WO2024100226A1

WO2024100226A1 - Cleaning composition

Info

Publication number: WO2024100226A1
Application number: PCT/EP2023/081368
Authority: WO
Inventors: Sorel MURESAN; Martin Heus; Paulus Johannes Cornelis VAN HAEREN; Riande Irmgard GARDENIER-DEKKER; Stuart Peter Robert Holt
Original assignee: Nouryon Chemicals International B.V.
Priority date: 2022-11-11
Filing date: 2023-11-09
Publication date: 2024-05-16

Abstract

A cleaning composition includes: A. a chelating agent present in an amount of from about 0.1 to about 25 weight percent actives based on a total weight of the cleaning composition; B. a biopolymer chosen from starch polycarboxylates, carboxymethyl celluloses, and combinations thereof and present in an amount of from about 0.1 to about 15 weight percent actives based on a total weight of the cleaning composition; C. a surfactant present in an amount of from about 1 to about 30 weight percent actives based on a total weight of the cleaning composition; D. an enzyme optionally present in an amount of from about 0.2 to about 4 weight percent actives based on a total weight of the cleaning composition; and E. a phosphorous-containing compound; wherein the cleaning composition has a phosphorous content of less than about 1 weight percent actives based on a total weight of the cleaning composition.

Description

CLEANING COMPOSITION

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63/383,324, filed November 11, 2022, which is expressly incorporated herein by reference in its entirety.

TECHNICAL FIELD

[0002] The present disclosure generally relates to cleaning compositions that include a chelating agent and a biopolymer. More specifically, this disclosure relates to cleaning compositions that include low phosphorous contents.

BACKGROUND

[0003] Phosphonates are a class of compounds often used in consumer goods for various purposes, including as chelating agents in detergents and cleaning products, as scale inhibitors in water treatment, and as corrosion inhibitors in various industrial applications. The functionality of phosphonates is generally threefold. First, phosphonates function to chelate (transition) metal ions. Second, phosphonates act as crystal growth inhibitors. Third, phosphonates act as anti-redeposition aids.

[0004] Phosphonates tend to be used in low quantities in many formulations. They tend to have desirable cost efficiency and tend to be stable such that phosphonates are a part of the toolbox of formulators in the art.

[0005] While phosphonates have proven effective for these purposes, there are several reasons why it is important to consider replacing them in consumer goods. Phosphonates can persist in the environment and may not easily biodegrade. When they enter water bodies, they can contribute to algal blooms and oxygen depletion. Because of these drawbacks, many governments are regulating phosphonates.

[0006] Accordingly, there remains an opportunity to develop sustainable products including eco- friendly alternatives to phosphonates. Furthermore, other desirable features and characteristics of the present disclosure will become apparent from the subsequent detailed description of the disclosure and the appended claims, taken in conjunction with the accompanying drawings and this background of the disclosure. BRIEF SUMMARY

[0007] This disclosure provides a cleaning composition comprising:

A. a chelating agent present in an amount of from about 0.1 to about 25 weight percent actives based on a total weight of the cleaning composition;

B. a biopolymer chosen from starch polycarboxylates, carboxymethyl celluloses, and combinations thereof and present in an amount of from about 0.1 to about 15 weight percent actives based on a total weight of the cleaning composition;

C. a surfactant present in an amount of from about 1 to about 30 weight percent actives based on a total weight of the cleaning composition;

D. an enzyme optionally present in an amount of from about 0.2 to about 4 weight percent actives based on a total weight of the cleaning composition; and

E. a phosphorous-containing compound; wherein the cleaning composition has a phosphorous content of less than about 1 weight percent actives based on a total weight of the cleaning composition.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The present disclosure will hereinafter be described in conjunction with the following drawing figures, wherein like numerals denote like elements, and

[0009] FIG. 1 is a bar graph of cleaning performance of various laundry compositions evaluated in the examples;

[0010] FIG.2 is also a bar graph of cleaning performance of various laundry compositions evaluated in the examples;

[0011] FIG.3 is a bar graph of cleaning performance of various automatic dishwashing compositions evaluated in the examples;

[0012] FIG. 4 is a photograph of various automatic dishwashing compositions evaluated in the examples showing secondary washing performance (e.g. filming and spotting);

[0013] FIG. 5 is a photograph of various automatic dishwashing compositions evaluated in the examples showing secondary washing performance (e.g. filming and spotting);

[0014] FIG. 6 is a photograph of various automatic dishwashing compositions evaluated in the examples showing secondary washing performance (e.g. filming and spotting) along with text descriptors describing that performance; [0015] FIG. 7 is a photograph of various automatic dishwashing compositions evaluated in the examples showing secondary washing performance (e.g. filming and spotting) along with text descriptors describing that performance;

[0016] FIG. 8 is a bar graph of cleaning performance of various automatic dishwashing compositions evaluated in the examples;

[0017] FIG. 9 is a photograph of various automatic dishwashing compositions evaluated in the examples showing secondary washing performance (e.g. filming and spotting); and

[0018] FIG. 10 is a photograph of various automatic dishwashing compositions evaluated in the examples showing secondary washing performance (e.g. filming and spotting).

DETAILED DESCRIPTION

[0019] The following detailed description is merely exemplary in nature and is not intended to limit the current composition. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.

[0020] Embodiments of the present disclosure are generally directed to cleaning compounds and polymers, compositions including the same, and methods for forming the same. For the sake of brevity, conventional techniques related to making such compounds and polymers and such compositions may not be described in detail herein. Moreover, the various tasks and process steps described herein may be incorporated into a more comprehensive procedure or process having additional steps or functionality not described in detail herein. In particular, various steps in the manufacture of compounds and polymers and associated compositions are well-known and so, in the interest of brevity, many conventional steps will only be described briefly herein or will be omitted entirely without providing the well-known process details.

[0021] In this disclosure, the terminology “about” can describe values ± 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%, in various embodiments. Moreover, it is contemplated that, in various non-limiting embodiments, it is to be appreciated that all numerical values as provided herein, save for the actual examples, are approximate values with endpoints or particular values intended to be read as “about” or “approximately” the value as recited. It is also contemplated that all isomers and chiral options for each compound described herein are hereby expressly contemplated for use herein in various non-limiting embodiments. [0022] Throughout this disclosure, the terminology percent "actives" is well recognized in the art and means the percent amount of active or actual compound or molecule present as compared to, for example, a total weight of a diluted solution of a solvent and such a compound. Some compounds, such as a solvent, are not described relative to a percent actives because it is well known to be approximately 100% actives. Any one or more of the values described herein may be alternatively described as percent actives as would be understood by the skilled person.

[0023] In various embodiments, the terminology “free of’ describes embodiments that include less than about 5, 4, 3, 2, 1, 0.5, or 0.1, weight percent (or weight percent actives) of the compound or element at issue using an appropriate weight basis as would be understood by one of skill in the art. In other embodiments, the terminology “free of’ describes embodiments that have zero weight percent of the compound or element at issue.

[0024] The terminology “consists essentially of’ may describe various non-limiting embodiments that are free of one or more optional compounds described herein and/or free of one or more compounds, polymers, surfactants, additives, solvents, etc.

[0025] It is to be understood that the subscripts of compounds and polymers are typically described as average values because the synthesis of compounds and polymers typically produces a distribution of various individual molecules.

[0026] The compounds, polymers and compositions disclosed herein may suitably comprise, consist of, or consist essentially of the components, elements, and process delineations described herein. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein.

Cleaning Composition

[0027] This disclosure provides a cleaning composition, hereinafter described as the composition. The cleaning composition is not particularly limited and may be a cleaning composition designed for any industry including, but not limited to, all-purpose cleaners, glass cleaners, kitchen cleaners, bathroom cleaners, disinfectants, floor cleaners, carpet cleaners, oven and grill cleaners, metal cleaners, toilet bowl cleaners, mold and mildew removers, stainless steel cleaners, specialty cleaners such as those used for removing rust, limescale, graffiti, or adhesive residues, and the like. In various embodiments, the cleaning composition can be further described as useful for household cleaning, industrial cleaning, all-purpose cleaning, car washing, acidic and caustic cleaning, deck and floor cleaning, hard surface cleaning, metal cleaning, food & beverage cleaning, automated and manual dishwash, laundry detergents and the like. In one embodiment, the composition is an automatic dishwashing composition. In another embodiment, the composition is a laundry composition.

[0028] The composition includes a (A) chelating agent, a (B) biopolymer, a (C) surfactant, a (D) optional enzyme, and a (E) phosphorous-containing compound. The cleaning composition may further include, or be free of, (F) water, (G) solvents, (H) additives, etc.

[0029] In various embodiments, the cleaning composition is, includes, consists essentially of, or consists of (A)-(C) and (E).

[0030] In various embodiments, the cleaning composition is, includes, consists essentially of, or consists of (A)-(E).

[0031] In other embodiments, the cleaning composition is, includes, consists essentially of, or consists of (A)-(F).

[0032] In other embodiments, the cleaning composition is, includes, consists essentially of, or consists of (A)-(G).

[0033] In other embodiments, the cleaning composition is, includes, consists essentially of, or consists of (A)-(H).

[0034] It is contemplated that any one or more of (D), (F), (G), and (H) may be used with, or in the absence of, any one or more of (F), (G), and (H), respectively. For example, the composition may be free of, or include less than 5, 4, 3, 2, 1, 0.5, or 0.1, weight percent actives of one or more of (F), (G), and/or (H), each based on a total weight of the composition.

(A) Chelating Agent

[0035] The composition includes the (A) chelating agent. The chelating agent is not particularly limited and may be any known in the art.

[0036] In one embodiment, the chelating agent is an aminocarboxylate chelate. In other embodiments, the chelating agent is chosen from methylglycinediacetic acid (MGDA), N,N- dicarboxymethyl glutamic acid (GEDA), N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraproprionic acid triethylenetetraaminehexaacetic acid (TTHA), tetracetyl ethylene diamine (TAED), iminodisuccinic acid (IDS), ethanol diglycine (EDG), the respective alkali metal, ammonium and substituted ammonium salts thereof, and combinations thereof. It is contemplated that any one of the above may be used with, or in the absence of, any one or more of the others described above. [0037] In another embodiment, the chelating agent is chosen from EDTA, GLDA, MGDA, salts thereof, and combinations thereof. In a further embodiment, the chelating agent is chosen from methylglycinediacetic acid (MGDA), N,N-dicarboxymethyl glutamic acid (GLDA), and combinations thereof. In further embodiment, the chelating agent is chosen from methylglycinediacetic acid (MGDA), N,N-dicarboxymethyl glutamic acid (GLDA), ethylenediaminetetraacetic acid (EDTA), and combinations thereof. Lor example, the chelating agent may be GLDA. In another embodiment, the chelating agent is MGDA. In another embodiment, the chelating agent is EDTA. It is contemplated that any one of the above may be used with, or in the absence of, any one or more of the others described above.

[0038] In another embodiment, the chelating agent is a non-aminocarboxylate chelate and may include carboxylate functionality but not a nitrogen atom. In one embodiment, the chelating agent is a divalent or higher valency carboxylic acid. In another embodiment, the chelating agent is chosen from citric acid, isocitric acid, 2,3 hydroxycitric acid, tricarballylic acid, ethanetricarboxylic acid (HETA), aconitic acid, succinic acid, maleic acid, fumaric acid, oxaloacetic acid, ketoglutaric acid, butanetetracarboxylic acid, polycarboxylic acid, the respective alkali metal, ammonium and substituted ammonium salts thereof, and combinations thereof. In a further embodiment, the chelating agent is chosen from citric acid, salts thereof, and combinations thereof. It is contemplated that any one of the above may be used with, or in the absence of, any one or more of the others described above.

[0039] The chelating agent is typically present in the composition in an amount of from about 0.1 to about 30, about 0.1 to about 25, about 0.1 to about 20, about 0.1 to about 15, about 0.1 to about 10, about 0.1 to about 5, or about 0.1 to about 1, weight percent actives based on a total weight of the cleaning composition. In various embodiments, the amount is from about 2 to about 24, about 3 to about 23, about 4 to about 22, about 5 to about 21, about 6 to about 20, about 7 to about 19, about 8 to about 18, about 9 to about 17, about 10 to about 16, about 11 to about 15, about 12 to about 14, or about 12 to about 13, weight percent actives based on a total weight of the cleaning composition. In other embodiments, the amount is from about 15 to about 20, about 16 to about 19, or about 17 to about 18, weight percent actives based on a total weight of the cleaning composition. In other embodiments, the amount is from about 1 to about 5, about 2 to about 4, or about 2 to about 3, weight percent actives based on a total weight of the cleaning composition. [0040] In other embodiments, the amount is from about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, or about 0.5 to about 0.6, weight percent actives based on a total weight of the cleaning composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0041] In one embodiment, the composition is further described as an automatic dishwashing composition and the chelating agent is present in an amount of from about 15 to about 20, about 16 to about 19, or about 17 to about 18, weight percent actives based on a total weight of the composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0042] In another embodiment, the composition is further described as a laundry composition and the chelating agent is present in an amount of from about 1 to about 5, about 2 to about 4, or about 2 to about 3, weight percent actives based on a total weight of the composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0043] In some embodiments, the composition does not include, or is substantially free of, a hygroscopic chelant, such as iron and/or manganese chelants, diethylenetriamine pentaacetate, diethylene triamine penta(methyl phosphonic acid), ethylenediamine-N,N'-disuccinic acid, ethylenediamine tetraacetate, ethylenediamine tetra(methylene phosphonic acid), hydroxyethane di(methylene phosphonic acid), 1-hydroxy ethanedipho sphonic acid and salts thereof, N,N- dicarboxymethyl-2-aminopentane- 1,5-dioic acid and salts thereof, and 2-phosphonobutane- 1,2,4- tricarboxylic acid and salts thereof.

(B) Biopolymer

[0044] The composition also includes the (B) biopolymer. The biopolymer may be chosen from starch polycarboxylates, carboxymethyl celluloses, and combinations thereof. Alternatively, the biopolymer may be chosen from starch polycarboxylates, a cellulose, and combinations thereof. In one embodiment, the biopolymer is a starch poly carboxy late. In another embodiment, the biopolymer is a carboxymethyl cellulose (CMC) or a substituted cellulose. In another embodiment, the biopolymer includes a combination of one or more starch polycarboxylates with one or more carboxymethyl celluloses or substituted celluloses.

[0045] In various embodiments, the biopolymer is present in an amount of from about 0.1 to about 15, about 2 to about 14, about 3 to about 13, about 4 to about 12, about 5 to about 11, about 6 to about 10, about 7 to about 9, or about 8 to about 9, weight percent actives based on a total weight of the cleaning composition. In other embodiments, the biopolymer is present in an amount of from about 8 to about 12, about 9 to about 11, or about 9 to about 10, weight percent actives based on a total weight of the composition. In other embodiments, the biopolymer is present in an amount of less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1, weight percent actives based on a total weight of the composition. Alternatively, the biopolymer may be present in an amount of greater than zero up to about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, weight percent actives based on a total weight of the composition. In other embodiments, the biopolymer may be present in an amount of from about 4 to about 6, about 4 to about 5, or about 5 to about 6, weight percent actives based on a total weight of the composition. In other embodiments, the biopolymer is present in an amount of from about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, or about 0.5 to about 0.6, weight percent actives based on a total weight of the composition. In various nonlimiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

Starch Polycarboxylate

[0046] The starch polycarboxylates can be produced by using hydroxyl-containing naturally derived materials as chain transfer agents during production. The hydroxyl containing naturally derived materials range from small molecules such as glycerol, citric acid, lactic acid, tartaric acid, gluconic acid, glucoheptonic acid, monosaccharides and disaccharides such as sugars, to larger molecules such as oligosaccharides and polysaccharides (e.g., maltodextrins and starches). Examples of these include sucrose, fructose, maltose, glucose, and saccharose, as well as reaction products of saccharides such as mannitol, sorbitol and so forth. The chain transfer agents include oxidatively, hydrolytically or enzymatically degraded monosaccharides, oligosaccharides and polysaccharides, as well as chemically modified monosaccharides, oligosaccharides and polysaccharides. Such chemically modified derivatives include carboxylates, sulfonates, phosphates, phosphonates, aldehydes, silanes, alkyl glycosides, alkyl-hydroxy alkyls, carboxyalkyl ethers and other derivatives. [0047] Polysaccharides useful herein can be derived from plant, animal and microbial sources. Examples of such polysaccharides include starch, cellulose, gums (e.g., gum arabic, guar and xanthan), alginates, pectin and gellan. Starches include those derived from maize and conventional hybrids of maize, such as waxy maize and high amylose (greater than 40% amylose) maize, as well as other starches such as potato, tapioca, wheat, rice, pea, sago, oat, barley, rye, and amaranth, including conventional hybrids or genetically engineered materials.

[0048] Also included are hemicellulose or plant cell wall polysaccharides such as D-xylans. Examples of plant cell wall polysaccharides include arabino-xylans such as corn fiber gum, a component of corn fiber. The hydroxyl groups of the polysaccharides provide sites for chain transfer during the polymerization process. The higher the number of secondary and tertiary hydroxyl groups in the molecule the more effective it will be as chain transfer agent.

[0049] Other polysaccharides useful as chain transfer agents include maltodextrins, which are polymers having D-glucose units linked primarily by a- 1,4 bonds and have a dextrose equivalent (‘DE’) of less than about 20. Maltodextrins are available as a white powder or concentrated solution and are prepared by the partial hydrolysis of starch with acid and/or enzymes. In one aspect, the chain transfer agents are glycerol, citric acid, maltodextrins and/or low molecular weight oxidized starches. Useful chain transfer agents have molecular weights of less than about 20,000. In another aspect, the chain transfer agents have molecular weights of less than about 2000. In even another aspect, chain transfer agents a have molecular weights of less than 1000. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0050] Polysaccharides can be modified or derivatized by etherification (e.g., via treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyltrimethylammonium chloride), esterification (e.g., via reaction with acetic anhydride, octenyl succinic anhydride (‘OSA’)), acid hydrolysis, dextrinization, oxidation or enzyme treatment (e.g., starch modified with a-amylase, 0-amylase, pullanase, isoamylase or glucoamylase), or various combinations of these treatments.

[0051] The hydroxyl-containing naturally derived chain transfer agents can be used in amounts of from about 0.1 to about 75 weight % based on total weight of the polymer. In one aspect, the range is from about 1 to about 50 weight % of chain transfer agents based on total weight of the polymer. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0052] In one embodiment, the starch polycarboxylates are prepared from at least one hydrophilic acid monomer as the synthetic constituent. Examples of such hydrophilic acid monomers include but are not limited to acrylic acid, methacrylic acid, ethacrylic acid, a-chloro- acrylic acid, a-cyano acrylic acid, 0-methyl-acrylic acid (crotonic acid), a-phenyl acrylic acid, 0- acryloxy propionic acid, sorbic acid, a-chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, 0-styryl acrylic acid (l-carboxy-4-phenyl butadiene- 1,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, 2-acryloxypropionic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodium methallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid and maleic acid. Moieties such as maleic anhydride or acrylamide that can be derivatized to an acid containing group can be used. Combinations of acid-containing hydrophilic monomers can also be used. In one aspect the acid-containing hydrophilic monomer is acrylic acid, maleic acid, methacrylic acid,

2-acrylamido-2-methyl propane sulfonic acid or mixtures thereof.

[0053] In addition to the hydrophilic monomers described above, hydrophobic monomers can also be used as a synthetic constituent. These hydrophobic monomers include, for example, ethylenically unsaturated monomers with saturated or unsaturated alkyl, hydroxyalkyl, alkylalkoxy groups, arylalkoxy, alkarylalkoxy, aryl and aryl-alkyl groups, alkyl sulfonate, aryl sulfonate, siloxane and combinations thereof. Examples of hydrophobic monomers include styrene, a-methyl styrene, methyl methacrylate, methyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl acrylamide, octyl acrylamide, lauryl acrylamide, stearyl acrylamide, behenyl acrylamide, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 1 -vinyl naphthalene, 2-vinyl naphthalene,

3-methyl styrene, 4-propyl styrene, t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2- ethyl-4-benzyl styrene, and 4-(phenyl butyl) styrene. Combinations of hydrophobic monomers can also be used.

[0054] The polymerization process can be a solution or suspension process. The process involves polymerization using free radical initiators with one or more of the above hydrophilic and/or hydrophobic monomers, and the hydroxyl containing natural products used as chain transfer agents or chain stoppers. These chain transfer agents can be added either at the beginning of the reaction or during reaction as the monomer(s) is (are) added.

[0055] One advantage of this system is that it makes use of typical free radical initiators. Unlike grafting systems, special redox systems such as Ce(IV) salts are not required. Instead, easy-to-use thermally activated initiators such as sodium persulfate can be used. One skilled in the art will recognize that most initiating systems are applicable here.

[0056] A high degree of chain transfer can lead to crosslinking and formation of an insoluble gel. In one embodiment, this can be avoided by ensuring that monomer and initiator are fed over the same approximate period of time. If initiator feed lasts much longer than monomer feed, a crosslinked gel can form, particularly when oligopolysaccharides and polysaccharides (those having a molecular weight greater than about 1000) are used as the chain transfer agent.

[0057] In some embodiments, the reaction product forms a hybrid gel during manufacture of these starch polycarboxylates. This is especially true if the synthetic monomer used is extremely reactive (e.g., acrylic acid reacted at low pH (protonated form)) or if the natural chain transfer agent has a molecular weight of greater than about 1000. A crosslinked gel starts to form after the monomer feed has ended and while the rest of the initiator is being fed in. This is undesirable in most cases, since the gel product cannot be diluted in water and therefore cannot be used in the applications described below. The exception to this is in the manufacture of super absorbents, rheology modifiers and gels used to treat wells in the oil field industry.

[0058] If an undesirable gel starts to form during the process due to a reactive monomer, it can be eliminated in a number of ways. This includes reducing monomer reactivity by neutralizing the monomer. Sodium acrylate is far less reactive than acrylic acid and therefore does not form gels that acrylic acid may form. In another embodiment, additional chain transfer agents like thiols, sodium hypophosphite and alcohols can also be used. Thiols and alcohols are particularly useful in controlling molecular weight and preventing the formation of crosslinked gels. Finally, these gels can be eliminated by shortening the initiator feeds so that the initiator and monomer feeds are pumped over the same period of time.

[0059] Stabilization of aqueous systems that include scale-forming salts and inorganic particulates involves a variety of mechanisms. Inhibition is one conventional mechanism for eliminating the deleterious effect of scale-forming salts. In inhibition, synthetic polymer(s) are added that increase the solubility of the scale-forming salt in the aqueous system. [0060] Another stabilization mechanism is the dispersion of precipitated salt crystals. Synthetic polymers having carboxylic acid groups function as good dispersants for precipitated salts such as calcium carbonates. In this mechanism, the crystals stay dispersed rather than dissolving in the aqueous solution.

[0061] A third stabilization mechanism involves interference and distortion of the crystal structure of the scale by the polymer, thereby making the scale less adherent to surfaces, other forming crystals and/or existing particulates.

[0062] In one aspect, the number average molecular weight of the starch polycarboxylate is between about 1000 and about 100,000. In another aspect, the number average molecular weight of the polymer is between about 2000 and about 25,000. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

Cellulose

[0063] In various embodiments, the biopolymer includes a cellulose or a substituted cellulose. As used herein, the term "celluloses" includes natural celluloses and synthetic celluloses. Celluloses can be extracted from plants or produced by microorganisms and sea creatures, like tunicates. The cellulose may be further defined as a substituted carboxymethyl cellulose.

[0064] In various embodiments, the substituted cellulose comprises a cellulose backbone consisting essentially of glucose units. The degree of substitution, DS, of the substituted cellulose is typically of from about 0.1 to about 1.5, e.g. about 0.2 to about 1.4, about 0.3 to about 1.3, about 0.4 to about 1.2, about 0.5 to about 1.1, about 0.6 to about 1, about 0.7 to about 0.9, or about 0.8 to about 0.9. The sum of the degree of substitution and the degree of blockiness, DS+DB, of the substituted cellulose may be of at least 1. The DB+2DS-DS² of the substituted cellulose may be of at least 1.10. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0065] It is contemplated that the substituted cellulose may be substituted with identical or different substituents. In various embodiments, the substituted cellulose comprises unsubstituted glucose units. Unsubstituted glucose units are glucose units having all their hydroxyl groups remaining unsubstituted. In the substituted cellulose, the weight ratio of unsubstituted glucose units to the total number of glucose units may be from about 0.01 to about 0.99. In various non- limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0066] Typically, the substituted cellulose comprises substituted glucose units. Substituted glucose units are glucose units having at least one of their hydroxyl groups being substituted. In the substituted cellulose, the weight ratio of substituted glucose units to the total number of glucose units is typically of from about 0.01 to about 0.99. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0067] The cellulose has a backbone that is typically substantially linear. By substantially linear it is to be understood that at least about 97%, for example at least about 99% (by weight), or all the glucose units of the polymer are in the main chain of the cellulose backbone. In various nonlimiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0068] Celluloses have a substantially P-1,4 linked backbone. By substantially P-1,4 linked backbone it is to be understood that at least about 97%, for example at least about 99% (by weight), or all the glucose units of the polymer are bounded with P-1,4 linkage. When present, the remaining glucose units of the cellulose backbone may be bounded in a variety of ways, such as a- or P-and 1-2, 1-3, 1-4, 1-6 or 2-3 linkages and mixtures thereof. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0069] Typically, the cellulose backbone consists essentially of glucose units. Consisting essentially of glucose units should be understood as comprising more than about 95% or about 97%, for example more than about 99%, or even comprising about 100% by weight of glucose units. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0070] In various embodiments, the substituted cellulose comprises at least one glucose unit of its backbone which is carboxymethyl substituted. The substituent can be a carboxymethyl group.

[0071] In other embodiments, the substituted cellulose of the invention has a DS of about 0.01 to about 0.99. The skilled person appreciates that the term "degree of substitution" (or DS) refers to average degree of substitution of the functional groups on the cellulose units of the cellulose backbone. Thus, as each of the glucose unit of the cellulose backbone comprises three hydroxyl groups, the maximum degree of substitution of the substituted cellulose is 3. DS values do not generally relate to the uniformity of substitution of chemical groups along the cellulose backbone and are not related to the molecular weight of the cellulose backbone. The degree of substitution of the substituted cellulose is typically of at least about 0.02 or about 0.05, in particular of at least about 0.10 or about 0.20 or even about 0.30. Typically, the degree of substitution of the cellulose backbone is from about 0.50 to about 0.95, in particular from about 0.55 to about 0.90, or from about 0.60 to about 0.85, or even from about 0.70 to about 0.80. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0072] The methods to measure the DS may vary as a function of the substituent. The skilled person knows or may determine how to measure the degree of substitution of a given substituted cellulose. By way of example, a method to measure the DS of a carboxymethylcellulose is disclosed thereafter.

[0073] For example, DS can be determined by igniting CMC to ash at high temperature (650°C) for 45 minutes in order to remove all the organic material. The remaining inorganic ashes can then be dissolved in distilled water and methyl red added. The sample can then be titrated with 0.1M hydrochloric acid until the solution turned pink. The DS can be calculated from the amount of titrated acid (b ml) and the amount of CMC (G g) using the formula:

DS=0.162*0. l*b/G/l-(0.08*0. l*b/G.

[0074] Alternatively, the DS of a substituted cellulose may be measured by conductimetry or 13C NMR. Experimental protocols for both approaches are given in D. Capitani et al, Carbohydrate Polymers, 2000, v42, pp283-286, which is expressly incorporated herein by reference in various non-limiting embodiments.

[0075] In still other embodiments, the substituted cellulose can have a degree of blockiness (DB) such as either DB+DS is at least of about 1 or DB+2DS-DS² is of at least about 1.20. The skilled person appreciates that term "degree of blockiness" (DB) refers to the extent to which substituted (or unsubstituted) glucose units are clustered on the cellulose backbone. Substituted celluloses having a lower DB may be described as having a more even distribution of the unsubstituted glucose units along the cellulose backbone. Substituted celluloses having a higher DB may be described as having more clustering of the unsubstituted glucose units along the cellulose backbone. More specifically, in a substituted cellulose comprising substituted and unsubstituted glucose units, the DB of the substituted cellulose is equal to B/(A+B), with A referring to the number of unsubstituted glucose units directly linked to at least one substituted glucose units, and B refers the number of unsubstituted glucose units not directly linked to a substituted glucose unit (i.e. only directly linked to unsubstituted glucose units).

[0076] In various embodiments, the substituted cellulose has a DB of at least about 0.35, or even from about 0.40 to about 0.90, from about 0.45 to about 0.80, or even from about 0.50 to about 0.70. The substituted cellulose may have a DB+DS of at least about 1. Typically the substituted cellulose has a DB+DS of from about 1.05 to about 2.00, or from about 1.10 to about 1.80, or from about 1.15 to about 1.60, or from about 1.20 to about 1.50, or even from about 1.25 to about 1.40. In other embodiments, the substituted cellulose has a DS of from about 0.01 to about 0.20 or about 0.80 to about 0.99 and/or may have a DB+DS of at least about 1, typically of from about 1.05 to about 2.00, or from about 1.10 to about 1.80, or from about 1.15 to about 1.60, or from about 1.20 to about 1.50, or even from about 1.25 to about 1.40. In other embodiments, the substituted cellulose has a DS of from about 0.20 to about 0.80 and may have a DB+DS of at least about 0.85, about 0.90 to about 1.80, or from about 1.00 to about 1.60, or from about 1.10 to about 1.50, or from about 1.20 to about 1.40. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0077] In further embodiments, the substituted cellulose may have a DB+2DS-DS² of at least about 1.20. Typically the substituted cellulose has a DB+2DS-DS² of from about 1.22 to about 2.00, or from about 1.24 to about 1.90, or from about 1.27 to about 1.80, or from about 1.30 to about 1.70, or even from about 1.35 to about 1.60. In other embodiments, the substituted cellulose has a DS comprised of from about 0.01 to about 0.20 and may have a DB+2DS-DS² of from at least about 1.02 or from about 1.05 to about 1.20. In other embodiments, the substituted cellulose has a DS of from about 0.20 to about 0.40 and may have a DB+2DS-DS² of from about 1.05 to about 1.10 or from about 1.10 to about 1.40. In other embodiments, the substituted cellulose has a DS of from about 0.40 to about 1.00, about 0.60 to about 1.00, or about 0.80 to about 1.00 and may have a DB+2DS-DS² of from about 1.10 to about 2.00, or from about 1.20 to about 1.90, or from about 1.25 to about 1.80, or from about 1.20 to about 1.70, or even from about 1.35 to about 1.60. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0078] The methods to measure the DB may vary as a function of the substituent. The skilled person knows or may determine how to measure the degree of blockiness of a given substituted cellulose. By way of example, a method to measure the DB of a substituted cellulose is disclosed herein. In the case of a substituted cellulose, the DB may correspond to the amount (A) of nonsubstituted glucose units released after a specific enzymatic hydrolysis with the commercial endoglucanase enzyme (Econase CE, AB Enzymes, Darmstadt, Germany) divided by the total amount of non-substituted glucose units released after acid hydrolysis (A+B). The enzymatic activity is specific to non-substituted glucose units in the polymer chain that are directly bounded to another non-substituted glucose unit. Further description of substituted cellulose blockiness and measurement is provided in detail in V. Stigsson et al., Cellulose, 2006, 13, pp705-712, which is expressly incorporated herein by reference in various non-limiting embodiments.

[0079] In various embodiments, enzymatic degradation is performed using the enzyme (Econase CE) in a buffer at pH 4.8 at 50°C for 3 days. To 25 ml of substituted cellulose sample, 250 pL of enzyme is used. The degradation is stopped by heating the samples to 90°C and keeping them hot for 15 minutes. The acid hydrolysis for both substitution pattern and blockiness is carried out in perchloric acid (15 min in 70% HCIO4 at room temperature and 3 hours in 6.4% HCIO4 at 120°C). The samples are analyzed using Anion Exchange Chromatography with Pulsed Amperiometric Detection (PAD detector: BioLC50 (Dionex, Sunnyvale, California, USA)). The HPAEC/PAD system is calibrated with C13 NMR. The monosaccharides are separated at 35°C using a flow rate of 0.2ml/min on a PA-1 analytical column using lOOmM NaOH as eluent with increasing sodium acetate (from 0 to IM sodium acetate in 30 mins). Each sample is analyzed three to five times and an average is calculated. The number of unsubstituted glucose that were directly linked to at least one substituted glucose (A), and the number of unsubstituted glucose that were not directly linked to a substituted glucose (B) are deduced and the DB of the substituted cellulose sample is calculated: DB = B/(A+B).

[0080] In further embodiments, the substituted cellulose has typically a viscosity at 25°C when dissolved at 2% by weight in water of at least about 100 mPa.s for example a viscosity of from about 250 to about 5000, or from about 500 to about 4000, from about 1000 to about 3000 or from about 1500 to about 2000 mPa.s. The viscosity of the cellulose may be measured according to the following test method. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0081] A solution 2% by weight of the cellulose is prepared by dissolving the cellulose in water. The viscosity of the solution is determined using a Haake VT500 viscometer at a shear rate of 5s' ¹, at 25°C. Each measurement is done for 1 minute with 20 measuring points collected and averaged.

[0082] Typically, the cellulose of this disclosure has a molecular weight of from about 10,000 to about 10,000,000, for example from about 20,000 to about 1,000,000, typically from about 50,000 to about 500,000, or even from about 60,000 to about 150,000 g/mol. In various nonlimiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0083] The substituted cellulose may have a total number of glucose units from about 10 to about 7000, or of at least about 20. Suitable substituted celluloses include celluloses with a degree of polymerization (DP) over about 40, typically from about 50 to about 100,000 and more typically from about 500 to about 50,000. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0084] In other embodiments, a total number of glucose units of the substituted cellulose is for example from about 10 to about 10,000, or about 20 to about 7,500, for example about 50 to about 5,000 and typically about 100 to about 3,000, or from about 150 to about 2,000. In various nonlimiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0085] The substituted cellulose may be synthesized by a variety of routes which are well known to those skilled in the art of polymer chemistry. For instance, carboxyalkyl ether-linked celluloses can be made by reacting a cellulose with a suitable haloalkanoic acid. The skilled person may obtain substituted cellulose with a higher degree of blockiness for example by choosing the solvent of the reaction, the rate of addition of the reactants, and the alkalinity of the medium during the substituted cellulose synthesis. The synthetic process can be optimized to control the DB, as discussed in V. Stigsson et al., Cellulose, 2006, 13, pp705-712; N. Olaru et al, Macromolecular Chemistry & Physics, 2001, 202, pp 207-211; J. Koetz et al, Papier (Heidelburg), 1998, 52, pp704- 712; G. Mann et al, Polymer, 1998, 39, pp3155-3165. Methods for producing carboxymethyl cellulose and hydroxyethyl cellulose having blocky characteristics are also disclosed in WO 2004/048418 (Hercules ) and WO 06/088953 (Hercules ).

[0086] In various embodiments, the cellulose is further defined as carboxymethyl cellulose (CMC). The CMC that may be utilized in this disclosure is not particularly limited and may be any known in the art. In various embodiments, the CMC may be described as a blocky CMC. Carboxymethylcellulose polymers can include Finnfix, hydrophobically modified carboxymethylcellulose, e.g., the alkyl ketene dimer derivative of carboxy methylcellulose or a blocky carboxymethylcellulose.

[0087] In one embodiment, the composition is further described as an automatic dishwashing composition and the biopolymer is present in an amount of from about 8 to about 12, about 9 to about 11, or about 9 to about 10, weight percent actives based on a total weight of the composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0088] In another embodiment, the composition is further described as a laundry composition and the chelating agent is present in an amount of from about 4 to about 6, about 4 to about 5, or about 5 to about 6, weight percent actives based on a total weight of the composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

(C) Surfactant

[0089] The composition also includes a surfactant. The surfactant may be any known in the art. The surfactant may be any one or more of a cationic, non-ionic, anionic, zwitterionic, and/or amphoteric surfactant. Alternatively, the composition may be free of one or more of the aforementioned compounds.

[0090] Non-limiting examples of anionic surfactants include ammonium lauryl sulfate, sodium laureth sulfate, sodium lauryl sarcosinate, sodium myreth sulfate, sodium pareth sulfate, sodium stearate, sodium lauryl sulfate, a olefin sulfonate, and ammonium laureth sulfate, and combinations thereof. In one embodiment, the surfactant is or includes sodium lauryl sulfate (SLS). In one embodiment, the surfactant is or includes ammonium lauryl sulfate (ALS). In one embodiment, the surfactant is or includes ammonium laureth sulfate (ALES). In one embodiment, the surfactant is or includes sodium stearate. In one embodiment, the surfactant is or includes potassium cocoate.

[0091] In other embodiments, the anionic surfactant may include, or be free of, one or more of the following carboxylates, sulphonates, petroleum sulphonates, alkylbenzenesulphonates, naphthalenesulphonates, olefin sulphonates, alkyl sulphates, sulphates, sulphated natural oils & fats, sulphated esters, sulphated alkanolamides, ethoxylated & sulphated alkylphenols, or combinations thereof.

[0092] In some embodiments, the anionic surfactant can be linear alkylbenzene sulfonic acid or a salt thereof, alkyl ethoxylated sulphate, alkyl propoxy sulphate, alkyl sulphate, or a mixture thereof.

[0093] In some embodiments, the nonionic surfactant can be alcohol ethoxylate, alcohol propoxylate, or a mixture thereof.

[0094] Non-limiting examples of nonionic surfactants includes ethoxylated aliphatic alcohols, polyoxyethylene surfactants, carboxylic esters, polyethylene glycol esters, anhydrosorbitol ester and ethoxylated derivatives, glycol esters of fatty acids, carboxylic amides, monoalkanolamine condensates, polyoxyethylene fatty acid amides, and combinations thereof.

[0095] In other embodiments, the non-ionic surfactant may be chosen from alkoxylated alcohols, polyoxyalkylene alkyl ethers (e.g., those marketed under the trade name Pluronic® (e.g., Pluronic® PE or Pluronic® RPE, available from BASF), polyoxyalkylene alkylphenyl ethers, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyalkylene glycol fatty acid esters, alkyl polyalkylene glycol fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyalkylene castor oils, polyoxyalkylene alkylamines, glycerol fatty acid esters, alkylglucosamides, alkylglucosides, alkylamine oxides, and combinations thereof.

[0096] In one embodiment, the non-ionic surfactant is an alcohol ethoxylate (AE).The AE may include primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles, or from 3 to 8 moles of ethylene oxide per mole of alcohol. Exemplary AEs are the condensation products of aliphatic C8-C20, preferably Cs-Ci6, primary or secondary, linear or branched chain alcohols with ethylene oxide. In some embodiments, the alcohol ethoxylates contain 1 to 20, or 3 to 8 ethylene oxide groups, and may optionally be end-capped by a hydroxylated alkyl group. In one embodiment, the AE has Formula: R2 — ( — O — C2H4 — )_m — OH wherein R2 is a hydrocarbyl group having 8 to 16 carbon atoms, 8 to 14 carbon atoms, 8 to 12 carbon atoms, or 8 to 10 carbon atoms; and m is from 1 to 20, or 3 to 8. The hydrocarbyl group may be linear or branched, and saturated or unsaturated. In some embodiments, R2is a linear or branched Cs-Ci6 alkyl or a linear group or branched Cs-C 16 alkenyl group. Preferably, R2 is a linear or branched Cs-Ci6 alkyl, Cs-Cu alkyl, or Cs-Cio alkyl group. In case (e.g., commercially available materials) where materials contain a range of carbon chain lengths, these carbon numbers represent an average. The alcohol may be derived from natural or synthetic feedstock. In one embodiment, the alcohol feedstock is coconut, containing predominantly C12-C14 alcohol, and oxo C12- C15 alcohols. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0097] One suitable AE is Tomadol® 25-7 (available from Evonik). Other suitable AEs include Genapol® C200 (available from Clariant), which is a coco alcohol having an average degree of ethoxylation of 20.

[0098] In some embodiments, the aqueous composition can be substantially free of a sulfate surfactant.

[0099] Non-limiting examples of cationic surfactants include quaternary ammonium salts, amines with amide linkages, polyoxyethylene alkyl & alicyclic amines, N,N,N',N' tetrakis substituted ethylenediamines, 2- alkyl 1- hydroxethyl 2-imidazolines, and combinations thereof. [00100] Non-limiting examples of amphoteric surfactants include N-coco 3 -aminopropionic acid/ sodium salt, N-tallow 3 -iminodipropionate, disodium salt, N-carboxymethyl-N-dimethyl-N-9 octadecenyl ammonium hydroxide, N-cocoamidethyl-N-hydroxyethylglycine, sodium salt, and the like, and combinations thereof.

[00101] In some embodiments, the surfactant is a zwitterionic surfactant or an amphoteric surfactant. A zwitterionic surfactant is a net-neutrally charged molecule that has positive and negative charges. Some simple amphoteric molecules can only form a net positive or negative charge depending on the pH. Other amphoteric molecules can form a net-neutral charge, depending on the pH. Examples of zwitterionic materials include betaine. Linear Alkylbenzene Sulfonate (LAS)

[00102] Linear alkylbenzenesulfonate (LAS) can be utilized as a surfactant. LAS is a water soluble salt of a linear alkyl benzene sulfonate having from about 8 to about 22 carbon atoms of the linear alkyl group. The salt can be an alkali metal salt, or an ammonium, alkylammonium, or alkanolammonium salt. In one embodiment, the LAS comprises an alkali metal salt of Cio- Ci6 alkyl benzene sulfonic acids, such as C11-C14 alkyl benzene sulfonic acids. Suitable LAS includes sodium and potassium linear, alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to about 14. Sodium C11-C14 (e.g., C12) LAS is one suitable anionic surfactant for use herein.

Alcohol Ethoxylsulfate (AES)

[00103] Alcohol ethoxysulfate (AES) also known as alkyl ether sulfates or alkyl polyethoxylate sulfates can also be utilizes. These are compounds having Formula: Ri — O — (C2H4O)_n — SO3M wherein Ri is a C8-C22 alkyl group, n is from 1 to 20, and M is a salt-forming cation. Preferably, Ri is a Cio-Cis alkyl, or a C10-C 15 alkyl, n is from 1 to 15, 1 to 10, or 1 to 8, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. More preferably, Ri is a C12- Ci6 alkyl, n is from 1 to 6, and M is sodium. In one embodiment, the alkyl ether sulfate is sodium lauryl ether sulphate (SLES).

[00104] In various embodiments, the surfactant is present in an amount of from about 1 to about 35, about 1 to about 25, about 2 to about 24, about 3 to about 23, about 4 to about 22, about 5 to about 21, about 6 to about 20, about 7 to about 19, about 8 to about 18, about 9 to about 17, about 10 to about 16, about 11 to about 15, about 12 to about 14, or from about 13 to about 14, weight percent actives based on a total weight of the composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[00105] It is also contemplated that the surfactant may have the formula (I):

wherein

R represents a fatty linear or branched, saturated or unsaturated alkyl group having 8- 30 carbon atoms;

R¹ represents a linear or branched, saturated or unsaturated lower alkyl group having 1-8 carbon atoms; n represents at least 8 and at most 25.

[00106] In various embodiments, in the compound of formula (I):

R represents typically Cs - C22 alkyl or alkenyl, more typically Cs - C20 alkyl or alkenyl, and most typically C10 - Cis alkyl or alkenyl;

R¹ represents Ci - C4 alkyl, more typically methyl or ethyl, and most typically methyl; and n represents typically at least 9, and most typically at least 10, and typically at most 20, and most typically at most 17.

In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [00107] In a typical embodiment, the compound of formula (I) derives from a secondary amine of the formula (II):

T¹

R - NH (II) wherein

R represents a fatty linear or branched, Cs - C20 alkyl or alkenyl, and most typically C10 - Cis alkyl or alkenyl; and

Ri represents a linear or branched, Ci - C4 alkyl, more typically methyl or ethyl, and most typically methyl.

In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [00108] In an especially typical embodiment, the secondary amine is selected from the group consisting of octylmethylamine, cocoalkylmethylamine, laurylmethylamine, n-decylmethylamine, tallowalkylmethylamine, soyaalkylmethylamine, oleylalkylamine and C 12/14 alkylmethylamine. [00109] In a more typical embodiment, the compound of formula (I) has the formula:

wherein

Rrepresents a fatty linear or branched, Cio - Cis alkyl or alkenyl;

Ri represents methyl or ethyl; and n represents 8-17.

In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [00110] In a most typical embodiment, the compound of the formula (I) has the formula (la):

wherein

R represents a fatty linear or branched, saturated or unsaturated alkyl group having 8- 14 carbon atoms.

In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [00111] The compound of the formula (I) can be prepared by a process comprising:

(a) ethoxylating an amine of the formula (II):

Ri

R - NH (II) wherein

R represents Cs - C22 hydrocarbyl, typically Cs - C22 alkyl or alkenyl, more typically Cs - C20 alkyl or alkenyl, and most typically Cio - Cis alkyl or alkenyl; and

R¹ represents Ci - C4 alkyl, typically methyl or ethyl, and most typically methyl; to form an ethoxylated amine of the formula (III):

T¹

R - N — (-CH₂CH₂O— H n (HD wherein R and R¹ have the meanings given above; and n represents at least 8, typically at least 9, and most typically at least 10, and at most 25, typically at most 20, and most typically at most 17; and

(b) oxidizing the ethoxylated amine of the formula (III) to give the N-oxide of formula (I).

In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. In various non-limiting embodiments, the surfactant may be as described in PCT/EP2023/067090, which is expressly incorporated herein by reference in its entirety in these non-limiting embodiments.

(D) Enzyme

[00112] The composition optionally includes an enzyme which may be any known in the art. In other words, the composition may include an enzyme or may be free of an enzyme. Non-limiting examples of suitable enzymes include those known in the art, such as amylolytic, proteolytic, cellulolytic or lipolytic types. One typical protease, sold under the trade name Savinase® by Novo Nordisk Industries A/S, is a subtillase from Bacillus lentus. Other suitable enzymes include proteases, amylases, lipases and cellulases, such as Alcalase® (bacterial protease), Everlase® (protein-engineered variant of Savinase®), Esperase® (bacterial protease), Lipolase® (fungal lipase), Lipolase Ultra (Protein-engineered variant of Lipolase), Lipoprime® (protein-engineered variant of Lipolase), Termamyl® (bacterial amylase), BAN (Bacterial Amylase Novo), Celluzyme® (fungal enzyme), and Carezyme® (monocomponent cellulase), sold by Novo Nordisk Industries A/S. Also suitable for use in the present disclosure are blends of two or more of these enzymes, for example a protease/lipase blend, a protease/amylase blend, a protease/amylase/lipase blend, and the like.

[00113] In various embodiments, the enzyme is present in an amount of from about 0.01 to about 5, about 0.05 to about 5, about 0.1 to about 5, about 0.2 to about 4, about 0.4 to about 3.8, about 0.6 to about 3.6, about 0.8 to about 3.4, about 1 to about 3.2, about 1.2 to about 3, about 1.4 to about 2.8, about 1.6 to about 2.6, about 1.8 to about 2.4, or about 2 to about 2.2, weight percent actives based on a total weight of the composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

(E) Phosphorous- Containing Compound

[00114] The composition also includes the phosphorous-containing compound. This compound is not particularly limited and may be any known in the art. In one embodiment, the phosphorous- containing compound is or includes a phosphonate salt such as a salt wherein the anion is a phosphonate and the cation is chosen from sodium, calcium, potassium, magnesium, quaternary ammonium, pyridinium, tris(2-hydroxyethyl)methyl ammonium, and combinations thereof.

[00115] In one embodiment, the phosphorous-containing compound is or includes a compound that includes a long chain hydrocarbon hydrophobic group and a hydrophilic group such as a phosphonate groups.

[00116] In one embodiment, the phosphorous-containing compound is or includes phosphates, phosphonates, polyphosphates or combinations thereof such as tripolyphosphate, sodium pyrophosphate and potassium pyrophosphate.

[00117] Overall, even in the presence of the phosphorous-containing compound, the cleaning composition has a phosphorous content of less than about 1 weight percent actives based on a total weight of the cleaning composition. In various embodiments, the cleaning composition has a phosphorous content of less than about 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1, weight percent actives based on a total weight of the cleaning composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

(F) Water

[00118] The composition can also include water. The amount of the water is not particularly limited and it depends also on the format of the cleaning composition (e.g. liquid or powder). In various embodiments, the water is present in an amount that balance the amounts of (A)-(E) such that a total weight is equal to about 100 wt% of the composition. For example, the water is typically present in an amount of from about 10% to about 99.9 % for liquid formulations and about 1% to about 10% for powder formulations, based on a total weight of the composition. In various embodiments, the amount of water is from about 1 to about 99, about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, about 50 to about 55, about 90 to about 99.9, about 95 to about 99.9, or about 99 to about 99.9, weight percent based on a total weight of the composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

(G) Solvents

[00119] The composition can also include, or be free of, one or more solvents. The solvents are not particularly limited and may be any known in the art. In various embodiments, the solvent(s) may be alcohols, alkoxylated compounds, ethers, esters, aromatic solvents, polar solvents, nonpolar solvents, hydrophilic solvents, hydrophobic solvents, or combinations thereof. In various embodiments, the composition is free of hygroscopic glycol or an organic solvent, such as alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol (PEG) of molecular weight between 300 and 600, or monoethanolamine. If included, the amount of the solvent is not particularly limited. In various embodiments, the solvent is present in an amount of from about 1 to about 20 wt% based on a total weight of the composition In various embodiments, this amount is from about 5 to about 20, about 10 to about 15, about 10 to about 20, or about 15 to about 20, weight percent, based on a total weight of the composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

(H) Additives

[00120] The composition can also include, or be free of, one or more additives, which may be any known in the art.

[00121] Non-limiting examples of additives that may be included or excluded include builders, anti-redeposition agents, fragrances, dyes (colorants), dispersing agents, defoamers, color components, bleaching catalysts, bleaching agents, bleach activators, whitening agents, brightening agents, anticorrosion agents, deodorizing agents, color/texture rejuvenating agents, soil releasing polymers, preservatives, bittering agents, or a combination thereof.

[00122] A defoamer is a chemical additive that prevents the formation of foam and/or breaks foam already formed. Examples of commonly used defoamers include fatty acids, poly dimethylsiloxanes, silicones, twin chain alcohols and some alcohols, glycols, stearates, and insoluble oils.

[00123] Suitable builders include organic or inorganic detergency builders. Examples of water- soluble inorganic builders that can be used, either alone or in combination with themselves or with organic alkaline sequestrant builder salts, are glycine, alkyl and alkenyl succinates, alkali metal carbonates, alkali metal bicarbonates, phosphates, polyphosphates and silicates. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium pyrophosphate and potassium pyrophosphate. Examples of organic builder salts that can be used alone, or in combination with each other, or with the preceding inorganic alkaline builder salts, are alkali metal polycarboxylates, water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediaminetetracetate, sodium and potassium N(2-hydroxyethyl)-nitrilo triacetates, sodium and potassium N-(2-hydroxyethyl)-nitrilo diacetates, sodium and potassium oxy disuccinates, and sodium and potassium tartrate mono- and di-succinates.

[00124] Fragrance (perfume) refer to and include any fragrant substance or mixture of substances including natural (obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (mixture of natural oils or oil constituents) and synthetically produced odoriferous substances. The fragrance can comprise an ester, an ether, an aldehyde, a ketone, an alcohol, a hydrocarbon, or a mixture thereof.

[00125] Typically, perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes). The essential oils themselves are volatile odoriferous compounds and also serve to dissolve the other components of the perfume.

[00126] In some embodiments, the fragrance component is in the form of free fragrance. In some embodiments, at least some of the fragrance can be encapsulated. The fragrance (perfume) can have, for example, a musky scent, a putrid scent, a pungent scent, a camphoraceous scent, an ethereal scent, a floral scent, a peppermint scent, or any combination thereof. The fragrance comprises methyl formate, methyl acetate, methyl butyrate, ethyl butyrate, isoamyl acetate, pentyl butyrate, pentyl pentanoate, octyl acetate, myrcene, geraniol, nerol, citral, citronellol, linalool, nerolidol, limonene, camphor, terpineol, alpha-ionone, thujone, benzaldehyde, eugenol, cinnamaldehyde, ethyl maltol, vanillin, anisole, anethole, estragole, thymol, indole, pyridine, 1 furaneol, 1 -hexanol, cis-3-hexenal, furfural, hexyl cinnamaldehyde, fructone, hexyl acetate, ethyl methyl phenyl glycidate, dihydrojasmone, oct-l-en-3-one, 2-acetyl-l -pyrroline, 6-acetyl-2, 3,4,5- tetrahydropyridine, gamma-decalactone, gamma-nonalactone, delta-octalone, jasmine lactone, massoia lactone, wine lactone, sotolon, grapefruit mercaptan, methanthiol, methyl phosphine, dimethyl phosphine, nerolin, 2,4,6-trichloroanisole, or any combination thereof.

[00127] All dyes (colorants) suitable for use in detergent composition can be used in herein. A variety of dye colors can be used, such as blue, yellow, green, orange, purple, clear, etc. Suitable dyes include, but are not limited to chromophore types, e.g., azo, anthraquinone, triarylmethane, methine quinophthalone, azine, oxazine thiazine, which may be of any desired color, hue or shade. Suitable dyes can be obtained from any major supplier such as Clariant, Ciba Speciality Chemicals, Dystar, Avecia or Bayer. In some embodiments, the colorant is Liquitint® Blue HP (available from Milliken Chemical), which can be added in the form of a 1% aqueous dye solution, i.e., 1% active dye+99% water.

[00128] Suitable biocidal agents include an anti-microbial, a germicide, or a fungicide. For example, a biocidal agent includes triclosan (5-chloro-2-(2,4-dichloro-phenoxy) phenol)), and the like.

[00129] Suitable optical brighteners include stilbenes such as Tinopal® AMS; di styrylbiphenyl derivatives such as TINOPAL® CBS-X, stilbene/naphthotriazole blends (e.g., Tinopal® RA-16, available from Ciba Geigy); oxazole derivatives, or coumarin brighteners.

[00130] Suitable foam stabilizing agents include a polyalkoxylated alkanolamide, amide, amine oxide, betaine, sultaine, C8-C18 fatty alcohols, and those disclosed in U.S. Pat. No. 5,616,781. An auxiliary foam stabilizing surfactant, such as a fatty acid amide surfactant, may also be included in the aqueous composition disclosed herein. Suitable fatty acid amides include C8-C20 alkanol amides, monoethanolamides, diethanolamides, or isopropanolamides.

[00131] Suitable anti-redeposition agents are typically polycarboxylate materials. Polycarboxylate materials, which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, are admixed in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40 wt % of the polymer.

[00132] Suitable polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerised acrylic acid. The average molecular weight of such polymers in the acid form ranges from about 2,000 to 10,000, from about 4,000 to 7,000, or from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. In one embodiment, the polycarboxylate is sodium polyacrylate. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[00133] Acrylic/maleic -based copolymers may also be used as a component of the antiredeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form ranges from about 2,000 to 100,000, from about 5,000 to 75,000, or from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30: 1 to about 1:1, or from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers are known materials. Other useful polymers include maleic/acrylic/vinyl alcohol terpolymers (e.g., a terpolymer containing 45/43/10 of acrylic/maleic/vinyl alcohol). In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[00134] Polyethylene glycol can act as a clay soil removal-anti-redeposition agent. Molecular weight of suitable polyethylene glycol can range from about 1,000 to about 50,000, or about 3,000 to about 10,000. Polyaspartate and polyglutamate dispersing agents may also be used herein. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[00135] Any polymeric soil release agent known to those skilled in the art can optionally be employed herein as well. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

[00136] Exemplary anti-redeposition agents include an acrylic polymer selected from Sokalan PA 30, Sokalan PA 20, Sokalan PA 15, and Sokalan CP 10 (BASF GmbH, Germany) and Acusol 445G and Acusol 445N (The Dow Chemical Company, Midland, Mich.); an acrylic acid/maleic acid copolymer selected from Acusol 460N and Acusol 505N (The Dow Chemical Company) and Sokalan CP 5, Sokalan CP 45, and Sokalan CP 7 (BASF GmbH, Germany); and an anionic polymer selected from Alcosperse 725 and Alcosperse 747 (Nouryon, Chattanooga, Tenn.) and Acusol 480N (The Dow Chemical Company, Midland, Mich.); and Dequest SPE 1202 (Italmatch Chemicals, Genova, Italy); and an ethoxylated polyethylene imine Sokalan HP 20 (BASF, Germany).

[00137] Suitable soil-releasing polymers include, but are not limited to, Texcare SRN — a nonionic polyester of polypropylene terephthalate (Clariant); REPEL-O-TEX SRP — a polyethylene glycol polyester (Solvay); end-capped and non-end-capped sulfonated and unsulfonated PET/POET polymers; polyethylene glycol/polyvinyl alcohol graft copolymers such as SOKALAN HP 22 (BASF, Germany); and anionic hydrophobic polysaccharides.

[00138] The composition may include a buffer. A wide range of buffers can be used herein. For example, the buffer may comprise a citrate or a formate, and optionally an amine (e.g., triethanolamine). In some embodiments, the liquid composition contains from about 1 to about 15 wt %, preferably from about 5 to about 10 wt % of the buffer, based on the total weight of the liquid composition.

Physical Properties

[00139] The composition is not limited to having any particular physical properties. In various embodiments, the composition has a Renewable Carbon Index (RCI) of at least 50, 55, 60, 65, 70, 75, 80, etc. % as of as determined using ISO 16128-2 2017 or DIN EN 16785-2. In various nonlimiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[00140] In other embodiments, the composition includes surfactants and/or chelating agents and/or biopolymers that may have a biodegradation in aerobic conditions of more than about 60, 65, 70, 75, 80, 85, 90, or even 95, % at 28 days as determined by OECD 301D or OECD 301B. These may be any described herein. Typically, inherent biodegradation is defined as degrading greater than about 20 percent to less than about 60 percent within 28 days. Readily biodegradable materials, on the other hand, degrade by about 60 percent or more within 28 days or less. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[00141] In other embodiments, the stain removal efficiency of the compositions is determined from the stain removal index (%SRI) on a scale 0% (unwashed) to 100% (complete stain removal) using a Minolta Spectrophotometer calibrated at D65/10+UV. The improvement is assessed by scaling the %SRI to reference (composition without varied component) and results reported from scale AE 0 (no improvement) to AE 100 (complete stain removal by composition). Additionally, the improvement on the anti-redeposition (ARD) effect is determined from ACIE Whiteness measured using a Minolta Spectrophotometer calibrated at D65/10+UV. The ACIE Whiteness is the difference between the CIE Whiteness of the reference (composition without varied component) and the composition. The CIE Whiteness scale is 0 (black) to 100 (white) and the ACIE Whiteness follows accordingly, i.e., the higher the value whiter results is obtained. In various embodiments, the improvement is at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, etc, up to 100. For example, the laundry composition may have a stain removal index of at least AE land an anti- redepositioning effect of at least ACIE 1 whiteness as determined using a Minolta Spectrophotometer. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[00142] In other embodiments, the composition has a filming and spotting performance of at least 3.5 as determined using ASTM D3556 or EN 50242:2016. Filming and spotting are estimated visually by trained panelists on a scale from 1 to 9 where 1 is poor performance and 9 is excellent performance. The usual target for commercial products is between 3 and 7. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

Additional Embodiments

[00143] This disclosure also provides an automatic dishwashing composition comprising: A. a chelating agent chosen from methylglycinediacetic acid (MGDA), N,N- dicarboxymethyl glutamic acid (GLDA), ethylenediaminetetraacetic acid (EDTA), and combinations thereof and present in an amount of from about 10 to about 20 weight percent actives based on a total weight of the automatic dishwashing composition;

B. a biopolymer chosen from starch polycarboxylates, carboxymethyl celluloses, and combinations thereof and present in an amount of from about 6 to about 12 weight percent actives based on a total weight of the automatic dishwashing composition;

C. a surfactant present in an amount of from about 2 to about 8 weight percent actives based on a total weight of the automatic dishwashing composition;

D. an enzyme optionally present in an amount of from about 0.2 to about 4 weight percent actives based on a total weight of the automatic dishwashing composition; and

E. a phosphorous-containing compound; wherein the cleaning composition has a phosphorous content of less than about 1 weight percent actives based on a total weight of the automatic dishwashing composition. In various nonlimiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[00144] This disclosure further provides a laundry composition comprising:

A. a chelating agent chosen from methylglycinediacetic acid (MGDA), N,N- dicarboxymethyl glutamic acid (GLDA), ethylenediaminetetraacetic acid (EDTA), and combinations thereof and present in an amount of from about 1 to about 5 weight percent actives based on a total weight of the laundry composition;

B. a biopolymer chosen from starch polycarboxylates, carboxymethyl celluloses, and combinations thereof and present in an amount of less than about 5 weight percent actives based on a total weight of the laundry composition;

C. a surfactant present in an amount of from about 5 to about 30 weight percent actives based on a total weight of the laundry composition;

D. an enzyme optionally present in an amount of from about 0.2 to about 4 weight percent actives based on a total weight of the laundry composition; and

E. a phosphorous-containing compound; wherein the laundry composition has a phosphorous content of less than about 1 weight percent actives based on a total weight of the laundry composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[00145] In various non-limiting embodiments, it is contemplated that the composition may include a naturally derived and/or synthetic polymeric structurant. Non-limiting examples of naturally derived polymeric structurants include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives and mixtures thereof. Suitable polysaccharide derivatives include: pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, guar gum and mixtures thereof.

[00146] In still other non-limiting embodiments, this disclosure may include or utilize one or more components, compounds, polymers, compositions, methods, etc. as set forth in EP2272941 and/or W 02018/060262, each of which is expres sly incorporated herein by reference in its entirety in these non-limiting embodiments.

EXAMPLES

First Series of Examples

[00147] A first series of laundry compositions are formed and evaluated to determine stain removal index. More specifically, the following base formulation is utilized and various additives are added thereto.

Base Formulation:

[00148] Varying compositions were then created by adding amounts of the three additives described above. These compositions were then evaluated to determine Average %SRI scaled to no additive. The results are shown in FIG. 1 wherein the applied stain swatches are set forth below:

Compositions 1-6 are set forth below:

[00149] DTPMP is diethylenetriamine penta(methylene phosphonic acid).

[00150] GLDA is Tetrasodium glutamate diacetate.

[00151] Starch Polycarboxylate is starch polyacrylic hybrid polymer obtained as a reaction product between acrylic acid and maltodextrin, e.g. about 20 to about 30 weight or mol% acrylic acid and about 70 to about 80 weight or mol% maltodextrin.

[00152] Carboxymethyl Cellulose is a sodium carboxymethyl cellulose with the polysaccharide having an average molecular weight no greater than from about 10,000 to 80,000 Dalton and with the CMC component having a substitution degree from about 0.2 to about 1.5

[00153] The test conditions used to determine stain removal index are as follows:

Apparatus: Miele W1935 WPS, Front loader

9x PE container IL filled with 500 mL of water: water hardness 18°DH

1.667 grams of base formulation dosed to PE bottle containing 500ml water

(= 50 ml detergent/ machine wash cycle [15L] ) corrected for 17.5% hole in base formulation

Additives dosed in formulation hole

All purpose monitor supplied to each PE bottle

SM-04 Monitor ex CFT: 20 stains targeted on bleach, enzyme, stain removal, particle and fat

Washing program: cotton program 40°C , 90 minutes

After the wash cycle the monitors are removed from the containers and rinsed with tap water (20 minutes rinse cycle)

The monitors are dried overnight on tissue paper

The cleaning performance is measured (stain removal index) by measuring color before and after washing

[00154] The results of these evaluations are set forth in Figure 1.

Second Series of Examples

[00155] A second series of laundry compositions are formed and evaluated to determine antiredeposition (ARD) according to a procedure by using a Tergotometer. More specifically, whiteness is measured of knitted cotton. 18 dH water is used along with soil and detergent. Samples of the cotton are washed for 60 minutes at about 25°C/40°C at 200 rpm. Then a 15 minute rinse cycle is completed. CIE Whiteness scaled to a reference is measured using a Minolta Spectrophotometer.

[00156] More specifically, the following base formulation is utilized and various additives are added thereto.

Base Formulation:

[00157] The components in the table above are the same as described above.

[00158] Varying compositions were then created by adding amounts of the three additives described above. These compositions were then evaluated to determine CIE whiteness as described above. The results are shown in FIG. 2.

[00159] Compositions 7-13 are set forth below:

[00160] DTPMP is diethylenetriamine penta(methylene phosphonic acid).

[00161] GLDA is Tetrasodium glutamate diacetate.

[00162] HEDP is Hydroxyethylidene Diphosphonic Acid.

[00163] Starch polycarboxylate is starch polyacrylate hybrid polymer.

[00164] The results of the evaluations of the first and second series of compositions shows that: GLDA shows similar or better stain removal performance compared with DTPMP at the same dosage level. Moreover, the combination GLDA with biopolymers outperforms DTPMP for stain removal. Phosphonate shows rather poor ARD effect and the same accounts for GLDA without the biopolymer. In addition, the combination of GLDA with the biopolymer shows significant ARD performance improvement.

Third Series of Examples

[00165] A third series of examples, i.e., automatic dishwashing compositions, are formed and evaluated to determine primary and secondary washing performance (e.g. filming and spotting). The test conditions used are as follows:

Machines: Miele GSL2

Program: R65/10/K165

Running time ~lh 35 min, washing, 2 rinses and drying

Water hardness: 21 dGH

Made synthetic from CaCh, MgSO4 and NaHCO

Cycles: 5, 10, 20 and 30

Evaluation by a panel on filming and spotting

Used powder per cycle: 18.8 g

Ballast soil: 25 g

[00166] The ballast soil includes the following components:

[00167] The compositions of this third series are as follows:

[00168] Starch Polycarboxylate is a starch polyacrylic hybrid polymer obtained as a reaction product between acrylic acid and maltodextrin, e.g. about 20 to about 30 weight or mol% acrylic acid and about 70 to about 80 weight or mol% maltodextrin.

[00169] Polycarboxylate is acrylate copolymer sodium salt, e.g. about 45-65mol % of acrylic acid and about 30-45 mol% of maleic acid and an average MW of about 3000-4000 Daltons.

[00170] Each of these Compositions 14-21 were evaluated to determine filming and spotting after both 20 and 30 washes. More specifically, the results are set forth in the Figures as follows:

Results of 20 washes: See Figures 3-7; and

Results of 30 washes: See Figures 8-10.

[00171] The results show that phosphonate concentrations can be significantly reduced (to 0.1%) without losing secondary cleaning performance. Without phosphonate, significant filming and spotting is observed. The performance of Compositions 16-19 is comparable to Compositions 14, 15, 20, 21 at moderate phosphonate concentrations (0.5 - 1.5%), but not as good at very low phosphonate concentrations (-0.1%). With these formulations, a complete replacement of phosphonate brings a significant loss in filming performance.

[00172] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the present disclosure in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the present disclosure. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the present disclosure as set forth in the appended claims.

Claims

CLAIMS What is claimed is:

1. A cleaning composition comprising:

2. The cleaning composition of claim 1 wherein the chelating agent is chosen from methylglycinediacetic acid (MGDA), N,N-dicarboxymethyl glutamic acid (GLDA), and combinations thereof.

3. The cleaning composition of claim 1 wherein the chelating agent is chosen from methylglycinediacetic acid (MGDA), N,N-dicarboxymethyl glutamic acid (GLDA), ethylenediaminetetraacetic acid (EDTA), and combinations thereof.

4. The cleaning composition of any one of claims 1-3 wherein the biopolymer is a starch polycarboxylate.

5. The cleaning composition of any one of claims 1-3 wherein the biopolymer is a carboxymethyl cellulose.

6. The cleaning composition of any one of claims 1-3 wherein the biopolymer is a combination of a starch polycarboxylates and a carboxymethyl celluloses.

7. The cleaning composition of any preceding claim wherein the chelating agent is present in an amount of from about 15 to about 20 weight percent actives based on a total weight of the cleaning composition.

8. The cleaning composition of any one of claims 1-6 wherein the chelating agent is present in an amount of from about 1 to about 5 weight percent actives based on a total weight of the cleaning composition.

9. The cleaning composition of any preceding claim wherein the biopolymer is present in an amount of from about 8 to about 12 weight percent actives based on a total weight of the cleaning composition.

10. The cleaning composition of any one of claims 1-8 wherein the chelating agent is present in an amount of less than about 5 weight percent actives based on a total weight of the cleaning composition.

11. The cleaning composition of any preceding claim having a phosphorous content of less than about 0.1 weight percent actives based on a total weight of the cleaning composition.

12. The cleaning composition of any preceding claim having a Renewable Carbon Index (RCI) of at least 50% as determined using ISO 16128-2 2017 or DIN EN 16785-2.

13. The cleaning composition of any preceding claim having surfactants and/or chelating agents and/or biopolymers with a biodegradation in aerobic conditions of 60% at 28 days as determined by OECD 30 ID or OECD 30 IB.

14. An automatic dishwashing composition comprising:

A. a chelating agent chosen from methylglycinediacetic acid (MGDA), N,N- dicarboxymethyl glutamic acid (GLDA), ethylenediaminetetraacetic acid (EDTA), and combinations thereof and present in an amount of from about 10 to about 20 weight percent actives based on a total weight of the automatic dishwashing composition;

E. a phosphorous-containing compound; wherein the cleaning composition has a phosphorous content of less than about 1 weight percent actives based on a total weight of the automatic dishwashing composition.

15. The automatic dishwashing composition of claim 14 having a phosphorous content of less than about 0.1 weight percent actives based on a total weight of the automatic dishwashing composition.

16. The automatic dishwashing composition of claim 14 or 15 having a Renewable Carbon Index (RCI) of at least 50% as determined using ISO 16128-2 2017 or DIN EN 16785-2.

17. The automatic dishwashing composition of any one of claims 14-16 having filming and spotting performance of at least 3.5 as determined using ASTM D3556 or EN 50242:2016

18. A laundry composition comprising:

A. a chelating agent chosen from methylglycinediacetic acid (MGDA), N,N- dicarboxymethyl glutamic acid (GLDA), ethylenediaminetetraacetic acid (EDTA), and combinations thereof and present in an amount of from about 1 to about 5 weight percent actives based on a total weight of the laundry composition; B. a biopolymer chosen from starch polycarboxylates, carboxymethyl celluloses, and combinations thereof and present in an amount of less than about 5 weight percent actives based on a total weight of the laundry composition;

E. a phosphorous-containing compound; wherein the laundry composition has a phosphorous content of less than about 1 weight percent actives based on a total weight of the laundry composition.

19. The laundry composition of claim 18 having a phosphorous content of less than about 0.1 weight percent actives based on a total weight of the laundry composition.

20. The laundry composition of claim 18 or 19 having a Renewable Carbon Index (RCI) of at least 50% as determined using ISO 16128-2 2017 or DIN EN 16785-2, having a stain removal index of at least AE 1, and having an anti-redepositioning effect of at least ACIE 1 whiteness as determined using a Minolta Spectrophotometer.