Tableware washing detergent formulation

Abstract

A dishwashing detergent formulation is provided, the dishwashing detergent formulation comprising a builder; a nonionic surfactant; and a carboxymethyl guar gum wherein the carboxymethyl guar gum has a weight average molecular weight MW of greater than 500,000 Daltons and a degree of carboxymethyl substitution DSCM of from 0.17 to 1.

Description

[0001] The present invention relates to a dishwashing detergent formulation. Specifically, the present invention relates to a dishwashing detergent formulation comprising: a builder; a nonionic surfactant; and carboxymethyl guar gum, wherein the carboxymethyl guar gum has a weight average molecular weight M greater than 500,000 daltons W and a degree of carboxymethyl substitution DS of from 0.17 to 1 CM .

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

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

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

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

[0006] Nonetheless, there is still a need for novel dispersant polymers for use in dishwashing detergents. Specifically, there is still a need for novel dispersant polymers for dishwashing detergents, where the dispersant polymer provides effective low filming properties; is of biological origin and biodegradable.

[0007] The present invention provides a dishwashing detergent formulation comprising: a builder; a nonionic surfactant; and carboxymethyl guar gum, where the carboxymethyl guar gum has a weight average molecular weight Mw greater than 500,000 daltons W and a degree of carboxymethyl substitution DS of from 0.17 to 1 CM .

[0008] The present invention provides a method of cleaning articles in an automatic dishwashing machine, the method comprising: providing at least one article; providing a dishwashing detergent formulation selected based on its ability to prevent the formation of phosphate scale on the at least one article, where the dishwashing detergent formulation is selected according to the present invention; and applying the selected dishwashing detergent formulation to the at least one article. DETAILED DESCRIPTION

[0009] Surprisingly, it has been found that carboxymethyl guar gum having a weight average molecular weight Mw greater than 500,000 daltons W and a degree of carboxymethyl substitution DS of from 0.17 to 1 CM provides good spotting and filming properties on glassware, while having the benefit of improving the overall sustainability of the dishwashing detergent formulation (i.e., is of biological origin and exhibits improved biodegradability relative to conventional dispersant polymers such as polyacrylic acid).

[0010] Unless otherwise specified, ratios, percentages, parts, etc. are by weight. The weight percentage (or wt%) in a composition is the percentage of dry weight, i.e., excluding any water that may be present in the composition. The percentage of monomer units in a polymer is the percentage of dry weight (i.e., excluding any water present in the polymer emulsion).

[0011] As used herein, unless otherwise specified, the terms "weight-average molecular weight" and "Mw" are used interchangeably and refer to the weight-average molecular weight measured in a conventional manner by gel permeation chromatography (GPC) using conventional standards such as polyacrylic acid standards. The GPC technique is described in detail in "Modern Size Exclusion Chromatography", W.W. Yau, J.J. Kirkland, D.D. Bly; Wiley-Interscience, 1979, and in "A Guide to Materials Characterization and Chemical Analysis", J.P. Sibilia; VCH, 1988, pp. 81-84. The weight-average molecular weight is reported herein in daltons.

[0012] Preferably, the dishwashing detergent formulation of the present invention comprises: a builder (preferably, 1% to 97% by weight (more preferably, 10% to 98.5% by weight; most preferably, 25% to 96% by weight) of the builder based on the dry weight of the dishwashing detergent formulation) (preferably, wherein the builder comprises at least one of carbonate, bicarbonate, citrate, and silicate); a nonionic surfactant (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 the nonionic surfactant based on the dry weight of the dishwashing detergent formulation); and carboxymethyl guar gum (preferably, 0.2% to 15% by weight (more preferably, 1% to 10% by weight; most preferably, 2.5% to 7.5% by weight) of the carboxymethyl guar gum based on the dry weight of the dishwashing detergent formulation), wherein the carboxymethyl guar gum has a weight-average molecular weight M of >500,000 daltons (preferably, 525,000 daltons to 2,500,000 daltons; more preferably, 600,000 daltons to 2,250,000 daltons; still more preferably, 750,000 daltons to 2,100,000 daltons; yet more preferably, 1,000,000 daltons to 2,000,000 daltons; still yet more preferably, 1,500,000 daltons to 2,000,000 daltons; most preferably, 1,600,000 daltons to 1,850,000 daltons) W and a degree of carboxymethyl substitution DS of 0.17 to 1 (preferably, 0.175 to 0.8; more preferably, 0.18 to 0.47; most preferably, 0.2 to 0.4) CM .

[0013] Preferably, the dishwashing detergent formulation of the present invention comprises a builder, wherein the builder comprises at least one of carbonate, hydrogencarbonate, citrate and 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 carbonate, hydrogencarbonate, citrate and silicate. Most preferably, the dishwashing detergent formulation of the present invention comprises: a builder, wherein the builder comprises a mixture of carbonate, citrate and silicate.

[0014] Preferably, the dishwashing detergent formulation of the present invention comprises: based on the dry weight of the dishwashing detergent formulation, 1 wt% to 97 wt% (preferably, 1 wt% to 97 wt%; more preferably, 10 wt% to 98.5 wt%; most preferably, 25 wt% to 96 wt%) of a builder. Preferably, the dishwashing detergent formulation of the present invention comprises: based on the dry weight of the dishwashing detergent formulation, ≥1 wt% (preferably, ≥10 wt%; more preferably, ≥25 wt%; most preferably, ≥40 wt%) of a builder. Preferably, the dishwashing detergent formulation of the present invention comprises: based on the dry weight of the dishwashing detergent formulation, ≤95 wt% (preferably, ≤90 wt%; more preferably, ≤85 wt%; most preferably, ≤80 wt%) of a builder. The weight percentages of carbonate, citrate and silicate are calculated based on the actual weight of the salt (including metal ions).

[0015] As used herein and in the appended claims, the term "carbonate" refers to an alkali metal or ammonium salt of carbonate, hydrogencarbonate and / or sesquicarbonate. Preferably, the carbonate (if any) used in the dishwashing detergent formulation is selected from the group consisting of carbonates of sodium, potassium and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium). More preferably, the carbonate (if any) used in the dishwashing detergent formulation comprises at least one of sodium carbonate and sodium hydrogencarbonate. Preferably, when the builder used in the dishwashing detergent formulation of the present invention comprises carbonate, the dishwashing detergent formulation preferably comprises: based on the dry weight of the dishwashing detergent formulation, 0 wt% to 97 wt% (preferably, 5 wt% to 75 wt%; more preferably, 10 wt% to 60 wt%; most preferably, 20 wt% to 50 wt%) of carbonate.

[0016] As used herein and in the appended claims, the term "citrate" refers to alkali metal citrate. Preferably, the citrate (if any) used in the dishwashing detergent formulation is selected from the group consisting of citrates of sodium, potassium, and lithium (more preferably, salts of sodium or potassium; most preferably, the salt of sodium). More preferably, the citrate (if any) used in the dishwashing detergent formulation is sodium citrate. Preferably, when the builder used in the dishwashing detergent formulation of the present invention contains citrate, the dishwashing detergent formulation preferably contains: 0 wt% to 97 wt% (preferably, 5 wt% to 75 wt%; more preferably, 10 wt% to 60 wt%; most preferably, 20 wt% to 40 wt%) of citrate, based on the dry weight of the dishwashing detergent formulation.

[0017] As used herein and in the appended claims, the term "silicate" refers to alkali metal silicate. Preferably, the silicate (if any) used in the dishwashing detergent formulation is selected from the group consisting of silicates of sodium, potassium, and lithium (more preferably, salts of sodium or potassium; most preferably, the salt of sodium). More preferably, the silicate (if any) used in the dishwashing detergent formulation is sodium disilicate. Preferably, the builder used in the dishwashing detergent formulation of the present invention contains silicate. Preferably, when the builder used in the dishwashing detergent formulation of the present invention contains silicate, the dishwashing detergent formulation preferably contains: 0 wt% to 97 wt% (preferably, 0.1 wt% to 10 wt%; more preferably, 0.5 wt% to 7.5 wt%; most preferably, 0.75 wt% to 3 wt%) of silicate, based on the dry weight of the dishwashing detergent formulation.

[0018] Preferably, the dishwashing preparation 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 preparation. More preferably, the dishwashing detergent preparation 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 preparation; wherein the nonionic surfactant is selected from the group consisting of: polyoxyalkylene surfactants, polyalkylene glycol esters, polyoxyethylene derivatives of polyol fatty acid esters, polyalkoxylated polyol fatty acid esters, polyalkoxylated natural fats and oils, polyoxyalkylene block copolymers, alkyl polyglucosides, sucrose esters, and mixtures thereof. Even more preferably, the dishwashing detergent preparation 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 preparation; wherein the nonionic surfactant comprises fatty alcohol alkoxylates. Most preferably, the dishwashing detergent preparation 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 preparation; wherein the nonionic surfactant is a fatty alcohol alkoxylate according to Formula I

[0019]

[0020] wherein w is an average value of 5 to 100 (preferably, 6 to 75; more preferably, 7 to 60; most preferably, 8 to 50); wherein R 1 is selected from the group consisting of: hydrogen and straight-chain or branched C 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); wherein R 2 is selected from the group consisting of: straight-chain or branched C 1-20 alkyl groups and straight-chain 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 is 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 therein is from 5 to 21 (preferably from 6 to 20 carbon atoms; more preferably from 7 to 20 carbon atoms).

[0021] 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 carboxymethyl guar gum, based on the dry weight of the dishwashing detergent formulation; wherein the carboxymethyl guar gum has a weight-average molecular weight M of >500,000 daltons (preferably from 525,000 daltons to 2,500,000 daltons; more preferably from 600,000 daltons to 2,250,000 daltons; still more preferably from 750,000 daltons to 2,100,000 daltons; yet more preferably from 1,000,000 daltons to 2,000,000 daltons; still yet more preferably from 1,500,000 daltons to 2,000,000 daltons; most preferably from 1,600,000 daltons to 1,850,000 daltons) W and a degree of carboxymethyl substitution DS of from 0.17 to 1 (preferably from 0.175 to 0.8; more preferably from 0.18 to 0.47; most preferably from 0.2 to 0.4). CM .

[0022] Preferably, based on the weight of the carboxymethyl guar gum, the carboxymethyl guar 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).

[0023] 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)); sources of alkalinity; bleaches (e.g., sodium percarbonate, sodium perborate); bleach activators (e.g., tetraacetylethylenediamine (TAED)); bleach catalysts (e.g., manganese(II) acetate, cobalt(II) chloride, bis(TACN)tri-magnesium diacetate); enzymes (e.g., proteases, amylases, lipases or cellulases); foam inhibitors; colorants; fragrances; silicates; additional builders; antibacterial agents; fillers (e.g., sodium sulfate); deposition control polymers and mixtures thereof. More preferably, the dishwashing detergent formulation of the present invention further comprises additives, wherein the additives are selected from the group consisting of: bleaches, bleach activators, enzymes, fillers and mixtures thereof. Still more preferably, the dishwashing detergent formulation of the present invention further comprises additives, wherein the additives include bleaches (e.g., sodium percarbonate, sodium perborate); bleach activators (e.g., tetraacetylethylenediamine (TAED)); enzymes (e.g., proteases, amylases, lipases or cellulases) and fillers (e.g., sodium sulfate). Most preferably, the dishwashing detergent formulation of the present invention further comprises additives, wherein the additives include: bleaches, wherein the bleaches include sodium percarbonate; bleach activators, wherein the bleach activators include tetraacetylethylenediamine (TAED); enzymes, wherein the enzymes include proteases and amylases; and fillers, wherein the fillers include sodium sulfate.

[0024] 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. Even 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 includes 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 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.

[0025] The filler contained in the dishwashing detergent formulation tablets or powders is an inert water-soluble substance, typically a sodium or potassium salt (e.g., sodium sulfate, potassium sulfate, sodium chloride, potassium chloride). In tablets and powders, the filler is typically present in an amount in the range of 0% to 75% by weight. The filler included in the gel formulation typically includes those mentioned for tablets and powders and also includes water.

[0026] Fragrances, dyes, foam inhibitors, enzymes, and antibacterial agents typically total no more than 10% by weight of the dishwashing detergent formulation, alternatively no more than 5% by weight.

[0027] The dishwashing detergent formulation of the present invention optionally further comprises: a source of alkalinity. Suitable sources of alkalinity 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, sesquisodium carbonate or sesquipotassium carbonate, sodium hydroxide, lithium hydroxide, or potassium hydroxide, or mixtures of the foregoing. Sodium hydroxide is preferred. The amount of the source of alkalinity (if any) in the dishwashing detergent formulation of the present invention 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.

[0028] The dishwashing detergent formulation of the present invention optionally further comprises: a bleaching agent (e.g., sodium percarbonate). The amount of the bleaching agent (if any) in the dishwashing detergent formulation of the present invention is preferably in a concentration of 1% to 25% by weight (more preferably, 5% to 20% by weight) based on the dry weight of the dishwashing detergent formulation.

[0029] The dishwashing detergent formulation of the present invention optionally further comprises: a bleach activator (e.g., tetraacetylethylenediamine (TAED)). The amount of the bleach activator (if any) in the dishwashing detergent formulation of the present invention is preferably in a concentration of 1% to 10% by weight (more preferably, 2.5% to 7.5% by weight) based on the dry weight of the dishwashing detergent formulation.

[0030] Preferably, the dishwashing detergent formulation of the present invention comprises: phosphates in an amount of <1% by weight (preferably, <0.5% by weight; more preferably, <0.2% by weight; still more preferably, <0.1% by weight; yet still more preferably, <0.01% by weight; most preferably, < the limit of detection) based on the dry weight of the dishwashing detergent formulation. Preferably, the dishwashing detergent formulation of the present invention does not contain phosphates (i.e., contains 0% by weight of phosphates).

[0031] Preferably, the dishwashing detergent formulation of the present invention comprises: builders in an amount of <1% by weight (preferably, <0.5% by weight; more preferably, <0.2% by weight; still more preferably, <0.1% by weight; yet still more preferably, <0.01% by weight; most preferably, < the limit of detection) based on the dry weight of the dishwashing detergent formulation, said builders being selected from the group consisting of: nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamate-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinic acid 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. Most preferably, the dishwashing detergent formulation of the present invention contains 0% by weight of builders selected from the group consisting of: nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamate-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinic acid 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.

[0032] Preferably, the dishwashing detergent formulation of the present invention comprises: based on the dry weight of the dishwashing detergent formulation, <1 wt% (preferably, <0.5 wt%; more preferably, <0.25 wt%; still more preferably, <0.1 wt%; even more preferably, <0.05 wt%; still even more preferably, <0.01 wt%; most preferably, less than the limit of detection) of phosphonates (e.g., hydroxyethane diphosphonic acid (HEDP)). Preferably, the dishwashing detergent formulation of the present invention does not contain phosphonates (i.e., contains 0 wt% of phosphonates).

[0033] Preferably, the dishwashing detergent formulation of the present invention comprises: based on the dry weight of the dishwashing detergent formulation, <1 wt% (preferably, <0.5 wt%; more preferably, <0.25 wt%; still more preferably, <0.1 wt%; even more preferably, <0.05 wt%; still even more preferably, <0.01 wt%; most preferably, less than the limit of detection) of phosphorus. Preferably, the dishwashing detergent formulation of the present invention does not contain phosphorus (i.e., contains 0 wt% of phosphorus).

[0034] Preferably, the dishwashing detergent formulation of the present invention comprises: based on the dry weight of the dishwashing detergent formulation, ≤0.4 wt% (preferably, <0.3 wt%; more preferably, <0.2 wt%; still more preferably, <0.1 wt%; even more preferably, <0.01 wt%; still even more preferably, <0.001 wt%; most preferably, less than the limit of detection) of urea. Preferably, the dishwashing detergent formulation of the present invention does not contain urea (i.e., contains 0 wt% of urea).

[0035] Preferably, the pH (1 wt% in water) of the dishwashing detergent formulation of the present invention is at least 9 (preferably, ≥10; more preferably, ≥11.5). Preferably, the pH (1 wt% in water) of the dishwashing detergent formulation of the present invention is not greater than 13.

[0036] Preferably, the dishwashing detergent formulation of the present invention can be formulated into any typical form, e.g., as tablets, powders, blocks, single-dose, sachets, pastes, liquids or gels. More preferably, the dishwashing detergent formulation of the present invention is formulated as a solid, e.g., formulated as tablets, granules, powders, blocks, pastes. Most preferably, the dishwashing preparation of the present invention is formulated as granules or powders.

[0037] Preferably, the dishwashing detergent formulation of the present invention contains: based on the weight of the dishwashing detergent formulation, less than 6 wt% (preferably, <5 wt%; more preferably, <2.5 wt%; still more preferably, <2 wt%; even more preferably, <1 wt%) of water.

[0038] The tableware washing detergent formulation of the present invention can be used to clean utensils such as eating and cooking utensils, tableware in an automatic dishwashing machine.

[0039] Preferably, the tableware washing 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 tableware washing detergent formulation, calculated 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 an appropriate product form and addition time, the tableware washing detergent formulation of the present invention can be present in the pre-wash, main wash, penultimate rinse, final rinse, or any combination of these cycles.

[0040] Preferably, the method for cleaning an article in an automatic dishwashing machine of the present invention includes: providing at least one soiled article (e.g., cooking utensils, baking utensils, tableware, dishes, flatware, and / or glassware; preferably, glassware); providing the tableware washing detergent formulation of the present invention selected based on its ability to prevent the formation of phosphonate scale on the at least one article; and applying the tableware washing detergent formulation to the at least one soiled article (preferably, in an automatic dishwashing machine) to provide a clean article.

[0041] Some embodiments of the present invention will now be described in detail in the following examples.

[0042] Degree of substitution : It is reported in the following examples and measured according to the non-aqueous titration method in ASTM D1439-15, which is specifically written for carboxymethyl cellulose. Nevertheless, the same principle applies to carboxymethyl guar gum. First, an accurately weighed amount of the polymer is refluxed in an excess of glacial acetic acid, and the sodium acetate formed is titrated with perchloric acid as a strong acid. Crystal violet is used as an indicator and the titrant changes from purple / blue to green at the end point.

[0043] Weight-average molecular weight M W : It is reported in the following examples and determined using gel permeation chromatography (GPC). An aqueous sample of the product polymer for GPC analysis is prepared at a concentration of about 2 mg / mL in 20 mM aqueous phosphate buffer at pH 7. Separation is carried out on a Waters UPLC system equipped with a refractive index detector, and the same phosphate buffer is used as the mobile phase. A column set 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 is used. The flow rate is maintained at 1.0 mL / minute and the column temperature is maintained at 35 °C. The results are calibrated with narrow polyacrylic acid standards with a peak molecular weight (M p ) from 216 g / mol to 1,100,000 g / mol and 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) is prepared in-house. The flow rate is 1.0 mL / minute and the column temperature is maintained at 35 °C. The weight-average molecular weight (M W ) of the exemplary carboxymethylated galactomannan polymer is calculated using Empower version 3 software (Waters Corporation).

[0044] Synthesis S1: Carboxymethyl guar gum

[0045] A 500 mL four-necked flask was equipped with a glass rod impeller connected to a Teflon blade and driven by an overhead mechanical stirrer, a condenser, and a thermocouple connected to a J-KEM temperature controller and providing input to a heating mantle. First, the flask was charged with guar gum powder A1 (30.05 g, corrected for volatile and ash content, Dabur DHV074), sodium chloroacetate B (15.12 g), anhydrous isopropanol C (192.82 g), and deionized water D1 (48.15 g). Stirring of the flask contents was started to provide good mixing, as indicated by small vortices at the surface of the contents in the flask, and a nitrogen layer was applied to remove entrained air. After one hour, a 50 wt% aqueous sodium hydroxide solution E (12.57 g) was added dropwise to the flask contents over about five minutes via syringe. After addition of the sodium hydroxide solution, the flask contents were stirred at ambient temperature for ten minutes. Then the temperature set point on the J-KEM temperature controller was raised to 70 °C. When 70 °C was reached, the flask contents were allowed to equilibrate for two and a half hours. Then the flask contents were cooled to ambient temperature in an ice-water bath under a continuous nitrogen stream, and glacial acetic acid F (4.29 g) was added dropwise to the flask contents to quench the reaction. After holding for ten minutes, the flask contents were transferred to a sintered Buchner funnel and (a) washed three times with a mixture of anhydrous isopropanol (240 g) and water (60 g), (b) washed twice with a mixture of anhydrous isopropanol (270 g) and water (30 g), and (c) washed twice with anhydrous isopropanol (300 g). The washed polymer was then dried overnight in a 50 °C vacuum oven, ground with a mortar and pestle, and passed through a metal sieve (US 30, mesh size: 600 microns). This procedure yielded 45.25 g of an off-white beige dry product powder. Then the volatile content of the product polymer was analyzed; the weight-average molecular weight M W , as measured by aqueous gel permeation chromatography; and the degree of carboxymethyl substitution DS CM , as measured by perchloric acid titration. The results are provided in Table 2.

[0046] Syntheses S2 - S5: Carboxymethyl guar gum

[0047] In syntheses S2 - S5, carboxymethyl guar gum was prepared substantially as described in synthesis S1, but with different flask volumes and reagent feeds as shown in Table 1. Then the volatile content of the product polymer was analyzed; the weight-average molecular weight M W , as measured by aqueous gel permeation chromatography; and the degree of carboxymethyl substitution DS CM , as measured by perchloric acid titration. The results are provided in Table 2.

[0048] Synthesis S8: Carboxymethyl dextran polymer

[0049] A 1000 mL four-necked flask is equipped with a glass rod agitator connected to a Teflon blade and driven by an overhead mechanical stirrer, a condenser, and a thermocouple connected to a J-KEM temperature controller and providing input to a heating mantle. First, the flask is charged with dextran dry powder A2 (107.75 g, corrected for volatile and ash content, Ultradex 531 from Fermworx), sodium chloroacetate B (54.1 g), and deionized water D1 (358.3 g). Stirring of the flask contents is initiated to provide good mixing, as indicated by small vortices at the surface of the contents in the flask, and a nitrogen layer is applied to remove entrained air. After one hour, the reaction mixture forms a clear colorless solution, and a 50 wt% aqueous sodium hydroxide solution E (45.2 g) is added dropwise to the flask contents via syringe. After addition of the sodium hydroxide solution, the flask contents are stirred for five minutes at ambient temperature. The temperature set point on the J-KEM temperature controller is then increased to 70 °C. When 70 °C is reached, the flask contents are allowed to equilibrate for three hours. The flask contents are then cooled to ambient temperature in an ice bath under a continuous nitrogen stream, and glacial acetic acid F (12.1 g) is added dropwise to the flask contents to quench the reaction. After holding for ten minutes, the flask contents are diluted with deionized water D2 (155.5 g) to form a clear light brown aqueous solution.

[0050] Approximately 100 g of this aqueous carboxymethyl dextran polymer solution is further diluted with approximately 50 g of deionized water and then precipitated into 2 L of methanol. The precipitated polymer is soaked in methanol overnight, transferred to a sintered Büchner funnel, washed with additional methanol, and dried overnight in a 50 °C vacuum oven. The product polymer is then analyzed for its weight-average molecular weight M W (measured by aqueous gel permeation chromatography) and carboxymethyl degree of substitution DS CM (measured by perchloric acid titration). The results are provided in Table 2.

[0051] Syntheses S9 - S12: Carboxymethyl dextran polymer

[0052] In syntheses S9 - S12, carboxymethyl dextran is prepared substantially as described in synthesis S8, but with different flask volumes and reagent feeds as shown in Table 1. Note that in syntheses S11 - S12, dextran A3 (Dextran grade D1662 from Sigma Aldrich) is used in place of A2. The product is diluted with approximately 50 g of deionized water and then precipitated into 2 L of methanol. The precipitated polymer is soaked in methanol overnight, transferred to a sintered Büchner funnel, washed with additional methanol, and dried overnight in a 50 °C vacuum oven. The product polymer is then analyzed for its weight-average molecular weight M W (measured by aqueous gel permeation chromatography) and carboxymethyl degree of substitution DS CM(as measured by perchloric acid titration). The results are provided in Table 2.

[0053] Table 1

[0054]

[0055] Table 2

[0056]

[0057]

[0058] Comparative Examples C1 - C8 and Examples 1 - 5: Dishwashing detergent formulations

[0059] In each of Comparative Examples C1 - C8 and Examples 1 - 5 having the group formulations determined in Table 3, a dishwashing composition was prepared.

[0060] Table 3

[0061]

[0062] Procedure for preparing food soil

[0063] The 80% margarine / 20% milk powder food soil as described in ASTM D - 3556 was prepared as follows:

[0064] a) Weigh 1,200 grams of Land - O - Lakes margarine (after pre - melting in a 40°C oven) into a suitable container;

[0065] b) Add 300 grams of Nestle Carnation non - fat milk powder to the container;

[0066] c) Mix well using a top - mounted mixer until the ingredients are uniform and there are no visible lumps;

[0067] and

[0068] d) Pour 40 - gram portions of the mixture into separate 2 - ounce glass jars and refrigerate until use.

[0069] Table 4

[0070] Ingredient wt% Land - O - Lakes margarine 80 Carnation non - fat dry milk 20

[0071] Dishwashing test conditions

[0072] Automatic dishwashing tests were conducted under US conditions according to the procedure described in ASTM D-3556 to evaluate cleaning performance. The tests were conducted in a Whirlpool WDF330PAHW type automatic dishwashing machine. Washing cycle: 49 °C wash / 60 °C rinse; Dishwasher cycle time 65 minutes. Water: 300 ppm total hardness, Ca +2 :Mg +2 = 2:1, and 100 ppm sodium bicarbonate. Food soil: 40 g of the composition shown in Table 4 was introduced into the wash liquor in a refrigerated 2 oz glass jar. After completion of the pre-wash step, the detergent was added during the main wash. Each dishwashing composition from Comparative Examples C1-C8 and Examples 1-5 was tested, as shown in Tables 5-6, at a dosage of 15 g per wash. Ballast (china plates, glass plates, plastic kitchen utensils and knives). Between dishwashing cycles, the dishwasher door was left open for 30 minutes as an additional drying step.

[0073] Film formation and spotting evaluation

[0074] After each of the 5 wash cycles under the above dishwashing test conditions, the Libbey Collins tumblers, poly(styrene / acrylic) plastic cups and stainless steel specimens were dried in the open air. After drying, the film formation and spotting grades were determined by trained evaluators as follows: The tumblers and plastic cups were viewed from below in a light box with controlled lighting; and the stainless steel specimens were viewed from above under controlled lighting. Film formation and spotting of the tumblers were rated according to the ASTM method, ranging from 1 (no film / spotting) to 5 (severe film formation / spotting). As reported in Table 5, the average values for film formation and spotting were determined to be from 1 to 5. Visual observations of the tumblers, plastic cups and stainless steel specimens are also reported in Table 6.

[0075] Table 5 :

[0076]

[0077] Table 6 :

[0078] Comparison Large glass Plastic cup SS specimen C1 Severe fouling (white) Severe fouling (white), spotting observed Severe fouling (white), spotting observed C2 Light fouling (blue) Light fouling (white), minimal spotting Minimal fouling (white), minimal spotting C3 Light fouling (white) Light fouling (white), no spotting Minimal fouling (white), minimal spotting C4 Severe fouling (white) Severe fouling (white) Severe fouling (white), spotting observed C5 Severe fouling (white) Severe fouling (white) Severe fouling (white), spotting observed C6 Severe fouling (white) Severe fouling (white) Severe fouling (white), spotting observed C7 Severe fouling (white) Severe fouling (white) Severe fouling (white), spotting observed C8 Severe fouling (white) Severe fouling (white) Severe fouling (white), spotting observed 1 Light fouling (white) Light fouling (white), no spotting Minimal fouling (white), moderate spotting 2 Light fouling (white) Light fouling (white), no spotting Minimal fouling (white), moderate spotting 3 Light fouling (white) Light fouling (white), minimal spotting Minimal fouling (white), moderate spotting 4 Light fouling (white) Light fouling (white), no spotting Minimal fouling (white), minimal spotting 5 Light fouling (white) Light fouling (white), no spotting Minimal fouling (white), moderate spotting

Claims

1. A dishwashing detergent formulation, the dishwashing detergent formulation comprising: A builder; A nonionic surfactant; and Carboxymethyl guar gum, wherein the carboxymethyl guar gum has a weight-average molecular weight M of >500,000 Daltons W and a degree of carboxymethyl substitution DS of 0.17 to 1 CM .

2. The dishwashing detergent formulation according to claim 1, wherein, based on the weight of the dishwashing detergent formulation, the dishwashing detergent formulation comprises <1% by weight of HEDP.

3. The dishwashing detergent formulation according to claim 1, wherein, based on the weight of the dishwashing detergent formulation, the dishwashing detergent formulation comprises ≤0.4% by weight of urea.

4. The dishwashing detergent formulation according to claim 1, wherein the dishwashing detergent formulation is a solid.

5. The dishwashing detergent formulation according to claim 1, wherein the dishwashing detergent formulation is anhydrous.

6. The dishwashing detergent formulation according to claim 1, wherein the builder is selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof.

7. The dishwashing detergent formulation according to claim 1, wherein, based on the dry weight of the dishwashing formulation, the dishwashing formulation comprises less than 0.1% by weight of phosphate measured as elemental phosphorus.

8. The dishwashing detergent formulation according to claim 1, wherein, based on the dry weight of the dishwashing detergent formulation, the dishwashing formulation contains 0% by weight of a builder selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methylglycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamate-N,N-diacetic acid; 3-hydroxy-2,2'-iminodisuccinate; S,S-ethylenediaminedisuccinic acid 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.

9. The dishwashing detergent formulation according to claim 1, the dishwashing detergent formulation further comprising an additive selected from the group consisting of bleaches, bleach activators, enzymes, fillers, and mixtures thereof.

10. A method of cleaning articles in an automatic dishwashing machine, the method comprising: Providing at least one article; Providing a dishwashing detergent formulation selected based on its ability to prevent the formation of phosphonate scale on the at least one article, wherein the dishwashing detergent formulation is selected according to claim 1; And Applying the selected dishwashing detergent formulation to the at least one article.

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