Dishwashing detergent formulations

Abstract

a builder, a nonionic surfactant, and a carboxymethyl guar gum having a weight average molecular weight MW of greater than 500,000 Daltons and a degree of carboxymethyl substitution DS of 0.17 to 1. CM and a carboxymethyl guar gum having the formula:

Description

[Technical Field]

[0001] The present invention relates to dishwashing detergent formulations. In particular, the present invention relates to a dishwashing detergent formulation comprising a builder, a nonionic surfactant, and carboxymethyl guar gum having a weight average molecular weight M of greater than 500,000 Daltons. W and carboxymethyl substitution degree DS of 0.17 to 1 CM The present invention relates to a dishwashing detergent formulation comprising carboxymethyl guar gum having the formula:

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

[0003] Phosphate-free dishwashing compositions are increasingly desirable. Phosphate-free dishwashing compositions typically rely on non-phosphate builders, such as citrates, carbonates, silicates, disilicates, bicarbonates, aminocarboxylates, and other salts, to scavenge calcium and magnesium from hard water, leaving insoluble visible deposits upon drying.

[0004] A family of polycarboxylate copolymers and their use as builders in detergent 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 that block copolymers containing 20 to 95 mole percent monomer units derived from itaconic acid or its homologs and 5 to 80 mole percent monomer units derived from vinyl alcohol or lower vinyl esters are excellent binders for divalent or polyvalent metals and are useful as potentially biodegradable builders in detergent compositions, as well as in machine dishwashing compositions and antiscaling rinse compositions.

[0005] A family of terpolymers, and their use as dispersants among others, is disclosed by Swift et al. in U.S. Patent No. 5,191,048. Swift et al. teach a terpolymer comprising, as polymerized units, about 15 to 55 mole percent of at least one first monomer selected from the group consisting of vinyl acetate, vinyl ether, and vinyl carbonate, about 10 to 70 mole percent of at least one second monomer of an ethylenically unsaturated monocarboxylic acid, and about 15 to 55 mole percent of at least one third monomer of a dicarboxylic acid anhydride, the terpolymer being formed in a non-aqueous system such that less than about 1 percent of the monomers are hydrolyzed during the polymerization.

[0006] Nevertheless, there remains a need for new dispersant polymers for use in dishwashing formulations. In particular, there remains a need for new dispersant polymers for use in dishwashing formulations that provide effective low film-forming performance and that are bio-derived and biodegradable.

[0007] The present invention provides a composition comprising a builder, a nonionic surfactant, and carboxymethyl guar gum having a weight average molecular weight M of greater than 500,000 Daltons. W and carboxymethyl substitution degree DS of 0.17 to 1 CM and a carboxymethyl guar gum having the formula:

[0008] The present invention provides a method of cleaning items in an automatic dishwashing machine, the method comprising providing at least one item; providing a dish detergent formulation selected based on its ability to prevent the formation of phosphonate scale on the at least one item, wherein the dish detergent formulation is selected to be in accordance with the present invention; and applying the selected dish detergent formulation to the at least one item. DETAILED DESCRIPTION OF THE INVENTION

[0009] Surprisingly, weight average molecular weight M >500,000 DaltonsW , and a carboxymethyl substitution degree DS of 0.17 to 1 CM Carboxymethyl guar gum, having the formula: has been found to provide good spotting and filming performance on glassware compared to conventional dispersant polymers, while having the benefit of improving the overall substantivity of the dish detergent formulation (i.e., being bio-derived and exhibiting improved biodegradability compared to conventional dispersant polymers such as polyacrylic acid).

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

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

[0012] Preferably, the dish detergent formulation of the present invention comprises a builder (preferably 1 to 97 wt. % (preferably 10 to 98.5 wt. %, most preferably 25 to 96 wt. %) builder, based on the dry weight of the dish detergent formulation) (preferably the builder comprises at least one of carbonate, bicarbonate, citrate, and silicate), a non-ionic surfactant (preferably 0.2 to 15 wt. % (more preferably 0.5 to 10 wt. %, most preferably 1.5 to 8.5 wt. %) non-ionic surfactant, based on the dry weight of the dish detergent formulation), and a carboxymethyl guar gum (preferably 0.2 to 15 wt. % (more preferably 1 to 10 wt. %, most preferably 2.5 to 7.5 wt. %) carboxymethyl guar gum, based on the dry weight of the dish detergent formulation), wherein the carboxymethyl guar gum has a weight average molecular weight M of >500,000 Daltons. W (preferably 525,000 to 2,500,000 daltons, more preferably 600,000 to 2,250,000 daltons, even more preferably 750,000 to 2,100,000 daltons, even more preferably 1,000,000 to 2,000,000 daltons, even more preferably 1,500,000 to 2,000,000 daltons, and most preferably 1,600,000 to 1,850,000 daltons), and a degree of carboxymethyl substitution DS of 0.17 to 1 CM (preferably 0.175 to 0.8, more preferably 0.18 to 0.47, most preferably 0.2 to 0.4).

[0013] Preferably, the dish detergent formulations of the present invention include a builder, wherein the builder comprises at least one of carbonate, bicarbonate, citrate, and silicate. More preferably, the dish detergent formulations of the present invention include a builder, wherein the builder comprises a mixture of at least two components selected from the group consisting of carbonate, bicarbonate, citrate, and silicate. Most preferably, the dish detergent formulations of the present invention include a builder, wherein the builder comprises a mixture of carbonate, citrate, and silicate.

[0014] Preferably, the dishwashing detergent formulations of the present invention comprise 1 to 97 wt. % (preferably 1 to 97 wt. % (more preferably 10 to 98.5 wt. %, most preferably 25 to 96 wt. %) of builder based on the dry weight of the dishwashing detergent formulation. Preferably, the dishwashing detergent formulations of the present invention comprise ≧1 wt. % (preferably ≧10 wt. %, more preferably ≧25 wt. %, most preferably ≧40 wt. %) of builder based on the dry weight of the dishwashing detergent formulation. Preferably, the dishwashing detergent formulations of the present invention comprise ≦95 wt. % (preferably ≦90 wt. %, more preferably ≦85 wt. %, most preferably ≦80 wt. %) of builder based on the dry weight of the dishwashing detergent formulation. The weight percentages of carbonate, citrate, and silicate are based on the actual weight of the salt containing the metal ion.

[0015] The term "carbonate" as used herein and in the appended claims refers to alkali metal or ammonium salts of carbonate, bicarbonate, and / or sesquicarbonate. Preferably, the carbonate (if present) used in the dishwashing detergent formulation is selected from the group consisting of sodium, potassium, and lithium carbonate (more preferably, sodium or potassium salts, most preferably, sodium salts). More preferably, the carbonate (if present) used in the dishwashing detergent formulation comprises at least one of sodium carbonate and sodium bicarbonate. Preferably, when the builder used in the dishwashing detergent formulation of the present invention comprises 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. %) of carbonate, based on the dry weight of the dishwashing detergent formulation.

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

[0017] As used herein and in the appended claims, the term "silicate" refers to an alkali metal silicate. Preferably, the silicate used in the dishwashing detergent formulation, if present, is selected from the group consisting of sodium, potassium, and lithium silicates (more preferably, the sodium or potassium salts, most preferably, the sodium salts). More preferably, the silicate used in the dishwashing detergent formulation, if present, is sodium disilicate. Preferably, the builder used in the dishwashing detergent formulation of the present invention comprises a silicate. Preferably, when the builder used in the dishwashing detergent formulation of the present invention comprises 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. %) of silicate, based on the dry weight of the dishwashing detergent formulation.

[0018] Preferably, the dishwashing formulations of the present invention comprise 0.2 to 15 wt. % (preferably 0.5 to 10 wt. %, most preferably 1.5 to 8.5 wt. %) of a nonionic surfactant based on the dry weight of the dishwashing detergent formulation. More preferably, the dishwashing detergent formulations of the present invention comprise 0.2 to 15 wt. % (preferably 0.5 to 10 wt. %, most preferably 1.5 to 8.5 wt. %) of a nonionic surfactant based on the dry weight of the dishwashing detergent formulation, the nonionic surfactant being selected from the group consisting of polyoxyalkylene surfactants, polyalkylene glycol esters, polyoxyethylene derivatives of fatty acid esters of polyhydric alcohols, polyalkoxylated fatty acid esters of polyhydric alcohols, polyalkoxylated natural fats and oils, polyalkylene oxide block copolymers, alkyl polyglucosides, sucrose esters, and mixtures thereof. Even more preferably, the dish detergent formulations of the present invention comprise 0.2 to 15 wt. % (preferably 0.5 to 10 wt. %, most preferably 1.5 to 8.5 wt. %) of a nonionic surfactant, based on the dry weight of the dish detergent formulation, wherein the surfactant comprises a fatty alcohol alkoxylate. Most preferably, the dish detergent formulations of the present invention comprise 0.2 to 15 wt. % (preferably 0.5 to 10 wt. %, most preferably 1.5 to 8.5 wt. %) of a nonionic surfactant, based on the dry weight of the dish detergent formulation, wherein the nonionic surfactant is a fatty alcohol alkoxylate according to Formula I:

[0019] [ka] In the formula, w is an average of 5 to 100 (preferably 6 to 75, more preferably 7 to 60, and most preferably 8 to 50), and R 1 is hydrogen and linear or branched C 1~20 Alkyl groups (preferably hydrogen and linear or branched C 1~20 Alkyl groups, more preferably hydrogen and linear C 1~20 alkyl groups), and R 2 is a linear or branched C 1~20 Alkyl groups and linear or branched C1~4 Hydroxyalkyl groups (preferably linear or branched C 1~20 Alkyl groups, more preferably linear C 1~20 alkyl group), and each R 3 are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, and 2-methyl-2-butyl (preferably hydrogen, methyl, and ethyl), with the proviso that R 1 and R 2 is provided that the total number of carbon atoms in the formula is 5 to 21 (preferably 6 to 20 carbon atoms, more preferably 7 to 20 carbon atoms).

[0020] Preferably, the dishwashing detergent formulations of the present invention comprise 0.2 to 15% (preferably 1 to 10% and most preferably 2.5 to 7.5% by weight) of carboxymethyl guar gum, based on the dry weight of the dishwashing detergent formulation, the carboxymethyl guar gum having a weight average molecular weight M of >500,000 Daltons. W (preferably 525,000 to 2,500,000 daltons, more preferably 600,000 to 2,250,000 daltons, even more preferably 750,000 to 2,100,000 daltons, even more preferably 1,000,000 to 2,000,000 daltons, even more preferably 1,500,000 to 2,000,000 daltons, and most preferably 1,600,000 to 1,850,000 daltons), and a degree of carboxymethyl substitution DS of 0.17 to 1 CM (preferably 0.175 to 0.8, more preferably 0.18 to 0.47, most preferably 0.2 to 0.4).

[0021] Preferably, the carboxymethyl guar 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 the weight of the carboxymethyl guar gum.

[0022] The dish detergent formulations of the present invention optionally further comprise additives. Preferably, the dish detergent formulations of the present invention further comprise additives selected from the group consisting of dispersant polymers, phosphonates (e.g., hydroxy ethylidene diphosphonic acid (HEDP)), alkalinity sources, 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) magnesium trioxide diacetate), enzymes (e.g., proteases, amylases, lipases, or cellulases), suds suppressors, colorants, fragrances, silicates, additional builders, antimicrobial agents, fillers (e.g., sodium sulfate), deposit control polymers, and mixtures thereof. More preferably, the dish detergent formulations of the present invention further comprise additives, which additives are selected from the group consisting of bleaches, bleach activators, enzymes, fillers, and and mixtures thereof. Even more preferably, the dish detergent formulations of the present invention further comprise additives comprising 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), and a filler (e.g., sodium sulfate). Most preferably, the dish detergent formulations of the present invention further comprise additives comprising a bleaching agent comprising sodium percarbonate, a bleach activator comprising tetraacetylethylenediamine (TAED), an enzyme comprising a protease and an amylase, and a filler comprising sodium sulfate.

[0023] Preferably, the dish detergent formulations of the present invention optionally further comprise 0 to 15 wt. % (preferably 0 to 10 wt. %, more preferably 0 to 7.5 wt. %, and most preferably 0 to 5 wt. %) of a phosphonate, based on the dry weight of the dish detergent formulation. More preferably, the dish detergent formulations of the present invention comprise 0 to 15 wt. % (preferably 0 to 10 wt. %, more preferably 0 to 7.5 wt. %, and most preferably 0 to 5 wt. %) of a phosphonate, based on the dry weight of the dish detergent formulation, wherein the phosphonate has a weight average molecular weight of ≦1,000 Daltons. Even more preferably, the dish detergent formulations of the present invention comprise 0 to 15 wt. % (preferably 0 to 10 wt. %, more preferably 0 to 7.5 wt. %, and most preferably 0 to 5 wt. %) of a phosphonate, based on the dry weight of the dish detergent formulation, the phosphonate comprising at least one of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and a salt of 1-hydroxyethylidene-1,1-diphosphonic acid. Most preferably, the dish detergent formulations of the present invention comprise 0 to 15 wt. % (preferably 0 to 10 wt. %, more preferably 0 to 7.5 wt. %, and most preferably 0 to 5 wt. %) of a phosphonate, based on the dry weight of the dish detergent formulation, the phosphonate being selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts thereof.

[0024] Fillers included in the tablets or powders of dishwashing detergent formulations are inert, water-soluble materials, 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% to 75% by weight. Fillers included in gel formulations typically include those mentioned for use in tablets and powders, as well as water.

[0025] Perfumes, dyes, suds suppressors, enzymes, and antimicrobial agents typically total no more than 10% by weight of the dish detergent formulation, alternatively no more than 5% by weight.

[0026] The dish detergent formulations of the present invention optionally further comprise an alkalinity source. Suitable alkalinity sources include, but are not limited to, alkali metal carbonates and alkali metal hydroxides, such as sodium or potassium carbonate, bicarbonates, sesquicarbonates, sodium hydroxide, lithium hydroxide, or potassium hydroxide, or mixtures of the foregoing. Sodium hydroxide is preferred. The amount of alkalinity source (if present) in the dish detergent formulations of the present invention is at least 1 wt. % (preferably at least 20 wt. %) and at most 80 wt. % (preferably at most 60 wt. %), based on the dry weight of the dish detergent formulation.

[0027] The dish detergent formulations of the present invention optionally further comprise a bleaching agent (e.g., sodium percarbonate). The amount of bleaching agent (if present) in the dish detergent formulations of the present invention is preferably at a level of 1 to 25% by weight (more preferably 5 to 20% by weight), based on the dry weight of the dish detergent formulation.

[0028] The dish detergent formulations of the present invention optionally further comprise a bleach activator (e.g., tetraacetylethylenediamine (TAED)). The amount of bleach activator (if present) in the dish detergent formulations of the present invention is preferably at a level of 1 to 10% by weight (more preferably 2.5 to 7.5% by weight), based on the dry weight of the dish detergent formulation.

[0029] Preferably, the dish detergent formulations of the present invention contain <1 wt. % (preferably <0.5 wt. %, more preferably <0.2 wt. %, even more preferably <0.1 wt. %, even more preferably <0.01 wt. %, and most preferably < the limit of detection) of phosphate, based on the dry weight of the dish detergent formulation. Preferably, the dish detergent formulations of the present invention are phosphate-free (i.e., contain 0 wt. % phosphate).

[0030] Preferably, the dish detergent formulations of the present invention contain <1 wt. % (preferably <0.5 wt. %, more preferably <0.2 wt. %, even more preferably <0.1 wt. %, even more preferably <0.01 wt. %, most preferably <detection limit) of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycine-N,N-diacetic acid, methylglycine-N,N-diacetic acid, 2-hydroxyethyl methyl esters, methyl glycine-N,N-diacetic acid, methyl glycine-N,N-diacetic acid, 2-hydroxyethyl methyl esters ... The builder is selected from the group consisting of iminodiacetic acid, glutamic acid-N,N-diacetic acid, 3-hydroxy-2,2'-iminodissuccinate, S,S-ethylenediaminedisuccinic acid aspartic acid-diacetic acid, N,N'-ethylenediaminedisuccinic acid, iminodisuccinic acid, aspartic acid, aspartic acid-N,N-diacetic acid, beta-alanine diacetic acid, polyaspartic acid, salts thereof, and mixtures thereof. Most preferably, the dishwashing detergent formulations of the present invention contain 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, glutamic acid-N,N-diacetic acid, 3-hydroxy-2,2'-iminodissuccinate, S,S-ethylenediaminedisuccinic acid aspartic acid-diacetic acid, N,N'-ethylenediaminedisuccinic acid, iminodisuccinic acid, aspartic acid, aspartic acid-N,N-diacetic acid, beta-alaninediacetic acid, polyaspartic acid, salts thereof, and mixtures thereof.

[0031] Preferably, the dish detergent formulations of the present invention comprise <1 wt. % (preferably <0.5 wt. %, more preferably <0.25 wt. %, even more preferably <0.1 wt. %, even more preferably <0.05 wt. %, even more preferably <0.01 wt. %, and most preferably below the detection limit) of phosphonate (e.g., hydroxyethylidene diphosphonic acid (HEDP)), based on the dry weight of the dish detergent formulation. Preferably, the dish detergent formulations of the present invention are phosphonate-free (i.e., contain 0 wt. % phosphonate).

[0032] Preferably, the dish detergent formulations of the present invention contain <1 wt.% (preferably <0.5 wt.%, more preferably <0.25 wt.%, even more preferably <0.1 wt.%, even more preferably <0.05 wt.%, even more preferably <0.01 wt.%, and most preferably below the detection limit) phosphorus, based on the dry weight of the dish detergent formulation. Preferably, the dish detergent formulations of the present invention are phosphorus-free (i.e., contain 0 wt.% phosphorus).

[0033] Preferably, the dish detergent formulations of the present invention comprise ≦0.4 wt.% (preferably <0.3 wt.%, more preferably <0.2 wt.%, even more preferably <0.1 wt.%, even more preferably <0.01 wt.%, even more preferably <0.001 wt.%, and most preferably below the detection limit) urea, based on the dry weight of the dish detergent formulation. Preferably, the dish detergent formulations of the present invention are urea-free (i.e., contain 0 wt.% urea).

[0034] Preferably, the dish detergent formulations of the present invention have a pH (at 1 wt. % in water) of at least 9 (preferably ≧10, more preferably ≧11.5). Preferably, the dish detergent formulations of the present invention have a pH (at 1 wt. % in water) of 13 or less.

[0035] Preferably, the dishwashing detergent formulations of the present invention can be formulated in any typical form, for example, as a tablet, powder, block, single dose, sachet, paste, liquid, or gel. More preferably, the dishwashing detergent formulations of the present invention are formulated as a solid, for example, as a tablet, granule, powder, block, paste. Most preferably, the dishwashing formulations of the present invention are formulated as granules or powder.

[0036] Preferably, the dish detergent formulations of the present invention comprise less than 6% by weight (preferably <5%, more preferably <2.5%, even more preferably <2%, and even more preferably <1%) of water, based on the weight of the dish detergent formulation.

[0037] The dishwashing detergent formulations of the present invention are useful for cleaning dishes and utensils, dishes, and other items in automatic dishwashers.

[0038] Preferably, the dishwashing detergent formulations of the present invention are suitable for use under typical operating conditions. For example, when used in an automatic dishwashing machine, the typical water temperature during the wash cycle is preferably 20°C to 85°C, preferably 30°C to 70°C. Typical concentrations of the dishwashing detergent formulations, as a percentage of the total liquid in the dishwashing machine, are preferably 0.1 to 1% by weight, preferably 0.2 to 0.7% by weight. By selecting the appropriate product form and addition time, the dishwashing detergent formulations of the present invention can be present in the pre-wash, main wash, penultimate rinse, final rinse, or any combination of these cycles.

[0039] Preferably, a method of cleaning items in an automatic dishwasher of the present invention includes providing at least one soiled item (e.g., cookware, heat-resistant ware, tableware, dishes, flatware, and / or glassware, preferably glassware), providing a dish detergent formulation of the present invention selected based on its ability to prevent the formation of phosphonate scale on the at least one item, and applying the dish detergent formulation to the at least one soiled item (preferably in an automatic dishwasher) to provide clean items.

[0040] Some embodiments of the present invention will now be described in detail in the following examples.

[0041] Degree of substitution: reported in the following examples was measured according to the non-aqueous titration method in ASTM D1439-15, specifically described for carboxymethyl cellulose. Nevertheless, the same principles apply to carboxymethyl guar. An accurately weighed amount of polymer was first refluxed in an excess of glacial acetic acid, and the sodium acetate formed was titrated with perchloric acid as a strong acid. Crystal violet served as an indicator, and the titrant changed color from purple / blue to green at the end point.

[0042] Weight average molecular weight M W The results reported in the following examples were determined using gel permeation chromatography (GPC). Aqueous samples of the product polymers were prepared for GPC analysis at a concentration of approximately 2 mg / mL in aqueous 20 mM phosphate buffer at pH 7. Separation was performed on a Waters UPLC system equipped with a refractive index detector, using the same phosphate buffer as the mobile phase. An APC column set consisting of a TOSOH Bioscience TSKgel G2500PWxl 7.8 mm ID x 30 cm, 7 μm column and a TOSOH Bioscience TSKgel GMPWxl 7.8 mm ID x 30 cm, 13 μm column was used. The flow rate was maintained at 1.0 mL / min, and the column temperature was maintained at 35°C. Peak molecular weights (M) of 216 g / mol to 1,100,000 g / mol were obtained. p Results were calibrated using narrow polyacrylic acid standards and fitted to a quadratic calibration curve. Standards 1–15 were obtained from American Polymer Standards, and standard 16 (M p The weighted average molecular weight (M) of exemplary carboxymethylated galactomannan polymers was determined using Empower Version 3 software (Waters Corporation). W ) was calculated.

[0043] Synthetic S1: Carboxymethyl Guar Gum A 500 mL four-neck flask was fitted with a glass rod propeller connected to a Teflon blade and driven by an overhead mechanical stirrer, a condenser, and a thermocouple connected to a J-KEM temperature controller providing power to a heating mantle. The flask was initially charged with guar gum powder A1 (30.05 g, corrected for volatiles and ash, Dabur DHV074), sodium chloroacetate B (15.12 g), anhydrous isopropyl alcohol C (192.82 g), and deionized water D1 (48.15 g). Stirring of the flask contents was initiated to produce good mixing, indicated by a small vortex on the surface of the contents within the flask, and a nitrogen blanket was applied to remove entrained air. After 1 hour, 12.57 g of a 50 wt % aqueous solution of sodium hydroxide E was added dropwise via syringe over approximately 5 minutes. After the addition of the sodium hydroxide solution, the flask contents were allowed to stir at ambient temperature for 10 minutes. The temperature set point of the J-KEM temperature controller was then increased to 70°C. After reaching 70°C, the flask contents were allowed to equilibrate for 2.5 hours. The flask contents were then cooled to ambient temperature in an ice-water bath using a continuous nitrogen flow, and glacial acetic acid F (4.29 g) was added dropwise to the flask contents to quench the reaction. After a 10-minute hold, the flask contents were transferred into a fritted Buchner funnel and washed (a) three times with a mixture of anhydrous isopropyl alcohol (240 g) and water (60 g), (b) twice with a mixture of anhydrous isopropyl alcohol (270 g) and water (30 g), and (c) twice with anhydrous isopropyl alcohol (300 g). The washed polymer was then dried overnight in a vacuum oven at 50°C, crushed with a mortar and pestle, and passed through a metal screen (US 30, mesh size: 600 micrometers). This procedure yielded 45.25 g of a dry, off-white, beige product powder. The product polymer is then separated into volatile components, weight average molecular weight M as measured by aqueous gel permeation chromatography. W , and the degree of carboxymethyl substitution DS measured by perchloric acid titration CM were analyzed. The results are provided in Table 2.

[0044] Synthetic S2-S5: Carboxymethyl guar gum For Syntheses S2-S5, carboxymethyl guar gum was prepared essentially as described for Synthesis S1, but with variations in flask volumes and reagent feeds as described in Table 1. The product polymer was then analyzed for volatile components, weight average molecular weight M as measured by aqueous gel permeation chromatography, and carboxymethyl guar gum as determined by aqueous gel permeation chromatography. W , and the degree of carboxymethyl substitution DS measured by perchloric acid titration CM were analyzed. The results are provided in Table 2.

[0045] Synthesis S8: Carboxymethyl Dextran Polymer A 1000 mL four-neck flask was fitted with a glass rod propeller connected to a Teflon blade and driven by an overhead mechanical stirrer, a condenser, and a thermocouple connected to a J-KEM temperature controller, providing power to a heating mantle. The flask was initially charged with dextran dry powder A2 (107.75 g, corrected for volatiles and ash, Ultradex 531 from Fermworx), sodium chloroacetate B (54.1 g), and deionized water D1 (358.3 g). Stirring of the flask contents was initiated to produce good mixing, indicated by a small vortex on the surface of the contents within the flask, and a nitrogen blanket was applied to remove entrained air. After 1 h, the reaction mixture formed a clear, colorless solution, and 45.2 g of 50 wt % aqueous sodium hydroxide solution E was added dropwise via syringe to the flask contents. After the addition of the sodium hydroxide solution, the flask contents were allowed to stir at ambient temperature for 5 minutes. The temperature set point of the J-KEM temperature controller was then increased to 70°C. After reaching 70°C, the flask contents were allowed to equilibrate for 3 hours. The flask contents were then cooled to ambient temperature in an ice-water bath using a continuous nitrogen flow, and glacial acetic acid F (12.1 g) was added dropwise to the flask contents to quench the reaction. After a 10-minute hold, the flask contents were diluted with deionized water D2 (155.5 g) to form a clear, light brown aqueous solution.

[0046] Approximately 100 g of this aqueous carboxymethyl dextran polymer solution was further diluted with approximately 50 g of deionized water and then precipitated into 2 L of methanol. The precipitated polymer was soaked in methanol overnight, transferred to a fritted Buchner funnel, washed with additional methanol, and dried overnight in a vacuum oven at 50° C. The product polymer was then purified to a weight average molecular weight, M, as measured by aqueous gel permeation chromatography. W , and the degree of carboxymethyl substitution DS measured by perchloric acid titration CM were analyzed. The results are provided in Table 2.

[0047] Synthesis S9-S12: Carboxymethyl dextran polymers For syntheses S9-S12, carboxymethyl dextran was prepared essentially as described for synthesis S8, with the exception of variations in flask volumes and reagent supplies noted in Table 1. Note that for syntheses S11-S12, dextran A3 (D1662 grade dextran supplied by Sigma-Aldrich) was used instead of A2. The product was diluted with approximately 50 g of deionized water and then precipitated into 2 L of methanol. The precipitated polymer was soaked in methanol overnight, transferred to a fritted Buchner funnel, washed with additional methanol, and dried overnight in a vacuum oven at 50 °C. The product polymer was then analyzed for weight-average molecular weight, M, as measured by aqueous gel permeation chromatography. W , and the degree of carboxymethyl substitution DS measured by perchloric acid titration CM were analyzed. The results are provided in Table 2.

[0048] [Table 1]

[0049] [Table 2]

[0050] Comparative Examples C1-C8 and Examples 1-5: Dishwashing Detergent Formulations Dishwashing compositions were prepared for each of Comparative Examples C1-C8 and Examples 1-5 having the ingredient formulations identified in Table 3.

[0051] [Table 3]

[0052] Procedure for preparing food stains An 80% margarine / 20% milk powder food soil as described in ASTM D-3556 was prepared as follows. a) Weigh 1,200 grams of Land-O-Lakes margarine (after pre-melting in a 40°C oven) into a suitable container; b) Add 300 grams of Nestle Carnation nonfat milk powder to the container; c) Mix thoroughly using an overhead mixer until the ingredients are homogeneous and free of visible lumps; d) 40 gram portions of the mixture were poured into separate 2 ounce glass bottles and refrigerated until use.

[0053] [Table 4]

[0054] Dishwashing test conditions Automatic dishwashing tests were conducted under US conditions according to the procedure described in ASTM D-3556 to evaluate cleaning performance. Tests were performed in a Whirlpool Model WDF330PAHW automatic dishwasher. Wash 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 soils: 40 g of the composition described in Table 4 was added to the wash solution in a refrigerated 2-ounce glass bottle. After the pre-wash step was completed, detergent was added during the main wash. Each dishwashing composition from Comparative Examples C1-C8 and Examples 1-5 was tested, as described in Tables 5-6, and 15 g was added per wash. Ballast load (porcelain plates, glass plates, plastic kitchenware, and cutlery). The dishwasher door was left open for 30 minutes between dishwashing cycles as an additional drying step.

[0055] Assessment of filming and spotting After each of five wash cycles under the dishwashing test conditions described above, Libbey Collins glass tumblers, plastic poly(styrene / acrylic) tumblers, and stainless steel coupons were air-dried. After drying, filming and spotting ratings were determined by trained evaluators by observing the glass and plastic tumblers in a light box with controlled lighting from below and the stainless steel coupons with controlled lighting from above. The glass tumblers were rated for filming and spotting according to the ASTM method, ranging from 1 (no film / spots) to 5 (severe filming / spots). Average scores of 1 to 5 for filming and spotting were determined, as reported in Table 5. Visual observations of the glass tumblers, plastic tumblers, and stainless steel coupons are also reported in Table 6.

[0056] [Table 5]

[0057] [Table 6]

Claims

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

2. 10. The dish detergent formulation of claim 1, wherein the dish detergent formulation comprises <1 wt. % HEDP, based on the weight of the dish detergent formulation.

3. 10. The dish detergent formulation of claim 1, wherein the dish detergent formulation comprises < 0.4 wt. % urea, based on the weight of the dish detergent formulation.

4. 10. The dish detergent formulation of claim 1, wherein the dish detergent formulation is a solid.

5. 10. The dish detergent formulation of claim 1, wherein the dish detergent formulation is anhydrous.

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

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

8. 10. The dish detergent formulation of claim 1, wherein the dish detergent formulation contains 0% by weight, based on the dry weight of the dish detergent formulation, 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, glutamic acid-N,N-diacetic acid, 3-hydroxy-2,2'-iminodissuccinate, S,S-ethylenediaminedisuccinic acid aspartic acid-diacetic acid, N,N'-ethylenediaminedisuccinic acid, iminodisuccinic acid, aspartic acid, aspartic acid-N,N-diacetic acid, beta-alaninediacetic acid, polyaspartic acid, salts thereof, and mixtures thereof.

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

10. 1. A method of cleaning items in an automatic dishwasher, comprising: providing at least one item; providing a dish detergent formulation selected based on its ability to inhibit the formation of phosphonate scale on said at least one item, wherein said dish detergent formulation is selected to be as recited in claim 1; applying the selected dish detergent formulation to the at least one article.

Images