Automatic dishwashing compositions

Abstract

Provided is an automatic dishwashing composition comprising a builder, a nonionic surfactant, and a carboxymethyl dextran polymer, wherein the carboxymethyl dextran polymer comprises a dextran-based polymer functionalized with carboxymethyl groups, the dextran-based polymer having a weight-average molecular weight of 10,000 to 3,000,000 Daltons before being functionalized with carboxymethyl groups, and a degree of substitution (DS) of the carboxymethyl groups on the carboxymethyl dextran polymer being 0.51 to 1.

Description

[Technical Field]

[0001] The present invention relates to an automatic dishwashing composition, specifically, the automatic dishwashing composition comprising a builder, a nonionic surfactant, and a carboxymethyl dextran polymer, wherein the carboxymethyl dextran polymer comprises a dextran-based polymer functionalized with carboxymethyl groups, the dextran-based polymer having a weight-average molecular weight of 10,000 to 3,000,000 daltons before being functionalized with carboxymethyl groups, and the degree of substitution (DS) of the carboxymethyl groups on the carboxymethyl dextran polymer is 0.51 to 1.

[0002] Automatic dishwashing compositions are generally recognized as a category of detergent compositions distinct from those used for fabric washing or water treatment, and are expected by users to result in a spot- and film-free appearance on washed items after the wash cycle is complete.

[0003] Phosphate-free automatic dishwashing compositions are increasingly desirable. Phosphate-free automatic 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 an insoluble, visible deposit upon drying.

[0004] Currently available polymers used in phosphate-free automatic dishwashing compositions to combat the formation of undesirable deposits on glassware include polyacrylic acid polymers and copolymers of acrylic acid with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and sodium styrene sulfonate (SSS). However, polyacrylic acid polymers are unable to prevent certain film deposits on glassware (e.g., magnesium silicate and calcium phosphonate limescale), which appear as a transparent blue to blue / white film on glassware and a brown film on stainless steel. While copolymers of acrylic acid and sulfonated monomers are excellent at preventing silicate and phosphonate limescale, such copolymers are not particularly effective at preventing carbonate limescale. Additionally, such polymers tend to have a negative effect on spotting and require the use of strong chelating agents or specialized surfactants, which undesirably increase the overall cost of the dishwashing composition.

[0005] Thus, there remains a need for new polymers for use in automatic dishwashing formulations, particularly new polymers for use in automatic dishwashing formulations that provide suitable spotting and / or filming performance when the polymers are incorporated into phosphate-free formulations and that provide an improved balance of biogenic and biodegradable components.

[0006] The present invention provides an automatic dishwashing composition comprising a builder, a nonionic surfactant, and a carboxymethyl dextran polymer, wherein the carboxymethyl dextran polymer comprises a dextran-based polymer functionalized with carboxymethyl groups, the dextran-based polymer having a weight-average molecular weight of 10,000 to 3,000,000 Daltons before being functionalized with carboxymethyl groups, and a degree of substitution (DS) of the carboxymethyl groups on the carboxymethyl dextran polymer being 0.51 to 1.

[0007] The present invention also provides a method of cleaning items in an automatic dishwashing machine, the method comprising providing at least one item, providing an automatic dishwashing composition according to the present invention, and applying the automatic dishwashing composition to the at least one item. DETAILED DESCRIPTION OF THE INVENTION

[0008] Surprisingly, it has been found that the carboxymethyl dextran polymers of the present invention, when incorporated into automatic dishwashing compositions (particularly phosphate-free automatic dishwashing compositions), surprisingly provide better spotting and filming performance on a variety of surfaces, including plastics, compared to conventional dispersant polymers and carboxymethyl dextran polymers having a carboxymethyl dextran degree of substitution, DS, outside the specified range of 0.51 to 1 (as measured by non-aqueous titration similar to the technique described in ASTM D1439 for determining the degree of substitution of carboxymethyl groups on carboxymethyl cellulose polymers).

[0009] 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 solids weight, i.e., excluding any water that may be present in the polymer emulsion.

[0010] 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 conventional manner using gel permeation chromatography (GPC) and conventional standards such as polyethylene glycol 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.

[0011] As used herein and in the appended claims, the term "phosphate-free" means a composition containing 1% by weight or less (preferably, 0.5% by weight or less, more preferably, 0.2% by weight or less, even more preferably, 0.01% by weight or less, still more preferably, 0.001% by weight or less, and most preferably below the detection limit) of phosphate (measured as elemental phosphorus).

[0012] Preferably, the automatic dishwashing composition of the present invention comprises a builder (preferably 1 to 99 wt. % (more preferably 10 wt. % or more, even more preferably 20 wt. % or more, even more preferably 25 wt. % or more, most preferably ≧50 wt. %, preferably 95 wt. % or less, more preferably 90 wt. % or less, even more preferably 85 wt. % or less, most preferably 80 wt. % or less) of the builder, based on the dry weight of the automatic dishwashing composition) (preferably the builder comprises a mixture of at least one carbonate and at least one citrate), and a nonionic surfactant (preferably 0.5 to 15 wt. % (more preferably 0.75 to 10 wt. %, most preferably 1.5 to 7.5 wt. %) of the nonionic surfactant, based on the dry weight of the automatic dishwashing composition) (preferably the nonionic surfactant is a fatty alcohol alkoxylate). and a carboxymethyl dextran polymer (preferably 0.5 to 15 wt. % (more preferably 1 to 10 wt. %, even more preferably 2 to 8 wt. %, and most preferably 4 to 7 wt. %) of a dispersant polymer, based on the dry weight of the automatic dishwashing composition), wherein the carboxymethyl dextran polymer comprises a dextran base polymer functionalized with carboxymethyl groups, the dextran base polymer having a weight average molecular weight of 10,000 to 3,000,000 Daltons before being functionalized with carboxymethyl groups, and the degree of substitution DS of the carboxymethyl groups on the carboxymethyl dextran polymer is 0.51 to 1 (preferably 0.54 to 0.75, more preferably 0.55 to 0.725, and most preferably 0.56 to 0.7) (ASTM C 10000:2004). D1439) (preferably, the carboxymethyl dextran polymer has inherent ultimate biodegradability as determined according to procedure OECD 302B).

[0013] Preferably, the automatic dishwashing compositions of the present invention comprise a builder. Preferably, the automatic dishwashing compositions of the present invention comprise a builder, wherein the builder comprises a mixture of at least one carbonate and at least one citrate. More preferably, the automatic dishwashing compositions of the present invention comprise a builder, wherein the builder comprises a mixture of at least one carbonate, at least one citrate, and at least one silicate. Most preferably, the automatic dishwashing compositions of the present invention comprise a builder, wherein the builder comprises a mixture of sodium carbonate, sodium citrate, and sodium silicate.

[0014] Preferably, the automatic dishwashing compositions of the present invention comprise 1 to 99 wt.% builder, based on the dry weight of the automatic dishwashing composition. Preferably, the automatic dishwashing compositions of the present invention comprise 1 wt.% or more (preferably 10 wt.% or more, more preferably 20 wt.% or more, even more preferably 25 wt.% or more, and most preferably ≧50 wt.%) builder, based on the dry weight of the automatic dishwashing composition. Preferably, the automatic dishwashing compositions of the present invention comprise 95 wt.% or less (preferably 90 wt.% or less, more preferably 85 wt.% or less, and most preferably ≦80 wt.%) builder, based on the dry weight of the automatic dishwashing composition. The weight percentages of carbonate, citrate, and silicate builders are based on the actual weight of the metal ion-containing salt.

[0015] The term "carbonate" as used herein and in the appended claims refers to alkali metal or ammonium carbonate, bicarbonate, and / or sesquicarbonate. Preferably, the carbonate (if present) used in the automatic dishwashing composition is selected from the group consisting of sodium, potassium, and lithium carbonate (more preferably, sodium or potassium salts, most preferably, sodium salts). Most preferably, the carbonate (if present) used in the automatic dishwashing composition comprises at least one of sodium carbonate and sodium bicarbonate. Preferably, when the builder used in the automatic dishwashing composition of the present invention comprises a carbonate, the automatic dishwashing composition preferably comprises 0 to 99 wt. % (preferably, 10 to 75 wt. %, more preferably, 25 to 60 wt. %, and most preferably, 40 to 50 wt. %) of the carbonate, based on the dry weight of the automatic dishwashing composition.

[0016] The term "citrate" as used herein and in the appended claims refers to an alkali metal citrate. Preferably, the citrate salt (if present) used in the automatic dishwashing composition 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 automatic dishwashing composition is sodium citrate. Preferably, when the builder used in the automatic dishwashing composition of the present invention comprises a citrate salt, the automatic dishwashing composition preferably comprises 0 to 99 wt. % (preferably, 5 to 75 wt. %, more preferably, 10 to 60 wt. %, and most preferably, 20 to 40 wt. %) of the citrate salt, based on the dry weight of the automatic dishwashing composition.

[0017] The term "silicate" as used herein and in the appended claims refers to an alkali metal silicate. Preferably, the silicate used in the automatic dishwashing composition (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 automatic dishwashing composition (if present) is sodium disilicate. Preferably, the builder used in the automatic dishwashing composition of the present invention includes a silicate. Preferably, when the builder used in the automatic dishwashing composition of the present invention includes a silicate, the automatic dishwashing composition preferably includes 0 to 99 wt. % (preferably 0.1 to 10 wt. %, more preferably 0.5 to 7.5 wt. %, most preferably 0.75 to 3 wt. %) of the silicate, based on the dry weight of the automatic dishwashing composition.

[0018] Preferably, the automatic dishwashing composition of the present invention comprises 0.5 to 15 wt. % (preferably 0.75 to 10 wt. %, more preferably 1.5 to 7.5 wt. %) of a nonionic surfactant, based on the dry weight of the automatic dishwashing composition. More preferably, the automatic dishwashing composition of the present invention comprises 0.5 to 15 wt. % (preferably 0.5 to 10 wt. %, more preferably 1.5 to 7.5 wt. %) of a nonionic surfactant, based on the dry weight of the automatic dishwashing composition, and the surfactant comprises a fatty alcohol alkoxylate. Most preferably, the automatic dishwashing composition of the present invention comprises 0.5 to 15 wt. % (preferably 0.5 to 10 wt. %, more preferably 1.5 to 7.5 wt. %) of a nonionic surfactant, based on the dry weight of the automatic dishwashing composition, and the surfactant is a fatty alcohol alkoxylate.

[0019] Preferably, the nonionic surfactant used in the automatic dishwashing compositions of the present invention is ROM) x -(N) y -OH, and ROM) x -(N) y -(P)z -OH wherein M represents an ethylene oxide structural unit and N represents a C 3~18 Represents the structural unit of 1,2-epoxyalkane, and P is C 6~18 where x is 5 to 40, y is 0 to 20, z is 0 to 3, and R is C 6~22 represents a straight or branched chain alkyl group).

[0020] Preferably, the nonionic surfactant used in the automatic dishwashing compositions of the present invention is ROM) x -(N) y -OH, and ROM) x -(N) y -O-R' wherein M and N are structural units derived from alkylene oxide (one of which is ethylene oxide), x is 5 to 40, y is 0 to 20, and R is C 6~22 represents a linear or branched alkyl group, and R' is an alcohol precursor and C 6~22 represents a group derived from the reaction of a linear or branched alkyl halide, an epoxyalkane, or a glycidyl ether.

[0021] Preferably, the nonionic surfactant used in the automatic dishwashing compositions of the present invention has the formula: ROM) x -OH (wherein M represents an ethylene oxide structural unit and x is at least 3 (preferably at least 5, preferably 10 or less, more preferably 8 or less). Preferably, in the formula, R and R' each have at least 8 (more preferably at least 10) carbon atoms.

[0022] Preferably, the automatic dishwashing composition of the present invention comprises 0.5 to 15 wt. % (preferably 1 to 10 wt. %, more preferably 2 to 8 wt. %, most preferably 4 to 7 wt. %) of carboxymethyl dextran polymer, based on the dry weight of the automatic dishwashing composition. More preferably, the automatic dishwashing composition of the present invention comprises 0.5 to 15 wt. % (preferably 1 to 10 wt. %, more preferably 2 to 8 wt. %, and most preferably 4 to 7 wt. %) of a carboxymethyl dextran polymer, based on the dry weight of the automatic dishwashing composition, the carboxymethyl dextran polymer comprising a dextran base polymer functionalized with carboxymethyl groups, the dextran base polymer having a weight average molecular weight of 10,000 to 3,000,000 Daltons prior to functionalization with carboxymethyl groups, and the degree of substitution of the carboxymethyl groups on the carboxymethyl dextran polymer, DS, is 0.51 to 1 (preferably 0.54 to 0.75, more preferably 0.55 to 0.725, and most preferably 0.56 to 0.7), as measured by non-aqueous titration similar to the technique described in ASTM D1439 for determining the degree of substitution of carboxymethyl groups on carboxymethyl cellulose polymers.Most preferably, the automatic dishwashing composition of the present invention comprises 0.5 to 15 wt. % (preferably 1 to 10 wt. %, more preferably 2 to 8 wt. %, and most preferably 4 to 7 wt. %) of a carboxymethyl dextran polymer, based on the dry weight of the automatic dishwashing composition, the carboxymethyl dextran polymer comprising a dextran base polymer functionalized with carboxymethyl groups, the dextran base polymer having a weight average molecular weight of 10,000 to 3,000,000 Daltons before being functionalized with carboxymethyl groups, the degree of substitution of the carboxymethyl groups on the carboxymethyl dextran polymer, DS, being 0.51 to 1 (preferably 0.54 to 0.75, more preferably 0.55 to 0.725, and most preferably 0.56 to 0.7) (as measured by non-aqueous titration similar to the technique described in ASTM D1439 for determining the degree of substitution of carboxymethyl groups on carboxymethyl cellulose polymers), the carboxymethyl dextran polymer being prepared according to procedure OECD 302B (preferably, the carboxymethyl dextran polymer has inherent ultimate biodegradability as determined according to procedure OECD 302B).

[0023] Preferably, the dextran-based polymer has a weight average molecular weight of 10,000 to 3,000,000 daltons (preferably 50,000 to 2,500,000 daltons, more preferably 75,000 to 2,000,000 daltons, even more preferably 100,000 to 1,000,000 daltons, and most preferably 125,000 to 750,000 daltons) before being functionalized with carboxymethyl groups. More preferably, the dextran-based polymer has a weight average molecular weight of 10,000 to 3,000,000 daltons (preferably 50,000 to 2,500,000 daltons, more preferably 75,000 to 2,000,000 daltons, even more preferably 100,000 to 1,000,000 daltons, and most preferably 125,000 to 750,000 daltons) before being functionalized with carboxymethyl groups. The dextran-based polymer is a branched-chain dextran polymer containing a plurality of glucose structural units, in which 90 to 98 mol % (preferably 92.5 mol % to 97.5 mol %, more preferably 93 to 97 mol %, and most preferably 94 to 96 mol %) of the glucose structural units are connected by α-1,6 bonds, and 2 to 10 mol % (preferably 2.5 to 7.5 mol %, more preferably 3 to 7 mol %, and most preferably 4 to 6 mol %) of the glucose structural units are connected by α-1,2 bonds, α-1,3 bonds, and / or α-1,4 bonds. Most preferably, the dextran-based polymer has a weight average molecular weight of 10,000 to 3,000,000 daltons (preferably 50,000 to 2,500,000 daltons, more preferably 75,000 to 2,000,000 daltons, even more preferably 100,000 to 1,000,000 daltons, and most preferably 125,000 to 750,000 daltons) before being functionalized with carboxymethyl groups.The dextran-based polymer is a branched dextran polymer containing a plurality of glucose structural units, in which 90 to 98 mol % (preferably 92.5 to 97.5 mol %, more preferably 93 to 97 mol %, and most preferably 94 to 96 mol %) of the glucose structural units are connected by α-D-1,6 bonds, and 2 to 10 mol % (preferably 2.5 to 7.5 mol %, more preferably 3 to 7 mol %, and most preferably 4 to 6 mol %) of the glucose structural units are represented by Formula I:

[0024] [ka] (In the formula, R 1 is hydrogen, C 1~4 Alkyl and hydroxy C 1~4 The alkyl groups are connected by α-1,3 bonds according to the following formula: the average branch from the dextran polymer backbone is 1 to 3 anhydroglucose units.

[0025] Preferably, the dextran-based polymer contains less than 0.01% by weight of alternan, based on the weight of the dextran-based polymer. More preferably, the dextran-based polymer contains less than 0.001% by weight of alternan, based on the weight of the dextran-based polymer. Most preferably, the dextran-based polymer contains less than the detectable limit of alternan.

[0026] Preferably, less than 0.1 mol % (preferably less than 0.01 mol %, more preferably less than 0.001 mol %, most preferably below the detection limit) of the glucose structural units in the dextran-based polymer are connected by β-1,4 linkages.

[0027] Preferably, less than 0.1 mol % (preferably less than 0.01 mol %, more preferably less than 0.001 mol %, most preferably below the detection limit) of the glucose structural units in the dextran-based polymer are connected by β-1,3 bonds.

[0028] Preferably, the carboxymethyl dextran polymer has a degree of substitution of carboxymethyl groups, DS (as measured by non-aqueous titration similar to the technique described in ASTM D1439 for determining the degree of substitution of carboxymethyl groups on carboxymethyl cellulose polymers) of 0.51 to 1 (preferably 0.54 to 0.75, more preferably 0.55 to 0.725, most preferably 0.56 to 0.7).

[0029] Preferably, the carboxymethyl dextran polymer is biodegradable as determined according to procedure OECD 302B. More preferably, the carboxymethyl dextran polymer has inherent ultimate biodegradability as determined according to procedure OECD 302B.

[0030] Methods for making the carboxymethyl dextran polymers used in the automatic dishwashing compositions of the present invention are known.

[0031] Preferably, the automatic dishwashing composition of the present invention further comprises 0.1 to 15 wt. % (more preferably 0.5 to 10 wt. %, even more preferably 0.75 to 7 wt. %, and most preferably 0.9 to 5 wt. %) of a phosphonate based on the dry weight of the automatic dishwashing composition. More preferably, the automatic dishwashing composition of the present invention further comprises 0.1 to 15 wt. % (more preferably 0.5 to 10 wt. %, even more preferably 0.75 to 7 wt. %, and most preferably 0.9 to 5 wt. %) of a phosphonate based on the dry weight of the automatic dishwashing composition, the phosphonate having a low molecular weight having a weight average molecular weight of 1,000 daltons or less. Even more preferably, the automatic dishwashing composition of the present invention further comprises 0.1 to 15 wt. % (more preferably, 0.5 to 10 wt. %, even more preferably, 0.75 to 7 wt. %, and most preferably, 0.9 to 5 wt. %) of a phosphonate salt, based on the dry weight of the automatic dishwashing composition, the phosphonate salt 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 automatic dishwashing composition of the present invention further comprises 0.1 to 15 wt. % (more preferably, 0.5 to 10 wt. %, even more preferably, 0.75 to 7 wt. %, and most preferably, 0.9 to 5 wt. %) of a phosphonate salt, based on the dry weight of the automatic dishwashing composition, the phosphonate salt being selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts thereof.

[0032] The automatic dishwashing compositions of the present invention optionally further comprise additives. Preferably, the automatic dishwashing compositions of the present invention further comprise an additive selected from the group consisting of an alkaline source, a bleaching agent (e.g., sodium percarbonate, sodium perborate), a bleach activator (e.g., tetraacetylethylenediamine (TAED)), 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 suppressor, a colorant, a fragrance, an additional builder, an antimicrobial agent, a filler, a deposit control polymer, and mixtures thereof. More preferably, the automatic dishwashing compositions of the present invention further comprise an additive selected from the group consisting of a bleaching agent, a bleach activator, an enzyme, a filler, and mixtures thereof. Even more preferably, the automatic dishwashing compositions of the present invention further comprise additives, including a bleaching agent (e.g., sodium percarbonate, sodium perborate), a bleach activator (e.g., tetraacetylethylenediamine (TAED)), and an enzyme (e.g., a protease, an amylase, a lipase, or a cellulase). Most preferably, the automatic dishwashing compositions of the present invention further comprise additives, including a bleaching agent comprising sodium percarbonate, a bleach activator comprising tetraacetylethylenediamine (TAED), and an enzyme, including a protease and an amylase.

[0033] Fillers included in tablets or powders 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 in water. Fragrances, dyes, suds suppressors, enzymes, and antimicrobial agents usually total no more than 10% by weight, alternatively no more than 5% by weight, of the automatic dishwashing composition.

[0034] The automatic dishwashing compositions of the present invention optionally further comprise an alkaline source. Suitable alkaline sources include, but are not limited to, alkali metal carbonates and alkali metal hydroxides, such as sodium or potassium carbonate, bicarbonates, sesquicarbonates, sodium, lithium or potassium hydroxide, or mixtures thereof. Sodium hydroxide is preferred. The amount of alkaline source (if present) in the automatic dishwashing compositions 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 automatic dishwashing composition.

[0035] The automatic dishwashing compositions of the present invention optionally further comprise a bleaching agent (e.g., sodium percarbonate). The amount of bleaching agent (if present) in the automatic dishwashing compositions of the present invention is preferably at a concentration of 1 to 25% by weight (more preferably 5 to 20% by weight), based on the dry weight of the automatic dishwashing composition.

[0036] The automatic dishwashing compositions of the present invention optionally further comprise a bleach activator, such as tetraacetylethylenediamine (TAED). The amount of bleach activator, if present, in the automatic dishwashing compositions of the present invention is preferably at a concentration of 1 to 10 wt. % (more preferably 2.5 to 7.5 wt. %), based on the dry weight of the automatic dishwashing composition.

[0037] Preferably, the automatic dishwashing compositions of the present invention contain 1% or less (preferably 0.5% or less, more preferably 0.2% or less, even more preferably 0.1% or less, even more preferably 0.01% or less, and most preferably below the detection limit) of phosphate (measured as elemental phosphorus) based on the dry weight of the automatic dishwashing composition. Preferably, the automatic dishwashing compositions of the present invention are phosphate-free.

[0038] Preferably, the automatic dishwashing compositions of the present invention contain 1% by weight (preferably, 0.5% by weight or less, more preferably, 0.2% by weight or less, even more preferably, 0.1% by weight or less, even more preferably, 0.01% by weight or less, and most preferably, below the limit of detection) of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycine-N,N-diacetic acid, methylglycine-N,N-diacetic acid, 2-hydroxybenzoates, methyl ... The composition further comprises a builder selected from the group consisting of diethyliminodiacetate, glutamic acid-N,N-diacetate, 3-hydroxy-2,2'-iminodisuccinate, S,S-ethylenediaminedisuccinic acid aspartic acid-diacetate, N,N'-ethylenediaminedisuccinic acid, iminodisuccinic acid, aspartic acid, aspartic acid-N,N-diacetate, beta-alanine diacetate, polyaspartic acid, salts thereof, and mixtures thereof. Most preferably, the automatic dishwashing compositions of the present invention contain 0 wt. % 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.

[0039] Preferably, the automatic dishwashing compositions of the present invention have a pH (at 1% by weight in water) of at least 7 (preferably 9 or more, more preferably 9.5 or more). Preferably, the automatic dishwashing compositions of the present invention have a pH (at 1% by weight in water) of 13 or less.

[0040] Preferably, the automatic dishwashing compositions of the present invention can be formulated in any typical form, such as a tablet, powder, loaf, single dose, sachet, paste, liquid, or gel. The automatic dishwashing compositions of the present invention are useful for cleaning items such as dishes and utensils, plates, and the like in automatic dishwashing machines.

[0041] Preferably, the automatic dishwashing compositions 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 automatic dishwashing compositions, 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 automatic dishwashing compositions of the present invention can be present in the pre-wash, main wash, penultimate rinse, final rinse, or any combination of these cycles.

[0042] Preferably, the method of cleaning articles in an automatic dishwasher of the present invention comprises providing at least one article (e.g., cookware, heat-resistant ware, tableware, cutlery, flatware, and / or glassware, preferably, the at least one article comprises glassware), providing an automatic dishwashing composition of the present invention, and applying the automatic dishwashing composition to the at least one article (preferably in an automatic dishwasher).

[0043] Preferably, the method of cleaning articles in an automatic dishwasher of the present invention comprises: (i) providing at least one article (e.g., cookware, heat-resistant ware, tableware, cutlery, flatware, and / or glassware, preferably, the at least one article comprises glassware); and (ii) providing an automatic dishwashing composition of the present invention, wherein the provided automatic dishwashing composition comprises 50 to 85 wt. % of a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof, including a mixture of at least one carbonate and at least one citrate; 0.75 to 7 wt. % of a phosphonate; and 1.5 to 7.5 wt. % of a non-ionic surfactant. and 2-6 wt. % carboxymethyl dextran polymer, the carboxymethyl dextran polymer comprising a dextran base polymer functionalized with carboxymethyl groups, the dextran base polymer having a weight average molecular weight of 10,000-3,000,000 Daltons prior to functionalization with the carboxymethyl groups, and a degree of substitution of the carboxymethyl groups on the carboxymethyl dextran polymer, DS, of 0.51-1 (preferably 0.54-0.75, more preferably 0.55-0.725, and most preferably 0.56-0.7) (as measured by non-aqueous titration similar to the technique described in ASTM D1439 for determining the degree of substitution of carboxymethyl groups on carboxymethyl cellulose polymers). (Preferably, the carboxymethyl dextran polymer is inherently ultimately biodegradable as determined according to procedure OECD 302B.)

[0044] Some embodiments of the present invention will now be described in detail in the following examples.

[0045] The volatiles and ash content of the carboxymethyl dextran polymers prepared herein were measured according to ASTM D2364-15. Although ASTM D2364-15 is written for hydroxyethyl cellulose, the same principles apply to carboxymethyl dextran polymers. Ash content is reported as sodium acetate equivalents.

[0046] The degree of substitution (DS) of the carboxymethyl dextran polymers prepared herein was measured according to the non-aqueous titration method of ASTM D1439-15. Although ASTM D1439-15 describes carboxymethyl cellulose, the same principles apply since both carboxymethyl dextran polymers and carboxymethyl cellulose are polysaccharides containing carboxymethyl substituents. An accurately weighed amount of carboxymethyl dextran polymer was first refluxed in glacial acetic acid, and the resulting sodium acetate was titrated with perchloric acid as a strong acid. Crystal violet was used as the indicator, and the titrant changed color from purple / blue to green at the end point.

[0047] Examples S1-S7: Synthesis of carboxymethyl dextran polymers 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 and providing power to a heating mantle. The flask was first charged with dextran powder, sodium chloroacetate, and deionized water, as shown in Table 1.

[0048] Stirring of the flask contents was initiated at 200 rpm, and a nitrogen blanket was applied to remove entrained air. After 1 hour, the reaction mixture formed a clear, colorless solution. A 50 wt. % aqueous sodium hydroxide solution, in the amount listed in Table 1, was then added dropwise to the flask contents. After the sodium hydroxide solution was added, the flask contents were stirred at ambient temperature for 5 minutes. The temperature setpoint of the J-KEM temperature controller was then increased to 70°C and held at that temperature for 3 hours. The flask contents were then cooled to ambient temperature in an ice / water bath (using a continuous nitrogen flow), and the reaction was quenched by adding glacial acetic acid, in the amount listed in Table 1, dropwise to the flask contents. After a 10-minute hold, the flask contents were diluted with 6 L of methanol. The flask contents were allowed to soak overnight, and the product polymer was collected in a fritted Buchner funnel, further washed with methanol, and dried overnight in a vacuum oven at 50°C. The product yield, weight % of volatiles, ash content as weight % of sodium acetate (NaOAc), and the degree of substitution of carboxymethyl groups on the base dextran, DS, measured by titration with perchloric acid for the product, are reported in Table 2.

[0049] [Table 1]

[0050] Example S8: Synthesis of carboxymethyl dextran polymer 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 first charged with dextran powder (40.17 g, Aldrich D4876, 150,000 Da, corresponding to an active substance content of 37.16 g), sodium chloroacetate (13.39 g), and deionized water (208.15 g).

[0051] Stirring of the flask contents was initiated at 200 rpm, and a nitrogen blanket was applied to remove entrained air. After 1 hour, the reaction mixture formed a clear, colorless solution. 50 wt. % aqueous sodium hydroxide solution (11.95 g) was then added dropwise to the flask contents. After the addition of the sodium hydroxide solution, the flask contents were stirred at ambient temperature for 5 minutes. The temperature setpoint of the J-KEM temperature controller was then increased to 70°C and held at that temperature 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 (4.70 g) was added dropwise to the flask contents to quench the reaction. After a 10-minute hold, the flask contents were transferred to 6 L of methanol. After 15 minutes, the precipitated polymer was collected in a fritted Buchner funnel, further washed with methanol, and dried overnight in a vacuum oven at 50°C. The above procedure was repeated using the following materials: dextran (39.95 g), sodium chloroacetate (13.41 g), water (208.61 g), 50 wt % aqueous NaOH solution (12.00 g), and glacial acetic acid (4.70 g). The dried precipitated polymer recovered from the two separate batches was then blended together to obtain the final product polymer. The product yield, weight percent volatiles, ash content as weight percent of sodium acetate (NaOAc), and the degree of substitution (DS) of carboxymethyl groups on the base dextran, as determined by titration with perchloric acid, for the product, are reported in Table 2.

[0052] [Table 2]

[0053] Comparative Examples CF1-CF8 and Examples F1-F2: Dishwashing Performance Dishwashing compositions were prepared in each of Comparative Examples CF1-CF8 and Examples F1-F2 having the ingredient formulations specified in Table 3.

[0054] [Table 3]

[0055] Steps for preparing food stains The STIWA food soils described in Table 4 were prepared by the following procedure. a) Boil water. b) Mix instant gravy, benzoic acid, and starch in a paper cup and then add the mixture to boiling water. c) Add milk and margarine to the product of (b). d) Cool the product of (c) to about 40°C and then add the mixture to a kitchen mixer (Polytron). e) In a separate paper cup, combine the egg yolks, ketchup, and mustard and mix with a spoon. f) Add the product of (e) to the mixture of (d) in the blender with continuous stirring. g) Blend the product of (f) in a blender for 5 minutes. h) Freeze the product food soil mixture from (g). i) Place 50g of this frozen slush into the dishwasher at the start of the main wash.

[0056] [Table 4]

[0057] Dishwashing test conditions Machine: Miele SS-ADW, model G1223SC Labor. Wash at 65°C - 30 minute wash cycle, followed by two rinse cycles at 65°C rinse water temperature, and a final 30 minute dry step. After the dry cycle was completed, the dishwasher door was left open for 30 minutes to allow steam to evaporate. Water: The initial water supplied to the dishwasher had a total water hardness of 40°F hardness, Ca 2+ :Mg 2+= 3:1, and a temporary water hardness of 27°fH. Food Soils: 50 g of the composition described in Table 4 was introduced into the wash liquor in a frozen cup. Each dishwashing composition from Comparative Examples CF1-8 and Examples F1-F2 was tested. The food soil was added at the beginning of the wash cycle. The test detergent was also dosed into the dishwasher at the beginning of the wash cycle. Each test detergent was dosed at 17 g (solids basis) per wash. The number of wash cycles used in this experiment to induce filming and spotting was 14.

[0058] Evaluation of Schott® Glass Filming and Spotting After 14 wash cycles under the above dishwashing test conditions, the Schott® glasses were allowed to air dry for at least 18 hours. After air drying following the 14th wash, filming and spotting ratings were determined in a light box with controlled lighting from below. The Schott® tumblers were scored for filming and spotting according to ASTM methods, ranging from 1 (no filming / spotting) to 5 (severe filming / spotting). Average scores of 1-5 for filming and spotting were calculated, as reported in Tables 5 and 6.

[0059] [Table 5]

[0060] [Table 6]

[0061] 304 Polished Stainless Steel Coupons and Spot Formation Evaluation After 14 wash cycles under the above dishwashing test conditions, the 304 polished stainless steel coupons were allowed to air dry for at least 18 hours. After air drying, filming and spotting ratings were determined in a light box with controlled lighting. The 304 polished stainless steel coupons were scored for filming and spotting on a scale of 1 (no filming / spotting) to 5 (severe filming / spotting). The average scores of 1 to 5 for filming and spotting were calculated, as reported in Tables 7 and 8.

[0062] [Table 7]

[0063] [Table 8]

Claims

1. 1. An automatic dishwashing composition comprising: Builder and a nonionic surfactant; a carboxymethyl dextran polymer; wherein the carboxymethyl dextran polymer comprises a dextran base polymer functionalized with carboxymethyl groups, the dextran base polymer having a weight average molecular weight of 10,000 to 3,000,000 Daltons prior to functionalization with carboxymethyl groups, and a degree of substitution DS of the carboxymethyl groups on the carboxymethyl dextran polymer is 0.51 to 1.

2. 10. The automatic dishwashing composition of claim 1, wherein the dextran-based polymer has a weight average molecular weight of 125,000 to 750,000 Daltons before being functionalized with carboxymethyl groups.

3. 3. The automatic dishwashing composition of claim 2 further comprising a phosphonate.

4. 4. The automatic dishwashing composition of claim 3, wherein the builder comprises a mixture of at least one carbonate salt and at least one citrate salt.

5. 5. The automatic dishwashing composition of claim 4 containing less than 0.1 wt. % phosphate, measured as elemental phosphorus, based on the dry weight of the automatic dishwashing composition.

6. 6. The automatic dishwashing composition of claim 5, wherein the dextran-based polymer has a weight average molecular weight of 150,000 to 500,000 Daltons before being functionalized with carboxymethyl groups.

7. 7. The automatic dishwashing composition of claim 6, wherein the automatic dishwashing composition contains 0 wt. % based on the dry weight of the automatic dishwashing composition 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.

8. 8. The automatic dishwashing composition of claim 7, further comprising an additive selected from the group consisting of bleaches, bleach activators, enzymes, fillers, and mixtures thereof.

9. 50 to 85 wt. % of the builder, based on the dry weight of the automatic dishwashing composition, wherein the builder is selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; 0.75 to 7 wt. % of said phosphonate, based on the dry weight of said automatic dishwashing composition; 1.5 to 7.5 wt. % of said nonionic surfactant, based on the dry weight of said automatic dishwashing composition; 2-6% by weight of the carboxymethyl dextran polymer, based on the dry weight of the automatic dishwashing composition; 4. The automatic dishwashing composition of claim 3, comprising:

10. 1. A method of cleaning items in an automatic dishwasher, comprising: providing at least one item; Providing an automatic dishwashing composition according to claim 1; applying said automatic dishwashing composition to said at least one item.

Images