Carboxyalkyl locust bean gum dishwashing detergent

Abstract

A dishwashing detergent formulation is provided including a builder; a nonionic surfactant; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan has a weight average molecular weight, MW, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54.

Description

CARBOXY ALKYL LOCUST BEAN GUM DISHWASHING DETERGENT

[0001] The present invention relates to a dishwashing detergent formulation. In particular, the present invention relates to a dishwashing detergent formulation comprising: a builder; a nonionic surfactant; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2: 1 ; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54.

[0002] Dishwashing compositions are generally recognized as a class of detergent compositions distinct from those used for fabric washing or water treatment. Dishwashing compositions are expected by users to produce a film-free appearance on washed articles after a complete cleaning cycle.

[0003] Phosphate-free dishwashing compositions are increasingly desirable. Phosphate-free dishwashing compositions typically rely on non-phosphate builders, such as salts of citrate, carbonate, silicate, disilicate, bicarbonate, aminocarboxylate, and others to sequester calcium and magnesium from hard water, and upon drying, leave an insoluble visible deposit.

[0004] A family of polycarboxylate copolymers and their use as builders in detergent compositions and rinse aid compositions is disclosed by Christopher et al. in U.S. Patent No. 5,431,846 for use in the final rinse step of a dish or warewashing machine. Christopher et al. disclose block copolymers comprising from 20 to 95 mole % of monomer units derived from itaconic acid or a homologue thereof and from 5 to 80 mole % of monomer units derived from vinyl alcohol or a lower vinyl ester are excellent binders of divalent or polyvalent metals and are useful as potentially biodegradable builders in detergent compositions as well as in machine dishwashing compositions and anti-scaling rinse compositions.

[0005] A family of terpolymers and their use, among other things, as dispersants is disclosed by Swift et al in U.S. Patent No. 5,191,048. Swift et al teach a terpolymer comprising as polymerized units from about 15 to 55 mole percent of at least one first monomer selected from the group consisting of vinyl acetate, vinyl ethers and vinyl carbonates, from about 10 to 70 mole percent of at least one second monomer of an ethylenically unsaturated monocarboxylic acid, and from about 15 to 55 mole percent of at least one third monomer of an anhydride of a dicarboxylic acid and wherein said terpolymer is formed in a non-aqueous system such that less than about one more percent of the monomers are hydrolyzed during said polymerization.

[0006] Notwithstanding there remains a need for new dispersant polymers for use in dishwashing formulations. In particular, there remains a need for new dispersant polymersfor use in dishwashing formulations, wherein the dispersant polymers provide effective low filming performance; are biosourced and biodegradable.

[0007] The present invention provides a dishwashing detergent formulation comprising: a builder; an nonionic surfactant; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54.

[0008] The present invention provides a dishwashing detergent formulation comprising: a builder; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxy alkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54.

[0009] The present invention provides a dishwashing detergent formulation comprising: a builder; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxy alkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxyalkyl tara gum, a carboxyalkyl locust bean gum, a carboxyalkyl cassia gum and mixtures thereof; and wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea.

[0010] The present invention provides a dishwashing detergent formulation comprising: a builder; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxy alkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxyalkyl tara gum, a carboxyalkyl locust bean gum, a carboxyalkyl cassia gum and mixtures thereof; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0011] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growthinhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxyalkyl tara gum, a carboxyalkyl locust bean gum, a carboxyalkyl cassia gum and mixtures thereof; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0012] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1 ; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxyalkyl tara gum, a carboxyalkyl locust bean gum, a carboxyalkyl cassia gum and mixtures thereof; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; wherein the dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the dishwashing formulation, of phosphate, measured as elemental phosphorus; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0013] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1 ; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxyalkyl tara gum, a carboxyalkyl locust bean gum, a carboxyalkyl cassia gum and mixtures thereof; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; wherein the dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the dishwashing formulation, of phosphate, measured as elemental phosphorus; wherein the dishwashing formulation contains 0 wt%, based on the dry weight of the dishwashing detergent formulation, of builders selected fromthe group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid;3-hydroxy-2,2’-iminodissuccinate; S,S -ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’ -ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta- alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0014] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growth inhibitor; an additive selected from the group consisting of a bleaching agent, a bleach activator, an enzyme, a filler, and mixtures thereof; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0. 1 to 0.54; wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxyalkyl tara gum, a carboxyalkyl locust bean gum, a carboxyalkyl cassia gum and mixtures thereof; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; wherein the dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the dishwashing formulation, of phosphate, measured as elemental phosphorus; wherein the dishwashing formulation contains 0 wt%, based on the dry weight of the dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2’-iminodissuccinate;S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’ -ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta-alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0015] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growth inhibitor; an additive selected from the group consisting of a bleaching agent, a bleach activator, an enzyme, a filler, and mixtures thereof; and a carboxyalkyl galactomannanhaving a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan is a carboxymethyl locust bean gum having a weight average molecular weight of 600,000 to 2,750,000 Daltons and a carboxymethyl degree of substitution, DSCA, of 0.3 to 0.46; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; wherein the dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the dishwashing formulation, of phosphate, measured as elemental phosphorus; wherein the dishwashing formulation contains 0 wt%, based on the dry weight of the dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid;3-hydroxy-2,2’-iminodissuccinate; S,S -ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’ -ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta- alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0016] The present invention provides a dishwashing detergent formulation comprising: a builder; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxy alkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; and wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea.

[0017] The present invention provides a dishwashing detergent formulation comprising: a builder; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxy alkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0018] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1 ; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of>500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0019] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1 ; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; wherein the dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the dishwashing formulation, of phosphate, measured as elemental phosphorus; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0020] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growth inhibitor; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; wherein the dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the dishwashing formulation, of phosphate, measured as elemental phosphorus; wherein the dishwashing formulation contains 0 wt%, based on the dry weight of the dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid;3-hydroxy-2,2’-iminodissuccinate; S,S -ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’ -ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta- alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0021] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growth inhibitor; an additive selected from the group consisting of a bleaching agent, a bleach activator, an enzyme, a filler, and mixtures thereof; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; wherein the dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the dishwashing formulation, of phosphate, measured as elemental phosphorus; wherein the dishwashing formulation contains 0 wt%, based on the dry weight of the dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2’-iminodissuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’-ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta-alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0022] The present invention provides a dishwashing detergent formulation comprising: a builder, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof; an nonionic surfactant; a phosphonate crystal growth inhibitor; an additive selected from the group consisting of a bleaching agent, a bleach activator, an enzyme, a filler, and mixtures thereof; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan is a carboxymethyl locust bean gum having a weight average molecular weight of 600,000 to 2,750,000 Daltons and a carboxymethyl degree of substition, DSCA, of 0.3 to 0.46; wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea; wherein the dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the dishwashing formulation, of phosphate, measured as elemental phosphorus; wherein the dishwashing formulation contains 0 wt%, based on the dry weight of the dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid;diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid;3-hydroxy-2,2’-iminodissuccinate; S,S -ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’ -ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta- alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof; and wherein the dishwashing detergent formulation is an anhydrous solid.

[0023] The present invention provides a method of cleaning an article in an automatic dishwashing machine, comprising: providing at least one soiled article; providing a dishwashing detergent formulation selected based on an ability to impede the formation of phosphonate scale on the at least one soiled article, wherein the dishwashing detergent formulation is selected to be 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 DESCRIPTION

[0024] Surprisingly, it has been found that, a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1 (preferably, carboxymethyl locust bean gum) having a weight average molecular weight, Mw, > 500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54, provides good spotting and filming performance on glassware and plastic tumblers compared to conventional dispersant polymers, while having the benefit of improving the overall sustainability of the dishwashing detergent formulation (i.e., being biosourced and exhibiting improved biodegradability relative to conventional dispersant polymers such as polyaspartic acid).

[0025] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight. Weight percentages (or wt%) in the composition are percentages of dry weight, i.e., excluding any water that may be present in the composition. Percentages of monomer units in the polymer are percentages of dry weight, i.e., excluding any water present in a polymer emulsion.

[0026] As used herein, unless otherwise indicated, the phrase "molecular weight" or MW refers to the weight average molecular weight as measured in a conventional manner with 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, Second Edition, A.M. Striegel, W. W. Yau, J. J. Kirkland, D. D. Bly; John Wiley & Sons, Inc. 2009. Molecular weights are reported herein in units of Daltons, or equivalently, g / mol.

[0027] The term “DSCA” as used herein and in the appended claims means the number of carboxyalkyl substituted OH groups per anhydroglycose unit in a carboxyalkyl galactomannan, as determined by the nonaqueous titration method as described in ASTM DI 439-22, which was written specifically for carboxymethyl cellulose. Notwithstanding, the same principle applies for carboxyalkyl hydroxyalkyl guar. The crude polymer first went through purification to remove any carboxylate-containing small-molecule impurities including but not limited to residual sodium chloroacetate, sodium glycolate, sodium acetate, and sodium citrate. A precisely weighted amount of the purified polymer was first refluxed in an excessive amount of glacial acetic acid, and the formed sodium acetate was titrated with perchloric acid as a strong acid. Crystal violet served as the indicator, and at the endpoint the titrate changed from violet / blue to green.

[0028] Preferably, the dishwashing detergent formulation of the present invention, comprises: a builder (preferably, 1 to 97 wt% (more preferably 10 to 98.5 wt%; most preferably, 25 to 96 wt%), based on dry weight of the dishwashing detergent formulation, of the builder)(preferably, wherein the builder includes at least one of a carbonate, a bicarbonate, a citrate and a silicate); a nonionic surfactant (preferably, 0.2 to 15 wt% (more preferably, 0.5 to 10 wt%; most preferably, 1.5 to 8.5 wt%), based on dry weight of the dishwashing detergent formulation, of the nonionic surfactant); and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1 (preferably, 0.2 to 15 wt% (more preferably, 1 to 10 wt%; most preferably, 2.5 to 7.5 wt%), based on dry weight of the dishwashing detergent formulation, of a carboxyalkyl galactomannan); wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of > 500,000 Daltons (preferably, 600,000 to 2,750,000 Daltons; more preferably, 750,000 to 2,750,000 Daltons; still more preferably, 1,000,000 to 2,500,000 Daltons; most preferably, 1,500,000 to 2,000,000 Daltons) and a carboxyalkyl degree of substitution, DSCA, of 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 carboxyalkyl galactomannan is selected from the group consisting of a carboxyalkyl tara gum, a carboxyalkyl locust bean gum, a carboxyalkyl cassia gum and mixtures thereof; more preferably, wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxy C1-4 alkyl tara gum, a carboxy C1-4 alkyl locust bean gum, a carboxy C1-4 alkyl cassia gum and mixtures thereof; still more preferably, wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxy C1-2 alkyl tara gum, a carboxy C1-2 alkyl locust bean gum, a carboxy C1-2 alkyl cassia gum and mixtures thereof; yet more preferably, wherein the carboxyalkyl galactomannan isselected from the group consisting of a carboxymethyl tara gum, a carboxymethyl locust bean gum, a carboxymethyl cassia gum and mixtures thereof; most preferably, wherein the carboxy alkyl galactomannan is a carboxymethyl locust bean gum).

[0029] Preferably, the dishwashing detergent formulation of the present invention, comprises a builder, wherein the builder comprises at least one of a carbonate, a bicarbonate, a citrate and a silicate. More preferably, the dishwashing detergent formulation of the present invention, comprises a builder, wherein the builder comprises a mixture of at least two components selected from the group consisting of a carbonate, a bicarbonate, a citrate and a silicate. Most preferably, the dishwashing detergent formulation of the present invention, comprises a builder, wherein the builder comprises a mixture of a carbonate, a citrate and a silicate.

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

[0031] The term "carbonate(s)" as used herein and in the appended claims refers to alkali metal or ammonium salts of carbonate, bicarbonate and / or sesquicarbonate. Preferably, the carbonate used in the dishwashing detergent formulation (if any) is selected from the group consisting of carbonate salts of sodium, potassium and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium). 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 builder used in the dishwashing detergent formulation of the present invention includes carbonate, the dishwashing detergent formulation preferably, comprises 0 to 97 wt% (preferably, 5 to 75 wt%; more preferably, 10 to 60 wt%; most preferably 20 to 50 wt%), based on dry weight of the dishwashing detergent formulation, of carbonate.

[0032] The term "citrate(s)" as used herein and in the appended claims 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 citrate salts 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 builder used in the dishwashing detergent formulation of the present invention includes citrate, the dishwashing detergent formulation preferably, comprises 0 to 97 wt% (preferably, 5 to 75 wt%; more preferably, 10 to 60 wt%; most preferably 20 to 40 wt%), based on dry weight of the dishwashing detergent formulation, of the citrate.

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

[0034] Preferably, the dishwashing formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; most preferably, 1.5 to 8.5 wt%), based on dry weight of the dishwashing detergent formulation, of a nonionic surfactant. More preferably, the dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; most preferably, 1 .5 to 8.5 wt%), based on dry weight of the dishwashing detergent formulation, of a nonionic surfactant; wherein the non-ionic surfactant is selected from the group consisting of polyoxyalkylene surfactants, polyalkylene glycol esters, polyoxyethylene derivatives of fatty acid esters of polyhydric alcohols, fatty acid esters of polyalkoxylated polyhydric alcohols, polyalkoxylated natural fats and oils, polyalkylene oxide block copolymers, alkyl polyglucosides, sucrose esters and mixtures thereof. Still more preferably, the dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; most preferably, 1.5 to 8.5 wt%), based on dry weight of the dishwashing detergent formulation, of a nonionicsurfactant; wherein the non-ionic surfactant includes a fatty alcohol alkoxylate. Most preferably, the dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; most preferably, 1.5 to 8.5 wt%), based on dry weight of the dishwashing detergent formulation, of a nonionic surfactant; wherein the non-ionic surfactant is a fatty alcohol alkoxylate according to formula Iwherein u is an average of 5 to 100 (preferably, 6 to 75; more preferably, 7 to 60; most preferably, 8 to 50); wherein R1is selected from the group consisting of a hydrogen and a linear or branched C1-20 alkyl group (preferably, a hydrogen, and a linear or branched C1-20 alkyl group; more preferably, a hydrogen and a linear C1-20 alkyl group); wherein R2is selected from the group consisting of a linear or branched Ci-20 alkyl group and a linear or branched C1-4 hydroxyalkyl group (preferably, a linear or branched C1-20 alkyl group; more preferably, a linear Ci-20 alkyl group); wherein each R3is independently selected from the group consisting of a hydrogen, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-butyl group and a 2-methyl-2-butyl group (preferably, a hydrogen, a methyl group and an ethyl group); and with the proviso that sum of the total number of carbon atoms in R1and R2is 5 to 21 (preferably, 6 to 20 carbon atoms; more preferably, 7 to 20 carbon atoms).

[0035] Preferably, the dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 1 to 10 wt%; most preferably, 2.5 to 7.5 wt%), based on dry weight of the dishwashing detergent formulation, of a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of > 500,000 Daltons (preferably, 600,000 to 2,750,000 Daltons; more preferably, 750,000 to 2,750,000 Daltons; still more preferably, 1,000,000 to 2,500,000 Daltons; most preferably, 1,500,000 to 2,000,000 Daltons) and a carboxyalkyl degree of substitution, DSCA, of 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 carboxyalkyl galactomannan is selected from the group consisting of a carboxyalkyl tara gum, a carboxyalkyl locust bean gum, a carboxyalkyl cassia gum and mixtures thereof; more preferably, wherein the a carboxyalkyl galactomannan is a locust bean gum). More preferably, the dishwashing detergent formulation of the present invention, comprises: 0.2 to15 wt% (preferably, 1 to 10 wt%; most preferably, 2.5 to 7.5 wt%), based on dry weight of the dishwashing detergent formulation, of a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1 ; wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxy Ci-4 alkyl tara gum, a carboxy Ci-4 alkyl locust bean gum, a carboxy C1-4 alkyl cassia gum and mixtures thereof (preferably, a carboxy C1-4 alkyl locust bean gum); wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of > 500,000 Daltons (preferably, 600,000 to 2,750,000 Daltons; more preferably, 750,000 to 2,750,000 Daltons; still more preferably, 1 ,000,000 to 2,500,000 Daltons; most preferably, 1,500,000 to 2,000,000 Daltons) and a carboxyalkyl degree of substitution, DSCA, of 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 wt% (preferably, 1 to 10 wt%; most preferably, 2.5 to 7.5 wt%), based on dry weight of the dishwashing detergent formulation, of a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxyalkyl galactomannan is selected from the group consisting of a carboxy C1-2 alkyl tara gum, a carboxy C1-2 alkyl locust bean gum, a carboxy C1-2 alkyl cassia gum and mixtures thereof (preferably, a carboxy C1-2 alkyl locust bean gum); wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of > 500,000 Daltons (preferably, 600,000 to 2,750,000 Daltons; more preferably, 750,000 to 2,750,000 Daltons; still more preferably, 1,000,000 to 2,500,000 Daltons; most preferably, 1,500,000 to 2,000,000 Daltons) and a carboxyalkyl degree of substitution, DSCA, of 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). Yet more preferably, the dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 1 to 10 wt%; most preferably, 2.5 to 7.5 wt%), based on dry weight of the dishwashing detergent formulation, of a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; wherein the carboxy alkyl galactomannan is selected from the group consisting of a carboxymethyl tara gum, a carboxymethyl locust bean gum, a carboxymethyl cassia gum and mixtures thereof (preferably, a carboxymethyl locust bean gum); wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of > 500,000 Daltons (preferably, 600,000 to 2,750,000 Daltons; more preferably, 750,000 to 2,750,000 Daltons; still more preferably, 1,000,000 to 2,500,000 Daltons; most preferably, 1,500,000 to 2,000,000 Daltons) and a carboxymethyl degree of substitution, DSCA, of 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 wt% (preferably, 1 to 10wt%; most preferably, 2.5 to 7.5 wt%), based on dry weight of the dishwashing detergent formulation, of a carboxyalkyl galactomannan having a mannose to galactose ratio of >2: 1 ; wherein the carboxyalkyl galactomannan is a carboxymethyl locust bean gum; wherein the carboxymethyl locust bean gum has a weight average molecular weight, Mw, of > 500,000 Daltons (preferably, 600,000 to 2,750,000 Daltons; more preferably, 750,000 to 2,750,000 Daltons; still more preferably, 1,000,000 to 2,500,000 Daltons; most preferably, 1,500,000 to 2,000,000 Daltons) and a carboxymethyl degree of substitution, DSCA, of 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).

[0036] Preferably, the carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1; also has a nitrogen content of < 0.1 wt% (preferably, < 0.05 wt%; more preferably, < 0.01 wt%; most preferably, < 0.001 wt%), based on weight of the carboxyalkyl galactomannan. More preferably, the carboxymethyl locust bean gum has a nitrogen content of < 0.1 wt% (preferably, < 0.05 wt%; more preferably, < 0.01 wt%; most preferably, < 0.001 wt%), based on weight of the carboxymethyl locust bean gum.

[0037] The carboxy alkyl galactomannan having a mannose to galactose ratio of >2: 1 may optionally contain further functionality including nonionic functionality such as alkoxy and hydroxyalkoxy. Examples include methoxy, ethoxy, hydroxyethyl, hydroxypropyl and hydroxybutyl functionalities.

[0038] The dishwashing detergent formulation of the present invention, optionally further comprises: an additive. Preferably, the dishwashing detergent formulation of the present invention, further comprises: an additive selected from the group consisting of a dispersant polymer; a phosphonate (e.g., hydroxy ethylidene diphosphonic acid (HEDP); an alkalinity source; a bleaching agent (e.g., sodium percarbonate, sodium perborate); a bleach activator (e.g., tetraacetylethylenediamine (TAED)); a grease cleaning booster (e.g., poly(ethylene glycol, polypropylene glycol), propyheptyl ether); a bleach catalyst (e.g., manganese(II) acetate, cobalt(II) chloride, bis(TACN)magnesium trioxide diacetate); an enzyme (e.g., protease, amylase, lipase, or cellulase); a foam suppressant; a coloring agent; a fragrance; a silicate; an additional builder; an antibacterial agent; a preservative; a filler (e.g., sodium sulfate); a deposit control polymer and mixtures thereof. More preferably, the dishwashing detergent formulation of the present invention, further comprises an additive, wherein the additive is selected from the group consisting of a phosphonate (e.g., hydroxy ethylidene diphosphonic acid (HEDP); a bleaching agent (e.g., sodium percarbonate, sodium perborate); a bleach activator (e.g., tetraacetylethylenediamine (TAED)); an enzyme (e.g., protease, amylase, lipase, or cellulase); a grease cleaning booster (e.g., poly(ethylene glycol),poly(propylene glycol), propylheptyl ether); and a filler (e.g., sodium sulfate). Most preferably, the dishwashing detergent formulation of the present invention, further comprises an additive, wherein the additive includes a phosphonate, wherein the phosphonate includes a hydroxy ethylidene diphosphonic acid (HEDP); a bleaching agent, wherein the bleaching agent includes sodium percarbonate; a bleach activator, wherein the bleach activator includes tetraacetylethylenediamine (TAED); an enzyme, wherein the enzyme includes a protease and an amylase; a grease cleaning booster, wherein the grease cleaning booster is a poly(ethylene glycol); and a filler, wherein the filler includes sodium sulfate.

[0039] Preferably, the dishwashing detergent formulation of the present invention optionally further comprises 0 to 15 wt% (preferably, 0 to 10 wt%; more preferably, 0 to 7.5 wt%; most preferably, 0 to 5 wt%), based on dry weight of the dishwashing detergent formulation, of a phosphonate. More preferably, the dishwashing detergent formulation of the present invention comprises 0 to 15 wt% (preferably, 0 to 10 wt%; more preferably, 0 to 7.5 wt%; most preferably, 0 to 5 wt%), based on dry weight of the dishwashing detergent formulation, of a phosphonate; wherein the phosphonate has a weight average molecular weight of < 1 ,000 Daltons. Still more preferably, the dishwashing detergent formulation of the present invention comprises 0 to 15 wt% (preferably, 0 to 10 wt%; more preferably, 0 to 7.5 wt%; most preferably, 0 to 5 wt%), based on dry weight of the dishwashing detergent formulation, of a phosphonate; wherein the phosphonate comprises at least one of 1-hydroxyethylidene- 1,1 -diphosphonic acid (HEDP) and a salt of1 -hydroxyethylidene- 1,1 -diphosphonic acid. Most preferably, the dishwashing detergent formulation of the present invention comprises 0 to 15 wt% (preferably, 0 to 10 wt%; more preferably, 0 to 7.5 wt%; most preferably, 0 to 5 wt%), based on dry weight of the dishwashing detergent formulation, of a phosphonate; wherein the phosphonate is selected from the group consisting of 1-hydroxyethylidene- 1,1 -diphosphonic acid (HEDP) and salts thereof.

[0040] Fillers included in dishwashing detergent formulation 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 typically present in amounts ranging from 0 wt% to 75 wt%. Fillers included in gel formulations typically include those mentioned for use in tablets and powders and also water.

[0041] Fragrances, dyes, foam suppressants, enzymes and antibacterial agents usually total no more than 10 wt%, alternatively no more than 5 wt%, of the dishwashing detergent formulation.

[0042] The dishwashing detergent formulation of the present invention, optionally further comprises: an alkalinity source. Suitable alkalinity sources include, without limitation, alkali metal carbonates and alkali metal hydroxides, such as sodium or potassium carbonate, bicarbonate, sesquicarbonate, sodium, lithium, or potassium hydroxide, or mixtures of the foregoing. Sodium hydroxide is preferred. The amount of alkalinity source in the dishwashing detergent formulation of the present invention (if any) is at least 1 wt% (preferably, at least 20 wt%) and up to 80 wt% (preferably, up to 60 wt%), based on dry weight of the dishwashing detergent formulation.

[0043] The dishwashing detergent formulation of the present invention, optionally further comprises: a bleaching agent (e.g., sodium percarbonate). The amount of the bleaching agent in the dishwashing detergent formulation of the present invention (if any) is preferably at a concentration of 1 to 25 wt% (more preferably, 5 to 20 wt%), based on dry weight of the dishwashing detergent formulation.

[0044] The dishwashing detergent formulation of the present invention, optionally further comprises: a bleach activator (e.g., tetraacetylethylenediamine (TAED)). The amount of the bleach activator in the dishwashing detergent formulation of the present invention (if any) is preferably at a concentration of 1 to 10 wt% (more preferably, 2.5 to 7.5 wt%), based on dry weight of the dishwashing detergent formulation.

[0045] Preferably, the dishwashing detergent formulation of the present invention comprises< 1 wt% (preferably, < 0.5 wt%; more preferably, < 0.2 wt%; still more preferably, < 0.1 wt%; yet still more preferably, < 0.01 wt%; most preferably, < the detectable limit), based on dry weight of the dishwashing detergent formulation, of phosphate. Preferably, the dishwashing detergent formulation of the present invention is phosphate free.

[0046] Preferably, the dishwashing detergent formulation of the present invention comprises< 1 wt% (preferably, < 0.5 wt%; more preferably, < 0.2 wt%; still more preferably, < 0.1 wt%; yet still more preferably, < 0.01 wt%; most preferably, < the detectable limit), based on dry weight of the dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid;3-hydroxy-2,2’-iminodissuccinate; S,S -ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’ -ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta- alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof. Most preferably, the dishwashing detergent formulation of the presentinvention contains 0 wt% of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2’-iminodissuccinate;S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’ -ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta-alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof.

[0047] Preferably, the dishwashing detergent formulation of the present invention comprises < 0.4 wt% (preferably, < 0.3 wt%; more preferably, < 0.2 wt%; still more preferably, < 0.1 wt%; yet more preferably, < 0.01 wt%; still yet more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the dishwashing detergent formulation, of urea. Preferably, the dishwashing detergent formulation of the present invention is urea free.

[0048] Preferably, the dishwashing detergent formulation of the present invention has a pH (at 1 wt% in water) of at least 9 (preferably, > 10; more preferably, > 11.5). Preferably, the dishwashing detergent formulation of the present invention has a pH (at 1 wt% in water) of no greater than 13.

[0049] Preferably, the dishwashing detergent formulation of the present invention can be formulated in any typical form, e.g., as a tablet, powder, block, monodose, sachet, paste, liquid or gel. More preferably, the dishwashing detergent formulation of the present invention is formulated as a solid, e.g., as a tablet, granule, powder, block, paste. Most preferably, the dishwashing formulation of the present invention is formulated as a granule or powder.

[0050] Preferably, the dishwashing detergent formulation of the present invention is anhydrous. The term “anhydrous” as used herein and in the appended claims means that the dishwashing detergent formulation contains less then 6 wt% (preferably, < 5 wt%; more preferably, < 2.5 wt%; still more preferably^ 2 wt%; yet more preferably, < 1 wt%) , based on weight of the dishwashing detergent formulation, of water.

[0051] The dishwashing detergent formulations of the present invention are useful for cleaning ware, such as glasses, plastic tumblers, dishes, and eating and cooking utensils, in an automatic dishwashing machine.

[0052] Preferably, the dishwashing detergent formulation of the present invention are suitable for use under typical operating conditions. For example, when used in an automatic dishwashing machine, typical water temperatures during the washing process preferably arefrom 20 °C to 85 °C, preferably 30 °C to 70 °C. Typical concentrations for the dishwashing detergent formulation as a percentage of total liquid in the dishwasher preferably are from 0.1 to 1 wt%, preferably from 0.2 to 0.7 wt%. With selection of an appropriate product form and addition time, the dishwashing detergent formulations of the present invention may be present in the pre wash, main wash, penultimate rinse, final rinse, or any combination of these cycles.

[0053] Preferably, the method of cleaning an article in an automatic dishwashing machine of the present invention, comprises: providing at least one soiled article (e.g., cookware, bakeware, tableware, dishware, flatware, glassware and / or plasticware; preferably, glasses and plastic tumblers); providing a dishwashing detergent formulation of the present invention selected based on an ability to impede 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 dishwasher) to provide a clean article.

[0054] Some embodiments of the present invention will now be described in detail in the following Examples.

[0055] Degree of substitution: Reported in the following examples was measured following the nonaqueous titration method in ASTM D1439-15, which was written specifically for carboxymethyl cellulose. Notwithstanding, the same principle applies for measuring the degree of carboxymethyl substitution in a carboxyalkyl galactomannan (e.g., carboxymethyl locust bean gum). About 1.0 g of carboxyalkyl galactomannan (e.g., carboxymethyl locust bean gum)(measured to the nearest 0.1 mg) was first mixed with 75 mL of glacial acetic acid and stirred under reflux conditions for 2 hours. The mixture was then cooled to room temperature, and the formed sodium acetate was titrated with perchloric acid (0.1 N in acetic acid) as a strong acid. Crystal violet served as the indicator, and at the endpoint the titrate changed from violet / blue to green. The measurement was carried out in duplicate, the degree of substitution, DSCA, was determined for each run, with the average value reported.

[0056] Weight average molecular weight, Mw: Reported in the following examples was determined using gel permeation chromatography (GPC). Aqueous samples of the product polymers were prepared for GPC analysis at a concentration of about 2 mg / mL in an aqueous 20 mM phosphate buffer at pH 7. The separation was performed on a Waters UPLC system equipped with a refractive index detector, and the same phosphate buffer was used as the mobile phase. A column set composed of a TOSOH Bioscience TSKgel G2500PWxl 7.8 mm ID x 30 cm, 7-pm column and a TOSOH Bioscience TSKgel GMPWxl 7.8 mm ID x 30 cm, 13-pm column was used. The flow rate was maintained at 1.0 mL / min and the columntemperature at 35 °C. Results were calibrated with narrow polyacrylic acid standards of a peak molecular weight (Mp) of 216 g / mol to 1,100,000 g / mol, fitted with a quadratic calibration curve. Standards 1-15 were obtained from American Polymer Standards and Standard 16 (AA trimer with Mp= 216 g / mol) was prepared internally. The flow rate was 1.0 mL / min and the column temperature was maintained at 35 °C. Empower Version 3 software (Waters Corporation) was used to calculate weighted-average molecular weight (Mw) of the example carboxymethylated galactomannan polymers.Synthesis SI: Carboxymethyl locust bean gum

[0057] A 500 mL, four necked flask fitted with a glass rod propeller connected to a Teflon blade and driven by an overhead mechanical sitter, a condenser and a thermocouple connected with a J-KEM temperature controller and providing input to a heating mantle. The flask was first charged with locust bean gum powder (45.08 g, of active corrected for volatile and ash content, G0753 grade from Sigma Aldrich), sodium chloroacetate (13.01 g), anhydrous isopropyl alcohol (288.60 g) and deionized water (72.27 g). Agitation of the flask contents was started to afford good mixing as indicated by a small vortex at the content surface in the flask and a nitrogen blanket was applied to remove entrained air. One hour later, a 50 wt% aqueous solution of sodium hydroxide (12.28 g) was added dropwise via a syringe to the flask contents over about five minutes. Following addition of the sodium hydroxide solution, the flask contents were allowed to stir for ten minutes at ambient temperature. The temperature set point on the J-KEM temperature controller was then raised to 70 °C. Upon reaching 70 °C, the flask contents continued to be equilibrated for two and a half hours. Then the flask contents were cooled in an ice water bath to ambient temperature with continuous nitrogen flow, and glacial acetic acid (6.28 g) was added dropwise to the flask contents to quench the reaction. Following a ten minute hold, the flask contents were transferred into a fritted Buchner funnel and washed (a) three times with a mixture of anhydrous isopropyl alcohol (360 g) and water (90 g) and (b) two times with a mixture of anhydrous isopropyl alcohol (405 g) and water (45 g), and (c) twice with anhydrous isopropyl alcohol (450 g). The washed polymer was then dried in 50 °C vacuum oven overnight, ground with a mortar and pestle and passed through a metal screen (US 30, mesh size: 600 micrometers). The procedure afforded 58.85 g of a dry product powder. The product polymer was then analyzed for volatile content — 5.73 wt%; weight average molecular weight, Mw, as measured by aqueous Gel permeation chromatography — 1,767,000 Daltons; and carboxymethyl degree of substitution, DSCA, as measured by perchloric acid titration — 0.395.Comparative Examples CF1-CF2 and Example Fl: Dishwashing detergents

[0058] Dishwashing compositions were prepared in each of Comparative Examples CF1-CF2 and Example Fl having the component formulations identified in TABLE 1.T BLE 1Procedure for preparing food soil

[0059] The food soil described in TABLE 2 was prepared by the following procedure. a) Bringing the water to a boil. b) Mixing in a paper cup the instant gravy, the benzoic acid and the starch; and then adding the mixture to the boiling water. c) Adding the milk and margarine to the product of (b). d) Letting the product of (c) cool down to approximately 40 °C, and then adding mixture to a kitchen mixer (Polytron). e) Combining in another paper cup, the egg yolk, the ketchup and the mustard and mixing with a spoon.f) Adding the product of (e) to the mixture of (d) in the blender with continuous stirring. g) Letting the product of (f) stir in the blender for 5 minutes. h) The freezing the product food soil mixture from (g). i) 50 g of the frozen slush is placed into the dishwasher at beginning of the main wash.TABLE 2Dishwashing Test Conditions

[0060] Machine: Miele SS-ADW, Model G1223SC Labor Prog 6. Wash at 65 °C - 20 min wash cycle, followed by two rinse cycles with a rinse water temperature of 65 °C and a final 30 minute drying step. After the drying cycle was complete, the dishwasher door was opened for 30 minutes to allow the steam to evaporate. Water: initial water supplied to the dishwasher had a target conductivity of 1,160 to 1,250 ps / cm. Food soil: 50 g of the composition noted in TABLE 2 was introduced to the wash liquor frozen in a cup. Each dishwashing composition from Comparative Examples CF1-CF2 and Example Fl were tested. The food soil was added at the beginning of the wash cycle. The test detergents were also charged to the dishwasher at the beginning of the wash cycle. The test detergents were each dosed at 15.3 g per wash (based on solids). The number of wash cycles used in this experiment to generate filming and spotting was 15.Filming and Spotting Evaluation

[0061] After each of 15 wash cycles under the above dishwashing test conditions, the glass tumblers (Schott Zwiesel Tritan® longdrink glasses), wine glasses (Stolzle™ stemless red wine glasses) and plastic tumblers (Clear Lido® from Cambro) were dried in open air. After drying, filming and spotting ratings were determined by trained evaluators by observations of glass tumblers, wine glasses and plastic tumblers in a light box with controlled illumination from below. Glass tumblers, wine glasses and plastic tumblers were rated for filming and spotting according to ASTM method ranging from 1 (no film / spots) to 5 (heavilyfilmed / spotted). An average value of 1 to 5 for filming and spotting was determined as reported in TABLE 3. Also reported in TABLE 3 are the values for overall spot, overall film and overall shine (i.e., overall spot + overall film) for each dishwashing composition.ABLE 3

Claims

We claim:

1. A dishwashing detergent formulation comprising: a builder; a nonionic surfactant; and a carboxyalkyl galactomannan having a mannose to galactose ratio of >2:1 ; and wherein the carboxyalkyl galactomannan has a weight average molecular weight, Mw, of >500,000 Daltons and a carboxyalkyl degree of substitution, DSCA, of 0.1 to 0.54.

2. The dishwashing detergent formulation of claim 1 , further comprising a phosphonate crystal growth inhibitor.

3. The dishwashing detergent formulation of claim 2, wherein the carboxy alkyl galactomannan is selected from the group consisting of a carboxyalkyl tara gum, a carboxyalkyl locust bean gum, a carboxyalkyl cassia gum and mixtures thereof; and wherein the dishwashing detergent formulation comprises < 0.4 wt%, based on weight of the dishwashing detergent formulation, of urea.

4. The dishwashing detergent formulation of claim 3, wherein the dishwashing detergent formulation is an anhydrous solid.

5. The dishwashing detergent formulation of claim 4, wherein the builder is selected from the group consisting of carbonate, bicarbonate, citrate, silicate and mixtures thereof.

6. The dishwashing detergent formulation of claim 5, wherein the dishwashing formulation comprises less than 0. 1 wt%, based on dry weight of the dishwashing formulation, of phosphate, measured as elemental phosphorus.

7. The dishwashing detergent formulation of claim 6, wherein the dishwashing formulation contains 0 wt%, based on the dry weight of the dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2’-iminodissuccinate; S,S -ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’ -ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta-alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof.

8. The dishwashing detergent formulation of claim 7, further comprising an additive selected from the group consisting of a bleaching agent, a bleach activator, an enzyme, a filler, and mixtures thereof.

9. The dishwashing detergent formulation of claim 8, wherein the carboxyalkyl galactomannan is a carboxymethyl locust bean gum having a weight average molecular weight of 600,000 to 2,750,000 Daltons and a carboxymethyl degree of substitution, DSCA, of 0.3 to 0.46.

10. A method of cleaning an article in an automatic dishwashing machine, comprising: providing at least soiled one article; providing a dishwashing detergent formulation selected based on an ability to impede the formation of phosphonate scale on the at least one soiled article, wherein the dishwashing detergent formulation is selected to be according to claim 1 ; and applying the selected dishwashing detergent formulation to the at least one soiled article to provide a cleaned article.

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