[0317] to about 8, even more preferably from about 5.0 to about 7.5, even more preferably from about 5.0 to about 7.25,

[0318] Or most preferably from about 5.0 to about 7.0.

[0319] 15. The method according to any one of 11 to 14, wherein the calcium binding efficiency of the at least one component is 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,

[0320] From about 2.0 to about 4.5, from about 2.0 to about 4.0, more preferably from about 2.5 to about 3.5 or from about 2.7 to about 3.1.

[0321] 16. The method of any one of 11 to 15, wherein the iron binding efficiency of the at least one component is greater than about 10, about 10 to about 20, or about 10.5 to about 14.1, or about 11 to about 12.9.

[0322] 17. The method according to any one of 11 to 16, wherein the at least one component is present in an amount of greater than about 0% to about 10% or about 0.5% to about 10% by weight of the liquid detergent composition.

[0323] 9.5%, or from about 0.5% to about 9.5% by weight, or from about 1.0% to about

[0324] 9.0%, or from about 1.5% to about 8.5% by weight, or from about 2.0% to about

[0325] 8.0%, or from about 2.5% to about 7.5% by weight, or from about 3.0% to about

[0326] 7.0%, or from about 3.5% to about 6.5% by weight, or from about 4.0% to about

[0327] 6.0%, or about 4.5% to about 5.5% by weight, or about 4.0% to about 5.0% by weight.

[0328] 18. The method according to any one of 11 to 17, further comprising:

[0329] The pH was maintained at less than about 10.

[0330] 19. The method according to any one of 11 to 18, wherein the solid detergent composition is delivered to the wash liquor in the form of beads or granules.

[0331] 20. According to the method described in any one of 11 to 19, the solid detergent composition further comprises a surfactant, which includes an anionic surfactant, a nonionic surfactant or a combination thereof, preferably an anionic surfactant includes alkylbenzene sulfonate, methyl ester sulfonate, alkyl ether carboxylate, alkyl sulfate, alkyl alkoxylated sulfate or a combination thereof; more preferably alkylbenzene sulfonate.

[0332] 21. Use of a solid detergent composition comprising at least one component according to one or more of formulas 7 to 12 for treating stains on fabrics,

[0333]

[0334] in:

[0335] R1 is hydroxyl, C1-C6 carboxyl, straight chain or branched C1-C6 alkyl; straight chain or branched

[0336] C2-C6 alkenyl; or a straight-chain or branched C2-C6 alkynyl group;

[0337] a is 0 to 5;

[0338] R2 is a fused C1-C6 cycloalkyl group, a fused C1-C6 cycloalkoxy group or a fused C1-C6 cycloalkenyl group;

[0339] b is 0 to 4;

[0340] R3 is oxygen or hydroxy; and

[0341] c is 0 to 4,

[0342] and combinations and salts thereof;

[0343]

[0344] 22. The use according to 21, wherein the at least one component according to formula 7 is tropolone or a salt thereof.

[0345] 23. The use according to any one of 21 or 22, wherein the at least one component according to formula 7 is hinokitiol or a salt thereof.

[0346] 24. The use according to any one of 21 to 23, wherein the pKa of the at least one component is

[0347] is about 8, preferably about 8 or less, more preferably about 7.5 or less, and even more preferably about 5

[0348] to about 8, even more preferably from about 5.0 to about 7.5, even more preferably from about 5.0 to about 7.25,

[0349] Or most preferably from about 5.0 to about 7.0.

[0350] 25. The use according to any one of 21 to 24, wherein the calcium binding efficiency of the at least one component is 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,

[0351] From about 2.0 to about 4.5, from about 2.0 to about 4.0, more preferably from about 2.5 to about 3.5 or from about 2.7 to about 3.1.

[0352] 26. The use according to any one of 21 to 25, wherein the iron binding efficiency of the at least one component is greater than about 10, about 10 to about 20, or about 10.5 to about 14.1, or about 11 to about 12.9.

[0353] 27. The use according to any one of 21 to 26, wherein the at least one component is present in an amount greater than about 0% to about 10% or about 0.5% to about 10% by weight of the liquid detergent composition.

[0354] 9.5%, or from about 0.5% to about 9.5% by weight, or from about 1.0% to about

[0355] 9.0%, or from about 1.5% to about 8.5% by weight, or from about 2.0% to about

[0356] 8.0%, or from about 2.5% to about 7.5% by weight, or from about 3.0% to about

[0357] 7.0%, or from about 3.5% to about 6.5% by weight, or from about 4.0% to about

[0358] 6.0%, or about 4.5% to about 5.5% by weight, or about 4.0% to about 5.0% by weight.

[0359] 28. The use according to any one of 21 to 27, wherein the detergent composition further comprises a surfactant, which comprises an anionic surfactant, a nonionic surfactant or a combination thereof, preferably an anionic surfactant comprises alkylbenzene sulfonate, methyl ester sulfonate, alkyl ether carboxylate, alkyl sulfate, alkyl alkoxylated sulfate or a combination thereof; more preferably alkylbenzene sulfonate.

[0360] 29. The use according to any one of 21 to 28, wherein the solid detergent composition is in the form of granules or beads.

[0361] 30. The use according to any one of 21 to 29, wherein a single unit dose comprises the solid detergent composition.

[0362] Example

[0363] The following examples are presented to provide a person of ordinary skill in the art with a complete disclosure and description of how to implement the method, how to prepare and how to use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some errors and deviations should be considered. The purpose of the following examples is not to limit the scope of the various embodiments, but rather to provide examples that illustrate specific embodiments only.

[0364] Decontamination Index Calculation Method

[0365] Image analysis can be used to compare each stain with an unstained fabric control. Software can be used to convert the captured images into standard chromaticity values, and these are compared with standards based on the commonly used Macbeth color reproduction chart, and chromaticity values ​​(stain levels) are assigned to each stain. The CIELAB color space, also known as L*a*b*, is a color space defined by the International Commission on Illumination (abbreviated as CIE) in 1976. It represents color as three values: L* for perceived brightness and a* and b* for four unique colors of human vision: red, green, blue and yellow. The brightness value L* defines black as 0 and white as 100. The a* axis is relative to the green-magenta opponent color, with negative values ​​toward green and positive values ​​toward magenta. The b* axis represents the blue-yellow opponent, with negative numbers toward blue and positive numbers toward yellow. In the following examples, the L*a*b* values ​​of various fabrics are analyzed using commercially available image analysis software. The SRI value is then calculated from the L*a*b* values ​​using the formula shown. The higher the SRI, the better the stain removal effect.

[0366]

[0367] in,

[0368]

[0369] Subscript 'b' indicates the data of stains before washing

[0370] Subscript 'a' indicates the stain data after washing

[0371] Subscript 'c' indicates data for undyed fabric

[0372] Therefore, L*a*b* values ​​were obtained from undyed fabric, dyed fabric before washing and dyed fabric after washing.

[0373] Example 1: Composition for use in dry laundry for stain removal benefits

[0374] Four powder compositions were prepared and tested as detailed below. The composition of each is provided below. Table 2A provides the amount of a given active ingredient in the wash solution, expressed in ppm. Table 2B provides the amount in the composition in wt %.

[0375]

[0376]

[0377]

[0378] As detailed in Table 3 below, the stain removal ability of the treatment composition in the washing process was tested using the following method. Each composition was added separately to the tank of the oscillating dirt washing instrument. The volume of each tank was 1L. The washing temperature was set to 27°C. Throughout the process, 7gpg water was used. The product was stirred for 1 minute (300rpm), and then fabrics (two internal repetitions of each stain, and additional knitted cotton ballast to bring the total fabric weight to 60g) were added. Once the fabrics were added, the washing solution was stirred for 17 minutes (208rpm). The washing solution was then discharged, and the fabrics were subjected to a 5-minute rinse step, then drained and spin-dried. The process was repeated three more times to obtain a total of four external repetitions. After washing, the stained fabrics were dried in a tumble dryer for 30 minutes.

[0379]

[0380] Table 4 summarizes the stain removal tests for each treatment.

[0381]

[0382] As can be seen in Table 4, Composition 1C and Composition 1D containing tropolone or hinokitiol showed significantly improved stain removal relative to the no-chelating agent reference, which was not observed with HEDP.

[0383] Example 2: Decontamination Beads

[0384] Four lozenge compositions (compositions C2-1 to C2-4) and a unit dose detergent composition (composition C2-5) were prepared and tested as described in detail below. The composition of each is provided below. Table 5A provides the amount of a given active ingredient in the washing solution, expressed in ppm. Table 5B provides the amount in the composition in % by weight.

[0385] The lozenges were prepared according to the following process. Polyethylene glycol 8000 was melted in an oven at 70°C overnight. The molten polyethylene glycol was weighed into a rapid mixer cup. The flavor and chelating agent were immediately weighed into the rapid mixer cup with the molten polyethylene glycol. The rapid mixer cup was placed in a rapid mixer and mixed at 3,500 rpm for 1 minute until uniform. The lozenges were formed by pouring the molten mixture into a siliconized rubber mold after rapid mixing and spreading using a 10-inch palette knife. The melt was then allowed to cool at room temperature to form lozenges.

[0386]

[0387]

[0388]

[0389]

[0390] As detailed in Table 6 below, the following method was used to test the stain removal ability of the treatment compositions during the wash process. Each composition was added individually to the tank of the oscillating detergent. The volume of each tank was 1 L. The wash temperature was set to 35°C. Throughout the process, 21 gpg of water was used. The product was stirred for 1 minute (400 rpm) and then fabrics (two internal replicates of each stain, 13×6 cm 2 SBL2004 (supplied by WFK) and another 6cm 2 knitted cotton ballast squares to bring the total fabric weight to 60 g). Once the fabric is added, the wash solution is stirred for 30 minutes (300 rpm). The wash solution is then drained and the fabric is subjected to two 5 minute rinse steps, then drained and spin dried. The process is repeated three more times, resulting in a total of four external repeats. After washing, the stained fabric is dried in a tumble dryer for 30 minutes.

[0391]

[0392] Table 7 summarizes the stain removal tests for each treatment.

[0393]

[0394] As can be seen in Table 7, Examples 2C and 2D containing tropolone and hinokitiol showed improved stain removal on tea stains (relative to no chelating agent (2A) or HEDP (2B)) while avoiding the negative effects of HEDP on distinguishing sebum from bacon grease.

[0395] Free-Flowing Solid Granular Laundry Detergent Composition Example:

[0396]

[0397]

[0398] Further definitions and cross references

[0399] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact numerical values ​​cited. Instead, unless otherwise indicated, each such dimension is intended to represent the stated value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0400] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art to any of the present invention disclosed or claimed herein, or an admission that it, by itself or in combination with any one or more of the references, proposes, suggests, or discloses any such invention. In addition, to the extent that any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this invention shall govern.

[0401] Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that many other changes and modifications may be made without departing from the spirit and scope of the present invention. Therefore, it is intended that all such changes and modifications within the scope of the present invention be covered in the appended claims.

Claims

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

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

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

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

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

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

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

9. A solid detergent composition according to any preceding claim, wherein the solid detergent composition is in the form of granules or beads.

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

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

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

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

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

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