Automatic dishwashing detergent formulation

Abstract

An automatic dishwashing detergent formulation is provided including a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid.

Description

Attorney Docket No.85928-WO-PCT AUTOMATIC DISHWASHING DETERGENT FORMULATION

[0001] The present invention relates to an automatic dishwashing detergent formulation. In particular, the present invention relates to an automatic dishwashing detergent formulation comprising: a builder; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid.

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

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

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

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

[0006] Notwithstanding there remains a need for new dispersant polymers for use in automatic dishwashing formulations. In particular, there remains a need for new dispersant polymers for use in automatic dishwashing formulations, wherein the dispersant polymers provide effective low filming performance; are biosourced and biodegradable.Attorney Docket No.85928-WO-PCT

[0007] The present invention provides an automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid.

[0008] The present invention provides an automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid; wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons.

[0009] The present invention provides an automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid; wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons; and wherein the poly(malic ester) polymer comprises ≤ 40 mol% of structural units selected from the group consisting of structural units of lactic acid; structural units of glycolic acid; structural units of hydroxystearic acid; and mixtures thereof.

[0010] The present invention provides an automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid; wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons; wherein the poly(malic ester) polymer comprises ≤ 40 mol% of structural units selected from the group consisting of structural units of lactic acid; structural units of glycolic acid; structural units of hydroxystearic acid; and mixtures thereof; and wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of tartaric acid or residues of tartaric acid.

[0011] The present invention provides an automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid; wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons; wherein the poly(malic ester) polymer comprises ≤ 40 mol% of structural units selected from the group consisting of structural units of lactic acid; structural units of glycolic acid; structural units ofAttorney Docket No.85928-WO-PCT hydroxystearic acid; and mixtures thereof; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of tartaric acid or a residue of tartaric acid; and wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of sodium alginate.

[0012] The present invention provides an automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid; wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons; wherein the poly(malic ester) polymer comprises ≤ 40 mol% of structural units selected from the group consisting of structural units of lactic acid; structural units of glycolic acid; structural units of hydroxystearic acid; and mixtures thereof; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of tartaric acid or residues of tartaric acid; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of sodium alginate; and wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of depentane oil.

[0013] The present invention provides an automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid; wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons; wherein the poly(malic ester) polymer comprises ≤ 40 mol% of structural units selected from the group consisting of structural units of lactic acid; structural units of glycolic acid; structural units of hydroxystearic acid; and mixtures thereof; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of tartaric acid or residues of tartaric acid; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of sodium alginate; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of depentane oil; and wherein the automatic dishwashing detergent formulation is an anhydrous solid.Attorney Docket No.85928-WO-PCT

[0014] The present invention provides an automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid; wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons; wherein the poly(malic ester) polymer comprises ≤ 40 mol% of structural units selected from the group consisting of structural units of lactic acid; structural units of glycolic acid; structural units of hydroxystearic acid; and mixtures thereof; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of tartaric acid or residues of tartaric acid; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of sodium alginate; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of depentane oil; wherein the automatic dishwashing detergent formulation is an anhydrous solid; and wherein the automatic dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the automatic dishwashing formulation, of phosphate, measured as elemental phosphorus; and wherein the automatic dishwashing formulation contains 0 wt%, based on the dry weight of the automatic dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2’-iminodissuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’-ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta-alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof.

[0015] The present invention provides an automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; an additive selected from the group consisting of a bleaching agent, a bleach activator, an enzyme, a filler, and mixtures thereof; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid; wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons; wherein the poly(malic ester) polymer comprises ≤ 40 mol% of structural units selected from the group consisting of structural units of lactic acid; structural units of glycolic acid; structural units of hydroxystearic acid; and mixtures thereof; wherein theAttorney Docket No.85928-WO-PCT automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of tartaric acid or residues of tartaric acid; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of sodium alginate; wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of depentane oil; wherein the automatic dishwashing detergent formulation is an anhydrous solid; and wherein the automatic dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the automatic dishwashing formulation, of phosphate, measured as elemental phosphorus; and wherein the automatic dishwashing formulation contains 0 wt%, based on the dry weight of the automatic dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2’-iminodissuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’-ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta-alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof.

[0016] The present invention provides a method of cleaning an article in an automatic dishwashing machine, comprising: providing at least one soiled article; providing an automatic dishwashing composition according to the present invention; and, applying the automatic dishwashing composition to the at least one soiled article to provide a cleaned article. DETAILED DESCRIPTION

[0017] Surprisingly, it has been found that, the poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid, provide good filming performance on glassware compared to conventional dispersant polymers, while having the benefit of improving the overall sustainability of the automatic dishwashing detergent formulation (i.e., being biosourced and exhibiting improved biodegradability relative to conventional dispersant polymers such as polyacrylic acid).

[0018] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight. Weight percentages (or wt%) in the composition are percentages of dry weight, i.e., excluding any water that may be present in the composition. Percentages of monomer units in the polymer are percentages of dry weight, i.e., excluding any water present in a polymer emulsion.Attorney Docket No.85928-WO-PCT

[0019] Preferably, the automatic dishwashing detergent formulation of the present invention, comprises: a builder (preferably, 1 to 97 wt% (more preferably 10 to 98.5 wt%; most preferably, 25 to 96 wt%), based on dry weight of the automatic dishwashing detergent formulation, of the builder), wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant (preferably, 0.2 to 15 wt% (more preferably, 0.5 to 10 wt%; most preferably, 1.5 to 8.5 wt%), based on dry weight of the automatic dishwashing detergent formulation, of the nonionic surfactant); and a poly(malic ester) polymer (preferably, 0.2 to 15 wt% (more preferably, 1 to 10 wt%; still more preferably, 2.5 to 7.5 wt%; yet more preferably, > 5 to 7.25 wt%; most preferably, 5.5 to 7 wt%), based on dry weight of the automatic dishwashing detergent formulation, of the poly(malic ester) polymer); wherein the poly(malic ester) polymer comprises > 60 mol% (preferably, 70 to 100 mol%; more preferably, 75 to 100 mol%; still more preferably, 80 to 100 mol%; yet more preferably, 90 to 100 mol%; still yet more preferably, 95 to 100 mol%; most preferably, 98 to 100 mol%), based on weight of the poly(malic ester) polymer, of structural units of malic acid (preferably, wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons (preferably, 1,000 to 4,000 Daltons; more preferably, 1,000 to 2,500 Daltons; most preferably, 1,000 to 2,000 Daltons)(measured by Matrix Assisted Laser Desorption / Ionization Mass Spectrometry (MALDI-MS)).

[0020] Preferably, the automatic dishwashing detergent formulation of the present invention, comprises a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate. More preferably, the automatic dishwashing detergent formulation of the present invention, comprises a builder, wherein the builder comprises a mixture of at least two components selected from the group consisting of a carbonate, a silicate and an organophosphonate.

[0021] Preferably, the automatic dishwashing detergent formulation of the present invention, comprises: 1 to 97 wt% (preferably, 1 to 97 wt% (more preferably 10 to 98.5 wt%; most preferably, 25 to 96 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a builder; wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate. Preferably, the automatic dishwashing detergent formulation of the present invention, comprises: ≥ 1 wt% (preferably, ≥ 10 wt%; more preferably, ≥ 25 wt%; most preferably, ≥ 40 wt%), based on dry weight of the automatic dishwashing detergent formulation, of the builder; wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate. Preferably, the automatic dishwashing detergent formulation of the present invention, comprises: ≤ 95 wt% (preferably, ≤ 90 wt%;Attorney Docket No.85928-WO-PCT more preferably, ≤ 85 wt%; most preferably, ≤ 80 wt%), based on dry weight of the automatic dishwashing detergent formulation, of the builder; wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate. Weight percentages of carbonates, citrates and silicates are based on the actual weights of the salts, including metal ions.

[0022] The term "carbonate(s)" as used herein and in the appended claims refers to alkali metal or ammonium salts of carbonate, bicarbonate and / or sesquicarbonate. Preferably, the carbonate used in the automatic dishwashing detergent formulation (if any) is selected from the group consisting of carbonate salts of sodium, potassium and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium). More preferably, the carbonate used in the automatic dishwashing detergent formulation (if any) includes at least one of sodium carbonate and sodium bicarbonate. Preferably, when the builder used in the automatic dishwashing detergent formulation of the present invention includes carbonate, the automatic dishwashing detergent formulation preferably, comprises 0 to 97 wt% (preferably, 5 to 75 wt%; more preferably, 10 to 60 wt%; most preferably 20 to 50 wt%), based on dry weight of the automatic dishwashing detergent formulation, of carbonate.

[0023] The term "silicate(s)" as used herein and in the appended claims refers to alkali metal silicates. Preferably, the silicate used in the automatic dishwashing detergent formulation (if any) is selected from the group consisting of silicate salts of sodium, potassium and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium). More preferably, the silicate used in the automatic dishwashing detergent formulation (if any) is sodium disilicate. Preferably, the builder used in the automatic dishwashing detergent formulation of the present invention includes a silicate. Preferably, when the builder used in the automatic dishwashing detergent formulation of the present invention includes a silicate, the automatic dishwashing detergent formulation preferably, comprises 0 to 97 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.5 to 7.5 wt%; most preferably 0.75 to 3 wt%), based on dry weight of the automatic dishwashing detergent formulation, of the silicate(s).

[0024] The term "organophosphonate(s)" as used herein and in the appended claims refers to a phosphonate; wherein the phosphonate comprises 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 detergent formulation of the present invention comprises 0 to 15 wt% (preferably, 0 to 10 wt%; more preferably, 0 to 7.5 wt%; most preferably, 0 to 5 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a phosphonate; wherein the phosphonate isAttorney Docket No.85928-WO-PCT selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts thereof.

[0025] Preferably, the automatic dishwashing formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; most preferably, 1.5 to 8.5 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a nonionic surfactant. More preferably, the automatic dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; most preferably, 1.5 to 8.5 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a nonionic surfactant; wherein the non-ionic surfactant is selected from the group consisting of polyoxyalkylene surfactants, polyalkylene glycol esters, polyoxyethylene derivatives of fatty acid esters of polyhydric alcohols, fatty acid esters of polyalkoxylated polyhydric alcohols, polyalkoxylated natural fats and oils, polyalkylene oxide block copolymers, alkyl polyglycosides (e.g., alkyl polyglucosides, alkyl polypentosides), sucrose esters and mixtures thereof. Still more preferably, the automatic dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; most preferably, 1.5 to 8.5 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a nonionic surfactant; wherein the non-ionic surfactant includes a fatty alcohol alkoxylate. Most preferably, the automatic dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; most preferably, 1.5 to 8.5 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a nonionic surfactant; wherein the non-ionic surfactant is a fatty alcohol alkoxylate according to formula I (I) wherein w is an7 to 60; most preferably, 8 to 50); wherein R1is selected from the group consisting of a hydrogen and a linear or branched C1-20 alkyl group (preferably, a hydrogen, and a linear or branched C1-20 alkyl group; more preferably, a hydrogen and a linear C1-20 alkyl group); wherein R2is selected from the group consisting of a linear or branched C1-20alkyl group and a linear or branched C1-4 hydroxyalkyl group (preferably, a linear or branched C1-20 alkyl group; more preferably, a linear C1-20alkyl group); wherein each R3is independently selected from the group consisting of a hydrogen, a methyl group, an ethyl group, a n-propyl group, an iso- propyl group, a n-butyl group, a 2-butyl group and a 2-methyl-2-butyl group (preferably, aAttorney Docket No.85928-WO-PCT hydrogen, a methyl group and an ethyl group); and with the proviso that sum of the total number of carbon atoms in R1and R2is 5 to 21 (preferably, 6 to 20 carbon atoms; more preferably, 7 to 20 carbon atoms).

[0026] Preferably, the automatic dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 1 to 10 wt%; more preferably, 2.5 to 7.5 wt%; still more preferably, > 5 to 7.25 wt%; most preferably, 5.5 to 7 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a poly(malic ester) polymer; wherein the poly(malic ester) polymer comprises > 60 mol% (preferably, 70 to 100 mol%; more preferably, 75 to 100 mol%; still more preferably, 80 to 100 mol%; yet more preferably, 90 to 100 mol%; still yet more preferably, 95 to 100 mol%; most preferably, 98 to 100 mol%) of structural units of malic acid. More preferably, the automatic dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 1 to 10 wt%; more preferably, 2.5 to 7.5 wt%; still more preferably, > 5 to 7.25 wt%; most preferably, 5.5 to 7 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a poly(malic ester) polymer; wherein the poly(malic ester) polymer comprises > 60 mol% (preferably, 70 to 100 mol%; more preferably, 75 to 100 mol%; still more preferably, 80 to 100 mol%; yet more preferably, 90 to 100 mol%; still yet more preferably, 95 to 100 mol%; most preferably, 98 to 100 mol%) of structural units of malic acid; and wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons (preferably, 1,000 to 4,000 Daltons; more preferably, 1,000 to 2,500 Daltons; most preferably, 1,000 to 2,000 Daltons)(measured by Matrix Assisted Laser Desorption / Ionization Mass Spectrometry (MALDI-MS)).

[0027] Preferably, the automatic dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 1 to 10 wt%; more preferably, 2.5 to 7.5 wt%; still more preferably, > 5 to 7.25 wt%; most preferably, 5.5 to 7 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a poly(malic ester) polymer; wherein the poly(malic ester) polymer comprises > 60 mol% (preferably, 70 to 100 mol%; more preferably, 75 to 100 mol%; still more preferably, 80 to 100 mol%; yet more preferably, 90 to 100 mol%; still yet more preferably, 95 to 100 mol%; most preferably, 98 to 100 mol%) of structural units of malic acid; and ≤ 40 mol% (preferably, 0 to 30 mol%; more preferably, 0 to 25 mol%; still more preferably, 0 to 20 mol%; yet more preferably, 0 to 10 mol%; still yet more preferably, 0 to 5 mol%; most preferably, 0 to 2 mol%) of structural units selected from the group consisting of structural units of lactic acid, structural units of glycolic acid, structural units of hydroxystearic acid and mixtures thereof. More preferably, the automaticAttorney Docket No.85928-WO-PCT dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 1 to 10 wt%; more preferably, 2.5 to 7.5 wt%; still more preferably, > 5 to 7.25 wt%; most preferably, 5.5 to 7 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a poly(malic ester) polymer; wherein the poly(malic ester) polymer comprises > 60 mol% (preferably, 70 to 100 mol%; more preferably, 75 to 100 mol%; still more preferably, 80 to 100 mol%; yet more preferably, 90 to 100 mol%; still yet more preferably, 95 to 100 mol%; most preferably, 98 to 100 mol%) of structural units of malic acid; and ≤ 40 mol% (preferably, 0 to 30 mol%; more preferably, 0 to 25 mol%; still more preferably, 0 to 20 mol%; yet more preferably, 0 to 10 mol%; still yet more preferably, 0 to 5 mol%; most preferably, 0 to 2 mol%) of structural units selected from the group consisting of structural units of lactic acid, structural units of glycolic acid, structural units of hydroxystearic acid and mixtures thereof; and wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons (preferably, 1,000 to 4,000 Daltons; more preferably, 1,000 to 2,500 Daltons; most preferably, 1,000 to 2,000 Daltons)(measured by Matrix Assisted Laser Desorption / Ionization Mass Spectrometry (MALDI-MS)).

[0028] Preferably, the poly(malic ester) polymer comprises < 1 wt% (preferably, < 0.5 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, < the detectable limit), based on weight of the poly(malic ester) polymer, of structural units of sulfonated monomer. More preferably, the poly(malic ester) polymer comprises < 1 wt% (preferably, < 0.5 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, < the detectable limit), based on weight of the poly(malic ester) polymer, of structural units of sulfonated monomer selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid (AMPS), 2-methacrylamido-2-methylpropane sulfonic acid, 4-styrenesulfonic acid, vinylsulfonic acid, 3-allyloxy sulfonic acid, 2-hydroxy-1-propane sulfonic acid (HAPS), 2-sulfoethyl(meth)acrylic acid, 2-sulfopropyl(meth)acrylic acid, 3-sulfopropyl(meth)acrylic acid, 4-sulfobutyl(meth)acrylic acid and salts thereof. Most preferably, the poly(malic ester) polymer comprises < 1 wt% (preferably, < 0.5 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, < the detectable limit), based on weight of the poly(malic ester) polymer, of structural units of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) monomer.

[0029] The automatic dishwashing detergent formulation of the present invention, optionally further comprises: an additive. Preferably, the automatic dishwashing detergent formulation of the present invention, further comprises: an additive selected from the group consisting ofAttorney Docket No.85928-WO-PCT a dispersant polymer; an alkalinity source; a bleaching agent (e.g., sodium percarbonate, sodium perborate); a bleach activator (e.g., tetraacetylethylenediamine (TAED)); a grease cleaning booster (e.g., poly(ethylene glycol, poly(propylene glycol), propyheptyl ether); a bleach catalyst (e.g., manganese(II) acetate, cobalt(II) chloride, bis(TACN)magnesium trioxide diacetate); an enzyme (e.g., protease, amylase, lipase, or cellulase); a foam suppressant; a coloring agent; a fragrance; a citrate; an additional builder; an antibacterial agent; a preservative; a filler (e.g., sodium sulfate); a deposit control polymer and mixtures thereof. More preferably, the automatic dishwashing detergent formulation of the present invention, further comprises an additive, wherein the additive is selected from the group consisting of a bleaching agent (e.g., sodium percarbonate, sodium perborate); a bleach activator (e.g., tetraacetylethylenediamine (TAED)); an enzyme (e.g., protease, amylase, lipase, or cellulase); a grease cleaning booster (e.g., poly(ethylene glycol), poly(propylene glycol), propylheptyl ether); and a filler (e.g., sodium sulfate). Most preferably, the automatic dishwashing detergent formulation of the present invention, further comprises an additive, wherein the additive includes a phosphonate, wherein the phosphonate includes a bleaching agent, wherein the bleaching agent includes sodium percarbonate; a bleach activator, wherein the bleach activator includes tetraacetylethylenediamine (TAED); an enzyme, wherein the enzyme includes a protease and an amylase; a grease cleaning booster, wherein the grease cleaning booster is a poly(ethylene glycol); and a filler, wherein the filler includes sodium sulfate.

[0030] Fillers included in automatic dishwashing detergent formulation tablets or powders are inert, water-soluble substances, typically sodium or potassium salts (e.g., sodium sulfate, potassium sulfate, sodium chloride, potassium chloride). In tablets and powders, fillers are typically present in amounts ranging from 0 wt% to 75 wt%. Fillers included in gel formulations typically include those mentioned for use in tablets and powders and also water.

[0031] Fragrances, dyes, foam suppressants, enzymes and antibacterial agents usually total no more than 10 wt%, alternatively no more than 5 wt%, of the automatic dishwashing detergent formulation.

[0032] The automatic dishwashing detergent formulation of the present invention, optionally further comprises: an alkalinity source. Suitable alkalinity sources include, without limitation, alkali metal carbonates and alkali metal hydroxides, such as sodium or potassium carbonate, bicarbonate, sesquicarbonate, sodium, lithium, or potassium hydroxide, or mixtures of the foregoing. Sodium hydroxide is preferred. The amount of alkalinity source in the automatic dishwashing detergent formulation of the present invention (if any) is at leastAttorney Docket No.85928-WO-PCT 1 wt% (preferably, at least 20 wt%) and up to 80 wt% (preferably, up to 60 wt%), based on dry weight of the automatic dishwashing detergent formulation.

[0033] The automatic dishwashing detergent formulation of the present invention, optionally further comprises: a bleaching agent (e.g., sodium percarbonate). The amount of the bleaching agent in the automatic dishwashing detergent formulation of the present invention (if any) is preferably at a concentration of 1 to 25 wt% (more preferably, 5 to 20 wt%), based on dry weight of the automatic dishwashing detergent formulation.

[0034] The automatic dishwashing detergent formulation of the present invention, optionally further comprises: a bleach activator (e.g., tetraacetylethylenediamine (TAED)). The amount of the bleach activator in the automatic dishwashing detergent formulation of the present invention (if any) is preferably at a concentration of 1 to 10 wt% (more preferably, 2.5 to 7.5 wt%), based on dry weight of the automatic dishwashing detergent formulation.

[0035] Preferably, the automatic dishwashing detergent formulation of the present invention comprises < 1 wt% (preferably, < 0.5 wt%; more preferably, < 0.2 wt%; still more preferably, < 0.1 wt%; yet still more preferably, < 0.01 wt%; most preferably, < the detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of phosphate. Preferably, the automatic dishwashing detergent formulation of the present invention is phosphate free (i.e., contains 0 wt% phosphate).

[0036] Preferably, the automatic dishwashing detergent formulation of the present invention comprises < 1 wt% (preferably, < 0.5 wt%; more preferably, < 0.2 wt%; still more preferably, < 0.1 wt%; yet still more preferably, < 0.01 wt%; most preferably, < the detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2’-iminodissuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’-ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta-alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof. Most preferably, the automatic dishwashing detergent formulation of the present invention contains 0 wt% of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2’-iminodissuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’-ethylene diamine disuccinicAttorney Docket No.85928-WO-PCT acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta-alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof.

[0037] Preferably, the automatic dishwashing detergent formulation of the present invention comprises ≤ 0.4 wt% (preferably, < 0.3 wt%; more preferably, < 0.2 wt%; still more preferably, < 0.1 wt%; yet more preferably, < 0.01 wt%; still yet more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of urea. Preferably, the automatic dishwashing detergent formulation of the present invention is urea free (i.e., contains 0 wt% urea).

[0038] Preferably, the automatic dishwashing detergent formulation of the present invention comprises < 0.01 wt% (preferably, < 0.001 wt%; more preferably, < 0.0001 wt%; still more preferably, < 0.00001 wt%; most preferably, less than detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of a color changing dye. The term "color changing dye" as used herein and in the appended claims means a dye having a visual color change within the pH ranges of 3 to 6 (e.g., methyl yellow, bromophenol blue, methyl orange, bromocresol green, methyl red and bromocresol purple) or within the pH range of 9 to 11 (e.g., alizarin yellow R, thymolphthalein, phenolphthalein and thymol blue).

[0039] Preferably, the automatic dishwashing detergent formulation of the present invention comprises < 1 wt% (preferably, < 0.1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of tartaric acid or residues of tartaric acid. The term "residues or tartaric acid" as used herein and in the appended claims refers to residues of tartaric acid in a polymer.

[0040] Preferably, the automatic dishwashing detergent formulation of the present invention comprises < 1 wt% (preferably, < 0.1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of sodium alginate.

[0041] Preferably, the automatic dishwashing detergent formulation of the present invention comprises < 1 wt% (preferably, < 0.1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of depentane oil.

[0042] Preferably, the automatic dishwashing detergent formulation of the present invention comprises < 1 wt% (preferably, < 0.1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of polymer comprising structural units ofAttorney Docket No.85928-WO-PCT sulfonated monomer. More preferably, the automatic dishwashing detergent formulation of the present invention comprises < 1 wt% (preferably, < 0.1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of polymer comprising structural units of sulfonated monomer selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid (AMPS), 2-methacrylamido-2-methylpropane sulfonic acid, 4-styrenesulfonic acid, vinylsulfonic acid, 3-allyloxy sulfonic acid, 2-hydroxy-1-propane sulfonic acid (HAPS), 2-sulfoethyl(meth)acrylic acid, 2-sulfopropyl(meth)acrylic acid, 3-sulfopropyl(meth)acrylic acid, 4-sulfobutyl(meth)acrylic acid and salts thereof. Most preferably, , the automatic dishwashing detergent formulation of the present invention comprises < 1 wt% (preferably, < 0.1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the automatic dishwashing detergent formulation, of polymer comprising structural units of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) monomer.

[0043] Preferably, the automatic dishwashing detergent formulation of the present invention has a pH (at 1 wt% in water) of at least 9 (preferably, ≥ 10; more preferably, ≥ 11.5). Preferably, the automatic dishwashing detergent formulation of the present invention has a pH (at 1 wt% in water) of no greater than 13.

[0044] Preferably, the automatic dishwashing detergent formulation of the present invention can be formulated in any typical form, e.g., as a tablet, powder, block, monodose, sachet, paste, liquid or gel. More preferably, the automatic dishwashing detergent formulation of the present invention is formulated as a solid, e.g., as a tablet, granule, powder, block, paste. Most preferably, the automatic dishwashing formulation of the present invention is formulated as a granule or powder.

[0045] Preferably, the automatic dishwashing detergent formulation of the present invention contains less than 6 wt% (preferably, < 5 wt%; more preferably, < 2.5 wt%; still more preferably¸< 2 wt%; yet more preferably, < 1 wt%), based on weight of the automatic dishwashing detergent formulation, of water.

[0046] The automatic dishwashing detergent formulations of the present invention are useful for cleaning ware, such as eating and cooking utensils, dishes and glassware, in an automatic dishwashing machine. In particular, the automatic dishwashing detergent formulations of the present invention are useful for cleaning glassware.

[0047] Preferably, the automatic dishwashing detergent formulation of the present invention are suitable for use under typical operating conditions. For example, when used in anAttorney Docket No.85928-WO-PCT automatic dishwashing machine, typical water temperatures during the washing process preferably are from 20 ºC to 85 ºC, preferably 30 ºC to 70 ºC. Typical concentrations for the automatic dishwashing detergent formulation as a percentage of total liquid in the dishwasher preferably are from 0.1 to 1 wt%, preferably from 0.2 to 0.7 wt%. With selection of an appropriate product form and addition time, the automatic dishwashing detergent formulations of the present invention may be present in the prewash, main wash, penultimate rinse, final rinse, or any combination of these cycles.

[0048] Preferably, the method of cleaning an article in an automatic dishwashing machine of the present invention, comprises: providing at least one soiled article (e.g., cookware, bakeware, tableware, dishware, flatware and / or glassware; preferably, glassware); providing a automatic dishwashing detergent formulation of the present invention; and applying the automatic dishwashing detergent formulation to the at least one soiled article (preferably, in an automatic dishwasher) to provide a cleaned article.

[0049] Some embodiments of the present invention will now be described in detail in the following Examples. Syntheses S1-S9: Malic Acid Polymers

[0050] A 4CV Helicone reactor (from Design Integrated Technology, Inc.) was charged through the side port with the monomer(s) noted in TABLE 1. The reactor was then sealed under nitrogen and heated to the temperature noted in TABLE 1. Once the monomer(s) were fully melted vacuum was applied to the reactor (1 mm Hg) and mixing was started. The contents of the reactor were then allowed to react for the time noted in TABLE 1. Once the reaction time was reached, the vacuum on the reactor was released and the product was collected. The number average molecular weight, MN, and weight average molecular weight, MW, of the malic acid polymers were measured by Matrix Assisted Laser Desorption / Ionization Mass Spectrometry (MALDI-MS) as reported in TABLE 1.Attorney Docket No.85928-WO-PCT TABLE 1 Monomer(s) in (g) Time Daltons Synthesis A B C D E Temp. (°C) (hrs) Mn Mw 0 0 0 0 0 0 0 0 0

[0051] Dishwashing compositions were prepared in each of Comparative Examples CF1-CF9 and Examples F1-F11 having the component formulations identified in TABLES 2-5.Attorney Docket No.85928-WO-PCT TABLE 2 Example (wt%) Ingredient CF1 CF2 CF3 F1 F2esAttorney Docket No.85928-WO-PCT TABLE 3 Example (wt%) Ingredient CF4 CF5 F3 F4 5 5Attorney Docket No.85928-WO-PCT TABLE 4 Example (wt%) Ingredient CF6 CF7 F5 F6 F7 5 5Attorney Docket No.85928-WO-PCT TABLE 5 Example (wt%) Ingredient CF8 CF9 F8 F9 F10 F11 5 534567

[0052] The STIWA food soil described in TABLE 6 was prepared by the following procedure. a) Bringing the water to a boil. b) Mixing in a paper cup the instant gravy, the benzoic acid and the starch; and then adding the mixture to the boiling water. c) Adding the milk and margarine to the product of (b). d) Letting the product of (c) cool down to approximately 40 °C, and then adding mixture to a kitchen mixer (Polytron). e) Combining in another paper cup, the egg yolk, the ketchup and the mustard and mixing with a spoon. f) Adding the product of (e) to the mixture of (d) in the blender with continuous stirring. g) Letting the product of (f) stir in the blender for 5 minutes. h) The freezing the product food soil mixture from (g). i) 50 g of the frozen slush is placed into the dishwasher at beginning of the main wash.Attorney Docket No.85928-WO-PCT TABLE 6 Ingredient wt% Water 70.9

[0053] Machine: Miele SS-ADW, Model G1223SC Labor Prog 6. Wash at 65 °C – 20 min wash cycle, followed by two rinse cycles with a rinse water temperature of 65 °C and a final 30 minute drying step. After the drying cycle was complete, the dishwasher door was opened for 30 minutes to allow the steam to evaporate. Water: initial water supplied to the dishwasher had a target conductivity of 1,160 to 1,280 μs / cm. Food soil: 50 g of the composition noted in TABLE 6 was introduced to the wash liquor frozen in a cup at the beginning of the wash cycle. The test detergents were also charged to the dishwasher at the beginning of the wash cycle. The test detergents were each dosed at 15.3 g per wash (based on solids). The number of wash cycles used in this experiment to generate filming and spotting was 15. Filming Evaluation

[0054] After each of 15 wash cycles under the above dishwashing test conditions, the glass tumblers (Schott Zwiesel Tritan®longdrink glasses) were dried in open air. After drying, filming ratings were determined by trained evaluators by observations of glass tumblers in a light box with controlled illumination from below rated for filming according to ASTM method ranging from 1 (no film) to 5 (heavily filmed). An average value of 1 to 5 for filming was determined as reported in TABLE 7. The film tint was also observed and recorded. A bluish tint to film is considered to be more discernible to end use customers of automatic dishwashing formulations, making the mitigation of blue film a significant performance improvement.Attorney Docket No.85928-WO-PCT TABLE 7 Substrate Glass tumblers

[0055] Machine: Whirlpool Model WDF330PAHW automatic dishwashing machines using ASTM D 3556 test procedure to evaluate the cleaning performance under US conditions. Water hardness: Total hardness = 300 ppm; temporary hardness = 100 ppm. Molar ratio: Ca2+ / Mg2+= 2:1. 40 g milk / margarine food soil as described in ASTM D 3556 test procedure was added at beginning of wash cycle. Detergent added during the main wash after completion of the prewash step. 1 hr wash cycle (49 °C wash temp; rinse water temperature of 60 °C; cycle time 65 min. 30 minute drying step between wash cycles and after filing cycle. The test detergents were each dosed at 15.3 g per wash (based on solids). The number of wash cycles used in this experiment to generate filming as reported in TABLES 8-10. Filming Evaluation

[0056] After the last cycle under the above dishwashing test conditions, the glass tumblers (Schott Zwiesel Tritan®longdrink glasses) were dried in open air. After drying, filming ratings were determined by trained evaluators by observations of glass tumblers in a light box with controlled illumination from below rated for filming according to ASTM method ranging from 1 (no film) to 5 (heavily filmed). An average value of 1 to 5 for filming was determined as reported in TABLES 8-10. The film tint was also observed and recorded. A bluish tint to film is considered to be more discernible to end use customers of automatic dishwashing formulations, making the mitigation of blue film a significant performance improvement.Attorney Docket No.85928-WO-PCT TABLE 8 10 Cycles Glass tumblers TGlass tumblers5 Cyc es Glass tumblers

Claims

Attorney Docket No.85928-WO-PCT We claim:

1. An automatic dishwashing detergent formulation comprising: a builder, wherein the builder comprises at least one of a carbonate, a silicate and an organophosphonate; a nonionic surfactant; and a poly(malic ester) polymer comprising > 60 mol% of structural units of malic acid.

2. The automatic dishwashing detergent formulation of claim 1, wherein the poly(malic ester) polymer has a number average molecular weight of 1,000 to 5,000 Daltons.

3. The automatic dishwashing detergent formulation of claim 2, wherein the poly(malic ester) polymer comprises ≤ 40 mol% of structural units selected from the group consisting of structural units of lactic acid; structural units of glycolic acid; structural units of hydroxystearic acid; and mixtures thereof.

4. The automatic dishwashing detergent formulation of claim 3, wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of tartaric acid or residues of tartaric acid.

5. The automatic dishwashing detergent formulation of claim 4, wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of sodium alginate.

6. The automatic dishwashing detergent formulation of claim 5, wherein the automatic dishwashing detergent formulation comprises < 1 wt%, based on weight of the automatic dishwashing detergent formulation, of depentane oil.

7. The automatic dishwashing detergent formulation of claim 6, wherein the automatic dishwashing detergent formulation is an anhydrous solid.

8. The automatic dishwashing detergent formulation of claim 7, wherein the automatic dishwashing formulation comprises less than 0.1 wt%, based on dry weight of the automatic dishwashing formulation, of phosphate, measured as elemental phosphorus; and wherein the automatic dishwashing formulation contains 0 wt%, based on the dry weight of the automatic dishwashing detergent formulation, of builders selected from the group consisting of nitrilotriacetic acid; ethylenediaminetetraacetic acid; diethylenetriaminepentaacetic acid; glycine-N,N-diacetic acid; methyl glycine-N,N-diacetic acid; 2-hydroxyethyliminodiacetic acid; glutamic acid-N,N-diacetic acid; 3-hydroxy-2,2’-iminodissuccinate; S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid; N,N’-ethylene diamine disuccinic acid; iminodisuccinic acid; aspartic acid; asparticAttorney Docket No.85928-WO-PCT acid-N,N-diacetic acid; beta-alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof.

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

10. A method of cleaning an article in an automatic dishwashing machine, comprising: providing at least one soiled article; providing an automatic dishwashing composition according to claim 1; and, applying the automatic dishwashing composition to the at least one soiled article to provide a cleaned article.

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