Carboxyalkyl locust bean gum dishwashing detergent

Abstract

A dishwashing detergent formulation is provided, comprising: a builder; a nonionic surfactant; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight (MW) >500,000 Daltons and a degree of carboxyl substitution (DS) of 0.1 to 0.54. CA .

Description

[0001] This invention relates to a dishwashing detergent formulation. Specifically, this invention relates to a dishwashing detergent formulation comprising: a detergent builder; a nonionic surfactant; and a carboxyalkyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyalkyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA .

[0002] Dishwashing compositions are generally considered a different class of detergent compositions from those used for washing fabrics or water treatment. Users expect dishwashing compositions to produce a film-free appearance on washed items after a complete cleaning cycle.

[0003] Phosphate-free dishwashing compositions are gaining popularity. Phosphate-free dishwashing compositions typically rely on non-phosphate builders, such as citrates, carbonates, silicates, disilicates, bicarbonates, aminocarboxylates, and other salts, to chelate with calcium and magnesium from hard water and leave insoluble, visible deposits after drying.

[0004] Christopher et al. disclosed a family of polycarboxylate copolymers and their use as builder agents in detergent compositions and rinsing aid compositions for the final rinsing step of dishwashing machines or utensil washers in U.S. Patent 5,431,846. Christopher et al. disclosed block copolymers comprising 20 mol% to 95 mol% monomer units derived from itaconic acid or its homologues and 5 mol% to 80 mol% monomer units derived from vinyl alcohol or low-carbon vinyl esters. These block copolymers are excellent binders for divalent or polyvalent metals and are suitable as potentially biodegradable builder agents in detergent compositions, as well as machine dishwashing compositions and anti-scalding rinsing compositions.

[0005] Swift et al. disclosed a family of terpolymers and their use as dispersants in U.S. Patent 5,191,048. Swift et al. taught terpolymers comprising about 15 mol% to 55 mol% of at least one first monomer selected from the group consisting of vinyl acetate, vinyl ether, and vinyl carbonate as polymerization units; about 10 mol% to 70 mol% of at least one second monomer of an olefinically unsaturated monocarboxylic acid; and about 15 mol% to 55 mol% of at least one third monomer of an anhydride of a dicarboxylic acid, wherein the terpolymer is formed in a non-aqueous system such that less than about one more percentage of the monomers hydrolyzes during polymerization.

[0006] Nevertheless, there remains a need for novel dispersant polymers for use in dishwashing formulations. Specifically, there remains a need for novel dispersant polymers for use in dishwashing formulations, wherein the dispersant polymer provides effective low film-forming properties; is of biological origin and is biodegradable.

[0007] This invention provides a dishwashing detergent formulation comprising: a detergent builder; a nonionic surfactant; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA .

[0008] This invention provides a dishwashing detergent formulation comprising: a detergent builder; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA .

[0009] This invention provides a dishwashing detergent formulation comprising: a detergent builder; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA The carboxyl galactomannan is selected from the group consisting of: carboxyl tara gum, carboxyl locust bean gum, carboxyl cinnamon gum, and mixtures thereof; and the dishwashing detergent formulation contains ≤0.4% by weight of urea based on the weight of the dishwashing detergent formulation.

[0010] This invention provides a dishwashing detergent formulation comprising: a detergent builder; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA The carboxyl galactomannan is selected from the group consisting of: carboxyl tara gum, carboxyl locust bean gum, carboxyl cinnamon gum, and mixtures thereof; the dishwashing detergent formulation contains ≤0.4% by weight of urea based on the weight of the dishwashing detergent formulation; and the dishwashing detergent formulation is anhydrous solid.

[0011] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA The carboxyl galactomannan is selected from the group consisting of: carboxyl tara gum, carboxyl locust bean gum, carboxyl cinnamon gum, and mixtures thereof; the dishwashing detergent formulation contains ≤0.4% by weight of urea based on the weight of the dishwashing detergent formulation; and the dishwashing detergent formulation is anhydrous solid.

[0012] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA The carboxyl galactomannan is selected from the group consisting of: carboxyl tara gum, carboxyl locust bean gum, carboxyl cinnamon gum, and mixtures thereof; the dishwashing detergent formulation contains ≤0.4% by weight of urea based on the weight of the dishwashing detergent formulation; the dishwashing detergent formulation contains less than 0.1% by weight of phosphate based on the dry weight of the dishwashing detergent formulation; and the dishwashing detergent formulation is anhydrous solid.

[0013] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CAThe carboxyl galactomannan is selected from the group consisting of: carboxyl tara gum, carboxyl locust bean gum, carboxyl cinnamon gum, and mixtures thereof; the dishwashing detergent formulation contains ≤0.4% by weight urea based on the weight of the formulation; the dishwashing detergent formulation contains less than 0.1% by weight phosphate measured as elemental phosphorus based on the dry weight of the formulation; the dishwashing detergent formulation contains 0% by weight of detergent builder based on the dry weight of the formulation, the detergent builder being selected from the group consisting of: nitrotriacetic acid; ethylenediaminetetraethyl... Acids; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N'-ethylenediaminedisuccinate; iminodisuccinate; aspartic acid; aspartic acid-N,N-diacetic acid; β-alanine diacetic acid; polyaspartic acid; their salts and mixtures thereof; and wherein the dishwashing detergent formulation is anhydrous solid.

[0014] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; an additive selected from the group consisting of bleaching agents, bleaching activators, enzymes, fillers, and mixtures thereof; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CAThe carboxyl galactomannan is selected from the group consisting of: carboxyl tara gum, carboxyl locust bean gum, carboxyl cinnamon gum, and mixtures thereof; the dishwashing detergent formulation contains ≤0.4% by weight urea based on the weight of the formulation; the dishwashing detergent formulation contains less than 0.1% by weight phosphate measured as elemental phosphorus based on the dry weight of the formulation; the dishwashing detergent formulation contains 0% by weight of detergent builder based on the dry weight of the formulation, the detergent builder being selected from the group consisting of: nitrotriacetic acid; ethylenediaminetetraethyl... Acids; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N'-ethylenediaminedisuccinate; iminodisuccinate; aspartic acid; aspartic acid-N,N-diacetic acid; β-alanine diacetic acid; polyaspartic acid; their salts and mixtures thereof; and wherein the dishwashing detergent formulation is anhydrous solid.

[0015] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; an additive selected from the group consisting of bleaching agents, bleaching activators, enzymes, fillers, and mixtures thereof; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight of 600,000 Daltons to 2,750,000 Daltons and a degree of carboxymethyl substitution (DS) of 0.3 to 0.46. CA The dishwashing detergent contains, based on the weight of the dishwashing detergent formulation, ≤0.4% by weight of urea; based on the dry weight of the dishwashing detergent formulation, less than 0.1% by weight of phosphate measured as elemental phosphorus; and based on the dry weight of the dishwashing detergent formulation, 0% by weight of a detergent builder selected from the group consisting of: hypozinotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diethyl... Acids; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N'-ethylenediaminedisuccinate; iminodisuccinate; aspartic acid; aspartic acid-N,N-diacetic acid; β-alanine diacetic acid; polyaspartic acid; their salts and mixtures thereof; and wherein the dishwashing detergent formulation is anhydrous solid.

[0016] This invention provides a dishwashing detergent formulation comprising: a detergent builder; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA Furthermore, based on the weight of the dishwashing detergent formulation, the dishwashing detergent formulation contains ≤0.4% by weight of urea.

[0017] This invention provides a dishwashing detergent formulation comprising: a detergent builder; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA The dishwashing detergent formulation contains ≤0.4% by weight of urea, based on the weight of the formulation; and the dishwashing detergent formulation is anhydrous solid.

[0018] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA The dishwashing detergent formulation contains ≤0.4% by weight of urea, based on the weight of the formulation; and the dishwashing detergent formulation is anhydrous solid.

[0019] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CAThe dishwashing detergent formulation contains ≤0.4% by weight of urea based on its weight; the dishwashing detergent formulation contains less than 0.1% by weight of phosphate based on its dry weight as elemental phosphorus; and the dishwashing detergent formulation is anhydrous solid.

[0020] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA The dishwashing detergent formulation contains ≤0.4% by weight of urea based on its weight; it also contains less than 0.1% by weight of phosphate based on its dry weight, measured in elemental phosphorus; and it contains 0% by weight of builder based on its dry weight, the builder being selected from the group consisting of: hypozinotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinate-aspartic acid-diacetic acid; N,N'-ethylenediaminedisuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; β-alanine diacetic acid; polyaspartic acid; their salts and mixtures thereof; and the dishwashing detergent formulation is anhydrous solid.

[0021] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; an additive selected from the group consisting of bleaching agents, bleaching activators, enzymes, fillers, and mixtures thereof; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CAThe dishwashing detergent formulation contains ≤0.4% by weight of urea based on its weight; it also contains less than 0.1% by weight of phosphate based on its dry weight, measured in elemental phosphorus; and it contains 0% by weight of builder based on its dry weight, the builder being selected from the group consisting of: hypozinotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinate-aspartic acid-diacetic acid; N,N'-ethylenediaminedisuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; β-alanine diacetic acid; polyaspartic acid; their salts and mixtures thereof; and the dishwashing detergent formulation is anhydrous solid.

[0022] This invention provides a dishwashing detergent formulation comprising: a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; a nonionic surfactant; a phosphonate crystal growth inhibitor; an additive selected from the group consisting of bleaching agents, bleaching activators, enzymes, fillers, and mixtures thereof; and a carboxyl galactomannan with a mannose to galactose ratio >2:1; wherein the carboxyl galactomannan has a weight-average molecular weight of 600,000 Daltons to 2,750,000 Daltons and a degree of carboxymethyl substitution (DS) of 0.3 to 0.46. CA The dishwashing detergent contains, based on the weight of the dishwashing detergent formulation, ≤0.4% by weight of urea; based on the dry weight of the dishwashing detergent formulation, less than 0.1% by weight of phosphate measured as elemental phosphorus; and based on the dry weight of the dishwashing detergent formulation, 0% by weight of a detergent builder selected from the group consisting of: hypozinotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diethyl... Acids; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N'-ethylenediaminedisuccinate; iminodisuccinate; aspartic acid; aspartic acid-N,N-diacetic acid; β-alanine diacetic acid; polyaspartic acid; their salts and mixtures thereof; and wherein the dishwashing detergent formulation is anhydrous solid.

[0023] The present invention provides a method for cleaning articles in an automatic dishwashing machine, the method comprising: providing at least one soiled article; providing a dishwashing detergent formulation selected based on its ability to prevent the formation of phosphonate scale on the at least one soiled article, wherein the dishwashing detergent formulation is selected according to the present invention; and applying the selected dishwashing detergent formulation to the at least one soiled article to provide a clean article. Detailed Implementation

[0024] Surprisingly, it has been found that polymers with a weight-average molecular weight M > 500,000 Daltons have been used as dispersants compared to conventional dispersants. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA Furthermore, carboxyalkyl galactomannans (preferably carboxymethyl locust bean gum) with a mannose to galactose ratio of >2:1 provide good speckling and film-forming properties on glassware and plastic cups, while also having the benefit of improving the overall sustainability of dishwashing detergent formulations (i.e., being of biological origin and exhibiting improved biodegradability relative to conventional dispersant polymers such as polyaspartic acid).

[0025] Unless otherwise specified, ratios, percentages, parts, etc., are all by weight. Weight percentages (or % by weight) in the composition are percentages of dry weight, i.e., excluding any water that may be present in the composition. The percentage of monomer units in the polymer is a percentage of dry weight (i.e., excluding any water present in the polymer emulsion).

[0026] As used herein, unless otherwise specified, the phrase "molecular weight" or MW refers to the weight-average molecular weight as measured in a conventional manner using gel permeation chromatography (GPC) and conventional standards, such as polystyrene molecular weight standards. GPC techniques are discussed in detail in *Modern Size-Exclusion Liquid Chromatography – Practice of Gel Permeation and Gel Filtration Chromatography*, 2nd Edition, AM Striegel, WW Yau, JJ Kirkland, DD Bly; John Wiley & Sons, Inc. 2009. Molecular weights are reported in Daltons or, equivalently, g / mol.

[0027] As used herein and in the appended claims, the term "DS" CA"" refers to the number of carboxyl-substituted OH groups in each dehydrated glucose unit of carboxyl galactomannan, determined by a non-aqueous titration method as described in ASTM D1439-22, which is specifically formulated for carboxymethyl cellulose. However, the same principle applies to carboxyl hydroxyalkyl guar gum. The crude polymer first undergoes purification to remove any small molecule impurities containing carboxylates, including but not limited to residual sodium chloroacetate, sodium glycolate, sodium acetate, and sodium citrate. An accurately weighed amount of the purified polymer is first refluxed in excess glacial acetic acid, and the resulting sodium acetate is titrated with perchloric acid, a strong acid. Crystal violet is used as an indicator and changes from purple / blue to green by the titrant at the endpoint.

[0028] Preferably, the dishwashing detergent formulation of the present invention comprises: a builder (based on the dry weight of the dishwashing detergent formulation, preferably, 1% to 97% by weight (more preferably, 10% to 98.5% by weight; most preferably, 25% to 96% by weight) of a builder) (preferably, wherein the builder comprises at least one of carbonate, bicarbonate, citrate, and silicate); a nonionic surfactant (based on the dry weight of the dishwashing detergent formulation, preferably, 0.2% to 15% by weight (more preferably, 0.5% to 10% by weight; most preferably, 1.5% to 8.5% by weight) of a nonionic surfactant); and a carboxyl galactomannan with a mannose to galactose ratio >2:1 (based on the dry weight of the dishwashing detergent formulation, preferably, 0.2% to 15% by weight (more preferably, 1% to 10% by weight; most preferably, 2.5% to 7.5% by weight) of carboxyl galactomannan); wherein the weight average molecular weight M of the carboxyl galactomannan is... W >500,000 Daltons (preferably, 600,000 Daltons to 2,750,000 Daltons; more preferably, 750,000 Daltons to 2,750,000 Daltons; still more preferably, 1,000,000 Daltons to 2,500,000 Daltons; most preferably, 1,500,000 Daltons to 2,000,000 Daltons) and the degree of carboxyl substitution DS CA The content is 0.1 to 0.54 (preferably, 0.3 to 0.46; more preferably, 0.35 to 0.45; most preferably, 0.38 to 0.41) (preferably, wherein the carboxyl galactomannan is selected from the group consisting of: carboxyl tara gum, carboxyl locust bean gum, carboxyl cinnamon gum and mixtures thereof; more preferably, wherein the carboxyl galactomannan is selected from the group consisting of: carboxyl C 1-4 Alkyl talc, carboxyl C 1-4 Alkyl locust bean gum, carboxyl C 1-4Alkyl cinnamon gum and mixtures thereof; more preferably, wherein the carboxyl galactomannan is selected from the group consisting of: carboxyl C 1-2 Alkyl talc, carboxyl C 1-2 Alkyl locust bean gum, carboxyl C 1-2 Alkyl cinnamon gum and mixtures thereof; more preferably, wherein the carboxyl galactomannan is selected from the group consisting of: carboxymethyl tara gum, carboxymethyl locust bean gum, carboxymethyl cinnamon gum and mixtures thereof; most preferably, wherein the carboxyl galactomannan is carboxymethyl locust bean gum).

[0029] Preferably, the dishwashing detergent formulation of the present invention comprises a detergent builder, wherein the detergent builder includes at least one selected from carbonates, bicarbonates, citrates, and silicates. More preferably, the dishwashing detergent formulation of the present invention comprises a detergent builder, wherein the detergent builder comprises a mixture of at least two components selected from the group consisting of carbonates, bicarbonates, citrates, and silicates. Most preferably, the dishwashing detergent formulation of the present invention comprises a detergent builder, wherein the detergent builder comprises a mixture of carbonates, citrates, and silicates.

[0030] Preferably, the dishwashing detergent formulation of the present invention comprises: 1% to 97% by weight (preferably 1% to 97% by weight (more preferably 10% to 98.5% by weight; most preferably 25% to 96% by weight) of a detergent builder based on the dry weight of the dishwashing detergent formulation. Preferably, the dishwashing detergent formulation of the present invention comprises: ≥1% by weight (preferably ≥10% by weight; more preferably ≥25% by weight; most preferably ≥40% by weight) of a detergent builder based on the dry weight of the dishwashing detergent formulation. Preferably, the dishwashing detergent formulation of the present invention comprises: ≤95% by weight (preferably ≤90% by weight; more preferably ≤85% by weight; most preferably ≤80% by weight) of a detergent builder based on the dry weight of the dishwashing detergent formulation. The weight percentages of carbonates, citrates, and silicates are based on the actual weight of the salts (including metal ions).

[0031] As used herein and in the appended claims, the term "carbonate" refers to an alkali metal or ammonium salt of carbonate, bicarbonate, and / or sesquicarbonate. Preferably, the carbonate used in the dishwashing detergent formulation (if any) is selected from the group consisting of sodium, potassium, and lithium carbonates (more preferably, sodium or potassium salts; most preferably, sodium salts). More preferably, the carbonate used in the dishwashing detergent formulation (if any) includes at least one of sodium carbonate and sodium bicarbonate. Preferably, when the detergent builder used in the dishwashing detergent formulation of the present invention contains a carbonate, the dishwashing detergent formulation preferably contains: 0% to 97% by weight (preferably, 5% to 75% by weight; more preferably, 10% to 60% by weight; most preferably, 20% to 50% by weight) of carbonate based on the dry weight of the dishwashing detergent formulation.

[0032] As used herein and in the appended claims, the term "citrate" refers to citric acid and alkali metal citrates. Preferably, the citrate used in the dishwashing detergent formulation (if any) is selected from the group consisting of citric acid and citrates of sodium, potassium, and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium). More preferably, the citrate used in the dishwashing detergent formulation (if any) is sodium citrate. Preferably, when the detergent builder used in the dishwashing detergent formulation of the present invention contains citrate, the dishwashing detergent formulation preferably contains: 0% to 97% by weight (preferably, 5% to 75% by weight; more preferably, 10% to 60% by weight; most preferably, 20% to 40% by weight) of citrate based on the dry weight of the dishwashing detergent formulation.

[0033] As used herein and in the appended claims, the term "silicate" refers to an alkali metal silicate. Preferably, the silicate used in the dishwashing detergent formulation (if any) is selected from the group consisting of sodium, potassium, and lithium silicates (more preferably, salts of sodium or potassium; most preferably, salts of sodium). More preferably, the silicate used in the dishwashing detergent formulation (if any) is sodium disilicate. Preferably, the detergent builder used in the dishwashing detergent formulation of the present invention comprises a silicate. Preferably, when the detergent builder used in the dishwashing detergent formulation of the present invention comprises a silicate, the dishwashing detergent formulation preferably comprises: 0% to 97% by weight (preferably, 0.1% to 10% by weight; more preferably, 0.5% to 7.5% by weight; most preferably, 0.75% to 3% by weight) of silicate based on the dry weight of the dishwashing detergent formulation.

[0034] Preferably, the dishwashing formulation of the present invention comprises: 0.2% to 15% by weight (preferably 0.5% to 10% by weight; most preferably 1.5% to 8.5% by weight) of a nonionic surfactant based on the dry weight of the dishwashing formulation. More preferably, the dishwashing formulation of the present invention comprises: 0.2% to 15% by weight (preferably 0.5% to 10% by weight; most preferably 1.5% to 8.5% by weight) of a nonionic surfactant based on the dry weight of the dishwashing formulation; wherein the nonionic surfactant is selected from the group consisting of: polyoxyethylene surfactants, polyalkylene glycol esters, polyoxyethylene derivatives of polyol fatty acid esters, polyalkoxylated polyol fatty acid esters, polyalkoxylated natural fats and oils, polyoxyethylene block copolymers, alkyl polyglucosides, sucrose esters, and mixtures thereof. More preferably, the dishwashing detergent formulation of the present invention comprises: 0.2% to 15% by weight (preferably 0.5% to 10% by weight; most preferably 1.5% to 8.5% by weight) of a nonionic surfactant based on the dry weight of the dishwashing detergent formulation; wherein the nonionic surfactant comprises a fatty alcohol alkoxylate. Most preferably, the dishwashing detergent formulation of the present invention comprises: 0.2% to 15% by weight (preferably 0.5% to 10% by weight; most preferably 1.5% to 8.5% by weight) of a nonionic surfactant based on the dry weight of the dishwashing detergent formulation; wherein the nonionic surfactant is a fatty alcohol alkoxylate according to Formula I.

[0035] (I)

[0036] Where w is an average value of 5 to 100 (preferably 6 to 75; more preferably 7 to 60; most preferably 8 to 50); where R 1 Choose from the following groups: hydrogen and straight-chain or branched C44. 1-20 Alkyl groups (preferably, hydrogen and straight-chain or branched C) 1-20 Alkyl groups; more preferably, hydrogen and straight-chain C 1-20 alkyl groups); where R 2 Choose from the following groups: straight chain or branched chain C 1-20 Alkyl groups and straight or branched C 1-4 Hydroxyalkyl groups (preferably straight-chain or branched C) 1-20 Alkyl groups; more preferably, straight-chain C 1-20 alkyl groups); wherein each R 3 Independently selected from the group consisting of: hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-butyl group, and 2-methyl-2-butyl group (preferably, hydrogen, methyl group, and ethyl group); and provided that R 1 and R2 The total number of carbon atoms in it is 5 to 21 (preferably 6 to 20 carbon atoms; more preferably 7 to 20 carbon atoms).

[0037] Preferably, the dishwashing detergent formulation of the present invention comprises: 0.2% to 15% by weight (preferably 1% to 10% by weight; most preferably 2.5% to 7.5% by weight) of a carboxyl galactomannan with a mannose to galactose ratio of >2:1, based on the dry weight of the dishwashing detergent formulation; wherein the weight average molecular weight M of the carboxyl galactomannan is... W >500,000 Daltons (preferably, 600,000 Daltons to 2,750,000 Daltons; more preferably, 750,000 Daltons to 2,750,000 Daltons; still more preferably, 1,000,000 Daltons to 2,500,000 Daltons; most preferably, 1,500,000 Daltons to 2,000,000 Daltons) and the degree of carboxyl substitution DS CA The content is 0.1 to 0.54 (preferably, 0.3 to 0.46; more preferably, 0.35 to 0.45; most preferably, 0.38 to 0.41) (preferably, wherein the carboxyl galactomannan is selected from the group consisting of: carboxyl tara gum, carboxyl locust bean gum, carboxyl cinnamon gum, and mixtures thereof; more preferably, wherein the carboxyl galactomannan is locust bean gum). More preferably, the dishwashing detergent formulation of the present invention comprises: 0.2% to 15% by weight (preferably, 1% to 10% by weight; most preferably, 2.5% to 7.5% by weight) of mannose to galactose in a ratio of >2:1 based on the dry weight of the dishwashing detergent formulation; wherein the carboxyl galactomannan is selected from the group consisting of: carboxyl C 1-4 Alkyl talc, carboxyl C 1-4 Alkyl locust bean gum, carboxyl C 1-4 Alkyl cinnamon gum and mixtures thereof (preferably, carboxyl C...) 1-4 Alkyl locust bean gum); wherein the weight average molecular weight M of carboxyl galactomannan is W >500,000 Daltons (preferably, 600,000 Daltons to 2,750,000 Daltons; more preferably, 750,000 Daltons to 2,750,000 Daltons; still more preferably, 1,000,000 Daltons to 2,500,000 Daltons; most preferably, 1,500,000 Daltons to 2,000,000 Daltons) and the degree of carboxyl substitution DS CAThe content is 0.1 to 0.54 (preferably, 0.3 to 0.46; more preferably, 0.35 to 0.45; most preferably, 0.38 to 0.41). Still more preferably, the dishwashing detergent formulation of the present invention comprises: 0.2% to 15% by weight (preferably, 1% to 10% by weight; most preferably, 2.5% to 7.5% by weight) of mannose to galactose in a ratio of >2:1 based on the dry weight of the dishwashing detergent formulation; wherein the carboxyl alkyl galactomannan is selected from the group consisting of: carboxyl C 1-2 Alkyl talc, carboxyl C 1-2 Alkyl locust bean gum, carboxyl C 1-2 Alkyl cinnamon gum and mixtures thereof (preferably, carboxyl C...) 1-2 Alkyl locust bean gum); wherein the weight average molecular weight M of carboxyl galactomannan is W >500,000 Daltons (preferably, 600,000 Daltons to 2,750,000 Daltons; more preferably, 750,000 Daltons to 2,750,000 Daltons; still more preferably, 1,000,000 Daltons to 2,500,000 Daltons; most preferably, 1,500,000 Daltons to 2,000,000 Daltons) and the degree of carboxyl substitution DS CA The content is 0.1 to 0.54 (preferably, 0.3 to 0.46; more preferably, 0.35 to 0.45; most preferably, 0.38 to 0.41). Even more preferably, the dishwashing detergent formulation of the present invention comprises: 0.2% to 15% by weight (preferably, 1% to 10% by weight; most preferably, 2.5% to 7.5% by weight) of mannose to galactose in a ratio >2:1 based on the dry weight of the dishwashing detergent formulation; wherein the carboxyalkyl galactomannan is selected from the group consisting of: carboxymethyl tara gum, carboxymethyl locust bean gum, carboxymethyl cinnamon gum, and mixtures thereof (preferably, carboxymethyl locust bean gum); wherein the weight-average molecular weight M of the carboxyalkyl galactomannan is... W >500,000 Daltons (preferably, 600,000 Daltons to 2,750,000 Daltons; more preferably, 750,000 Daltons to 2,750,000 Daltons; still more preferably, 1,000,000 Daltons to 2,500,000 Daltons; most preferably, 1,500,000 Daltons to 2,000,000 Daltons) and the degree of carboxymethyl substitution DS CAThe content is 0.1 to 0.54 (preferably, 0.3 to 0.46; more preferably, 0.35 to 0.45; most preferably, 0.38 to 0.41). Most preferably, the dishwashing detergent formulation of the present invention comprises: 0.2% to 15% by weight (preferably, 1% to 10% by weight; most preferably, 2.5% to 7.5% by weight) of mannose to galactose in a ratio of >2:1 based on the dry weight of the dishwashing detergent formulation; wherein the carboxyalkyl galactomannan is carboxymethyl locust bean gum; wherein the weight average molecular weight M of the carboxymethyl locust bean gum is 0.1 to 0.54 (preferably, 0.3 to 0.46; more preferably, 0.35 to 0.45; most preferably, 0.38 to 0.41). W The content is >500,000 Daltons (preferably, 600,000 Daltons to 2,750,000 Daltons; more preferably, 750,000 Daltons to 2,750,000 Daltons; still more preferably, 1,000,000 Daltons to 2,500,000 Daltons; most preferably, 1,500,000 Daltons to 2,000,000 Daltons) and the degree of carboxymethyl substitution DS CA It is 0.1 to 0.54 (preferably, 0.3 to 0.46; more preferably, 0.35 to 0.45; most preferably, 0.38 to 0.41).

[0038] Preferably, based on the weight of the carboxylgalactomannan, the carboxylgalactomannan has a mannose to galactose ratio >2:1; and also has a nitrogen content of <0.1% by weight (preferably, <0.05% by weight; more preferably, <0.01% by weight; most preferably, <0.001% by weight). More preferably, based on the weight of carboxymethyl locust bean gum, the carboxymethyl locust bean gum has a nitrogen content of <0.1% by weight (preferably, <0.05% by weight; more preferably, <0.01% by weight; most preferably, <0.001% by weight).

[0039] Carboxyalkyl galactomannans with a mannose to galactose ratio >2:1 may optionally contain other functional groups, including nonionic functional groups such as alkoxy and hydroxyalkoxy groups. Examples include methoxy, ethoxy, hydroxyethyl, hydroxypropyl, and hydroxybutyl functional groups.

[0040] The dishwashing detergent formulation of the present invention optionally further comprises: additives. Preferably, the dishwashing detergent formulation of the present invention further comprises additives selected from the group consisting of: dispersant polymers; phosphonates (e.g., hydroxyethylidene diphosphonic acid (HEDP)); alkalinity sources; bleaching agents (e.g., sodium percarbonate, sodium perborate); bleaching activators (e.g., tetraacetylethylenediamine (TAED)); grease cleaning promoters (e.g., poly(ethylene glycol), poly(propylene glycol), propylheptaethyl ether); bleaching catalysts (e.g., manganese(II) acetate, cobalt(II) chloride, bis(TACN) magnesium trioxide diacetate); enzymes (e.g., proteases, amylases, lipases, or cellulases); foam inhibitors; colorants; fragrances; silicates; additional detergent builders; antibacterial agents; preservatives; fillers (e.g., sodium sulfate); deposition control polymers and mixtures thereof. More preferably, the dishwashing detergent formulation of the present invention further comprises an additive selected from the group consisting of: phosphonates (e.g., hydroxyethylidene diphosphonic acid (HEDP)); bleaching agents (e.g., sodium percarbonate, sodium perborate); bleaching activators (e.g., tetraacetylethylenediamine (TAED)); enzymes (e.g., proteases, amylases, lipases, or cellulases); grease cleaning promoters (e.g., poly(ethylene glycol), poly(propylene glycol), propylheptaethyl ether); and fillers (e.g., sodium sulfate). Most preferably, the dishwashing detergent formulation of the present invention further comprises an additive comprising a phosphonate, wherein the phosphonate comprises hydroxyethylidene diphosphonic acid (HEDP); a bleaching agent, wherein the bleaching agent comprises sodium percarbonate; a bleaching activator, wherein the bleaching activator comprises tetraacetylethylenediamine (TAED); an enzyme, wherein the enzyme comprises proteases and amylases; a grease cleaning promoter, wherein the grease cleaning promoter is poly(ethylene glycol); and a filler, wherein the filler comprises sodium sulfate.

[0041] Preferably, the dishwashing detergent formulation of the present invention optionally further comprises: 0% to 15% by weight (preferably 0% to 10% by weight; more preferably 0% to 7.5% by weight; most preferably 0% to 5% by weight) of phosphonate based on the dry weight of the dishwashing detergent formulation. More preferably, the dishwashing detergent formulation of the present invention comprises: 0% to 15% by weight (preferably 0% to 10% by weight; more preferably 0% to 7.5% by weight; most preferably 0% to 5% by weight) of phosphonate based on the dry weight of the dishwashing detergent formulation; wherein the phosphonate has a weight-average molecular weight of ≤1,000 Daltons. More preferably, the dishwashing detergent formulation of the present invention comprises: 0% to 15% by weight (preferably 0% to 10% by weight; more preferably 0% to 7.5% by weight; most preferably 0% to 5% by weight) of a phosphonate based on the dry weight of the dishwashing detergent formulation; wherein the phosphonate comprises at least one of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts of 1-hydroxyethylidene-1,1-diphosphonic acid. Most preferably, the dishwashing detergent formulation of the present invention comprises: 0% to 15% by weight (preferably 0% to 10% by weight; more preferably 0% to 7.5% by weight; most preferably 0% to 5% by weight) of a phosphonate based on the dry weight of the dishwashing detergent formulation; wherein the phosphonate is selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and its salts.

[0042] Fillers included in dishwashing detergent formulations, whether tablets or powders, are inert, water-soluble substances, typically sodium or potassium salts (e.g., sodium sulfate, potassium sulfate, sodium chloride, potassium chloride). In tablets and powders, fillers are generally present in amounts ranging from 0% to 75% by weight. Fillers included in gel formulations typically include those mentioned for tablets and powders and also include water.

[0043] Fragrances, dyes, foam inhibitors, enzymes and antimicrobial agents generally do not exceed 10% by weight of the dishwashing detergent formulation, and alternatively, not more than 5% by weight.

[0044] The dishwashing detergent formulation of the present invention optionally further comprises an alkalinity source. Suitable alkalinity sources include, but are not limited to, alkali metal carbonates and alkali metal hydroxides, such as sodium carbonate or potassium carbonate, sodium bicarbonate or potassium bicarbonate, sodium sesquicarbonate or potassium sesquicarbonate, sodium hydroxide, lithium hydroxide or potassium hydroxide, or mixtures thereof. Sodium hydroxide is preferred. The amount of alkalinity source in the dishwashing detergent formulation of the present invention (if any) is at least 1% by weight (preferably at least 20% by weight) and at most 80% by weight (preferably at most 60% by weight) based on the dry weight of the dishwashing detergent formulation.

[0045] The dishwashing detergent formulation of the present invention optionally further comprises: a bleach (e.g., sodium percarbonate). The amount of bleach in the dishwashing detergent formulation of the present invention (if any) is based on the dry weight of the dishwashing detergent formulation, preferably a concentration of 1% to 25% by weight (more preferably, 5% to 20% by weight).

[0046] The dishwashing detergent formulation of the present invention optionally further comprises a bleaching activator (e.g., tetraacetylethylenediamine (TAED)). The amount of bleaching activator in the dishwashing detergent formulation of the present invention (if any) is based on the dry weight of the dishwashing detergent formulation, preferably at a concentration of 1% to 10% by weight (more preferably, 2.5% to 7.5% by weight).

[0047] Preferably, the dishwashing detergent formulation of the present invention comprises: <1% by weight (preferably, <0.5% by weight; more preferably, <0.2% by weight; still more preferably, <0.1% by weight; even more preferably, <0.01% by weight; most preferably, <detectable limit) of phosphate based on the dry weight of the dishwashing detergent formulation. Preferably, the dishwashing detergent formulation of the present invention is phosphate-free.

[0048] Preferably, the dishwashing detergent formulation of the present invention comprises: a detergent builder, based on the dry weight of the dishwashing detergent formulation, <1% by weight (preferably <0.5% by weight; more preferably <0.2% by weight; still more preferably <0.1% by weight; even more preferably <0.01% by weight; most preferably <detectable limit), the detergent builder being selected from the group consisting of: hypozinotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinate-aspartic acid-diacetic acid; N,N'-ethylenediaminedisuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; β-alanine diacetic acid; polyaspartic acid; salts thereof; and mixtures thereof. Most preferably, the dishwashing detergent formulation of the present invention contains 0% by weight of a builder selected from the group consisting of: hypozinotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinate-aspartic acid-diacetic acid; N,N'-ethylenediaminedisuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; β-alanine diacetic acid; polyaspartic acid; their salts and mixtures thereof.

[0049] Preferably, the dishwashing detergent formulation of the present invention comprises ≤0.4% by weight (preferably <0.3% by weight; more preferably <0.2% by weight; still more preferably <0.1% by weight; even more preferably <0.01% by weight; still more preferably <0.001% by weight; most preferably, less than the detectable limit) of urea based on the dry weight of the dishwashing detergent formulation. Preferably, the dishwashing detergent formulation of the present invention is urea-free.

[0050] Preferably, the pH of the dishwashing detergent formulation of the present invention (1% by weight in water) is at least 9 (preferably ≥10; more preferably ≥11.5). Preferably, the pH of the dishwashing detergent formulation of the present invention (1% by weight in water) is not greater than 13.

[0051] Preferably, the dishwashing detergent formulation of the present invention can be formulated into any typical form, for example, as tablets, powders, blocks, single-agent formulations, sachets, pastes, liquids, or gels. More preferably, the dishwashing detergent formulation of the present invention is formulated as a solid, for example, as tablets, granules, powders, blocks, or pastes. Most preferably, the dishwashing formulation of the present invention is formulated as granules or powders.

[0052] Preferably, the dishwashing detergent formulation of the present invention is anhydrous. As used herein and in the appended claims, the term "anhydrous" means that the dishwashing detergent formulation contains less than 6% by weight (preferably, <5% by weight; more preferably, <2.5% by weight; still more preferably, <2% by weight; even more preferably, <1% by weight) of water based on the weight of the dishwashing detergent formulation.

[0053] The dishwashing detergent formulation of the present invention can be used to clean utensils such as glasses, plastic cups, plates, dishes, and cookware in automatic dishwashing machines.

[0054] Preferably, the dishwashing detergent formulation of the present invention is suitable for use under typical operating conditions. For example, when used in an automatic dishwashing machine, the typical water temperature during the washing process is preferably 20°C to 85°C, preferably 30°C to 70°C. The typical concentration of the dishwashing detergent formulation, as a percentage of the total liquid in the dishwashing machine, is preferably 0.1% to 1% by weight, preferably 0.2% to 0.7% by weight. By selecting appropriate product form and addition time, the dishwashing detergent formulation of the present invention can be present in pre-wash, main wash, penultimate rinse, final rinse, or any combination of these cycles.

[0055] Preferably, the method of cleaning articles in the automatic dishwashing machine of the present invention includes: providing at least one soiled article (e.g., cookware, baking utensils, tableware, plates, flatware, glassware and / or plasticware; preferably, glass cups and plastic cups); providing a dishwashing detergent formulation of the present invention selected based on its ability to prevent the formation of phosphonate scale on the at least one soiled article; and applying the dishwashing detergent formulation to the at least one soiled article (preferably in an automatic dishwashing machine) to provide a clean article.

[0056] Some embodiments of the present invention will now be described in detail in the following examples.

[0057] Substitutability The following examples report measurements were performed according to a non-aqueous titration method as described in ASTM D1439-15, which is specifically designed for carboxymethyl cellulose. However, the same principle applies to the measurement of the degree of carboxymethyl substitution in carboxyalkyl galactomannans (e.g., carboxymethyl acacia gum). Approximately 1.0 g of carboxyalkyl galactomannan (e.g., carboxymethyl acacia gum) (measured to the nearest 0.1 mg) was first mixed with 75 mL of glacial acetic acid and stirred under reflux for 2 hours. The mixture was then cooled to room temperature and the resulting sodium acetate was titrated with perchloric acid (0.1 N, in acetic acid) as a strong acid. Crystal violet was used as an indicator and changed from purple / blue to green by the titrant at the endpoint. Measurements were performed in duplicate, with the degree of substitution DS determined for each run. CA And report the average value.

[0058] Weight-average molecular weight M W The following examples report the determination using gel permeation chromatography (GPC). An aqueous sample of the product polymer for GPC analysis was prepared at a concentration of approximately 2 mg / mL in 20 mM aqueous phosphate buffer at pH 7. Separation was performed on a Waters UPLC system equipped with a refractive index detector, using the same phosphate buffer as the mobile phase. A column array consisting of a TOSOH Bioscience TSKgel G2500PWxl 7.8 mm ID × 30 cm, 7 µm column and a TOSOH Bioscience TSKgel GMPWxl 7.8 mm ID × 30 cm, 13 µm column was used. The flow rate was maintained at 1.0 mL / min, and the column temperature was maintained at 35 °C. The results were expressed as peak molecular weight (M). p Calibration was performed using narrow-band polyacrylic acid standards ranging from 216 g / mol to 1,100,000 g / mol, fitted with a quadratic calibration curve. Standards 1-15 are available from American Polymer Standards, and standard 16 (M...) p=216 g / mol AA trimer) was prepared internally. The flow rate was 1.0 mL / min, and the column temperature was maintained at 35 °C. The weight-average molecular weight (Mn) of the exemplary carboxymethylated galactomannan polymer was calculated using Empower software version 3 (Waters Corporation). W ).

[0059] Synthesis S1: Carboxymethyl Locust Bean Gum

[0060] A 500 mL four-necked flask was equipped with a glass rod pusher connected to a Teflon blade and driven by a top-mounted mechanical stirrer, a condenser, and a thermocouple connected to a J-KEM temperature controller and providing input to the heating mantle. First, locust bean gum powder (45.08 g, active material corrected for volatiles and ash content, G0753 grade from Sigma Aldrich), sodium chloroacetate (13.01 g), anhydrous isopropanol (288.60 g), and deionized water (72.27 g) were added to the flask. The contents of the flask were stirred to provide good mixing, as indicated by small eddies at the surface of the contents, and a nitrogen layer was applied to remove entrained air. After one hour, a 50% by weight aqueous solution of sodium hydroxide (12.28 g) was added dropwise to the contents of the flask over approximately five minutes using a syringe. After adding the sodium hydroxide solution, the contents of the flask were stirred at ambient temperature for ten minutes. The temperature setpoint on the J-KEM temperature controller was then raised to 70°C. At 70°C, the flask contents were allowed to equilibrate for two and a half hours. The flask contents were then cooled to ambient temperature in an ice-water bath under a continuous nitrogen flow, and glacial acetic acid (6.28 g) was added dropwise to quench the reaction. After holding for ten minutes, the flask contents were transferred to a sintered Buchner funnel and washed three times with a mixture of anhydrous isopropanol (360 g) and water (90 g), twice with a mixture of anhydrous isopropanol (405 g) and water (45 g), and twice with anhydrous isopropanol (450 g). The washed polymer was then dried overnight in a vacuum oven at 50°C, ground with a mortar and pestle, and passed through a metal sieve (US 30, sieve size: 600 microns). This procedure yielded 58.85 g of dried product powder. The product polymer was then analyzed, with a volatile content of 5.73 g / L and a weight-average molecular weight M. W 1,767,000 Daltons, as measured by aqueous gel permeation chromatography; and the degree of carboxymethyl substitution DS. CA : 0.395, as measured by perchloric acid titration.

[0061] Comparative Examples CF1-CF2 and Example F1: Dishwashing Detergent

[0062] Dishwashing compositions were prepared in each of Comparative Examples CF1-CF2 and Example F1, which have the component formulations identified in Table 1.

[0063] Table 1

[0064]

[0065] Procedure for preparing food stains

[0066] Prepare the food stains described in Table 2 using the following procedure.

[0067] a) Boil the water.

[0068] b) Mix the instant gravy, benzoic acid, and starch in a paper cup; then add the mixture to boiling water.

[0069] c) Add milk and margarine to the product of (b).

[0070] d) Cool the product from (c) to about 40°C, and then add the mixture to a kitchen mixer (Polytron).

[0071] e) Combine the egg yolk, ketchup, and mustard in another paper cup and mix with a spoon.

[0072] f) The product of (e) is added to the mixture of (d) in the mixer under continuous stirring.

[0073] g) Stir the product from (f) in a mixer for 5 minutes.

[0074] h) Frozen food dirt mixture from (g).

[0075] i) At the start of the main wash, add 50g of frozen sludge to the dishwasher.

[0076] Table 2

[0077]

[0078] Dishwashing test conditions

[0079] Machine: Miele SS-ADW, model G1223SC Labor Prog 6. Washing was performed at 65°C for 20 minutes, followed by two rinse cycles with rinsing water at 65°C and a final 30-minute drying step. After the drying cycle was completed, the dishwasher door was left open for 30 minutes to allow steam to evaporate. Water: The initial water supplied to the dishwasher had a target conductivity of 1,160 μs / cm to 1,250 μs / cm. Food stains: 50 g of the composition specified in Table 2 was introduced into a cup of chilled washing liquid. Each dishwasher composition from Comparative Examples CF1-CF2 and Example F1 was tested. Food stains were added at the start of the wash cycle. Test detergents were also added to the dishwasher at the start of the wash cycle. Each test detergent was administered at a dose of 15.3 g (based on solids) per wash. The number of wash cycles used to generate film and spots in this experiment was 15.

[0080] Film formation and spot formation assessment

[0081] After each of the 15 washing cycles under the above dishwashing test conditions, the glass (Schott Zwiesel Tritan) was... ® Long drinking glass, wine glass (Stolzle) ™ Stemless red wine glass) and plastic cup (Clear Lido from Cambro) ® The products were dried in the open air. After drying, film formation and speckle formation grades were determined by trained evaluators by observing the glass, wine glass, and plastic cups from below in a lightbox with controlled illumination. Film formation and speckle formation on the glass, wine glass, and plastic cups were evaluated according to ASTM methods, ranging from 1 (no film / spots) to 5 (heavy film / spots). As reported in Table 3, the mean values ​​for film formation and speckle formation were determined to be 1 to 5. The values ​​for total spots, total film, and total gloss (i.e., total spots + total film) for each dishwashing composition are also reported in Table 3.

[0082] Table 3

[0083]

Claims

1. A dishwashing detergent formulation, said dishwashing detergent formulation comprising: Builder; Nonionic surfactants; and Carboxyalkyl galactomannans with a mannose to galactose ratio >2:1; and wherein said carboxyalkyl galactomannans has a weight-average molecular weight M >500,000 Daltons. W and a degree of carboxyl substitution of 0.1 to 0.54 DS CA .

2. The dishwashing detergent formulation according to claim 1, wherein the dishwashing detergent formulation further comprises a phosphonate crystal growth inhibitor.

3. The dishwashing detergent formulation of claim 2, wherein the carboxyl galactomannan is selected from the group consisting of: carboxyl tara gum, carboxyl locust bean gum, carboxyl cinnamon gum, and mixtures thereof; and wherein, based on the weight of the dishwashing detergent formulation, the dishwashing detergent formulation contains ≤0.4% by weight of urea.

4. The dishwashing detergent formulation according to claim 3, wherein the dishwashing detergent formulation is anhydrous solid.

5. The dishwashing detergent formulation according to claim 4, wherein the detergent aid is selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof.

6. The dishwashing detergent formulation of claim 5, wherein, based on the dry weight of the dishwashing formulation, the dishwashing formulation comprises less than 0.1% by weight of phosphate as measured by elemental phosphorus.

7. The dishwashing detergent formulation according to claim 6, wherein, based on the dry weight of the dishwashing detergent formulation, the dishwashing formulation contains 0% by weight of a builder, the builder being selected from the group consisting of: hypozinotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinate-aspartic acid-diacetic acid; N,N'-ethylenediaminedisuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; β-alanine diacetic acid; polyaspartic acid; salts thereof; and mixtures thereof.

8. The dishwashing detergent formulation according to claim 7, further comprising an additive selected from the group consisting of bleaching agents, bleaching activators, enzymes, fillers, and mixtures thereof.

9. The dishwashing detergent formulation of claim 8, wherein the carboxyl galactomannan has a weight-average molecular weight of 600,000 Daltons to 2,750,000 Daltons and a degree of carboxyl substitution of 0.3 to 0.46 DS. CA Carboxymethyl locust bean gum.

10. A method for cleaning items in an automatic dishwashing machine, the method comprising: Provide at least one soiled item; Provides a dishwashing detergent formulation selected based on its ability to prevent the formation of phosphonate scale on the at least one soiled article, wherein the dishwashing detergent formulation is selected according to claim 1; as well as The selected dishwashing detergent formulation is applied to the at least one soiled item to provide a clean item.

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