An emulsifier / surfactant / dispersant polymer

Abstract

An emulsifier / surfactant / dispersant polymer is provided including structural units of malic acid and structural units of hydroxystearic acid.

Description

AN EMULSIFIER / SURFACTANT / DISPERSANT POLYMER

[0001] The present invention relates to an emulsifier / surfactant / dispersant polymer. In particular, the present invention relates to an emulsifier / surfactant / dispersant polymer comprising: structural units of malic acid; and structural units of hydroxystearic acid.

[0002] Ingredients that function as an emulsifier / surfactant / dispersant have utility in an array of different formulations including dishwashing compositions. Many existing emulsifier / surfactant / dispersant materials lack biodegradability, which is an increasingly favorable property desired by formulators.

[0003] 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.

[0004] 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.

[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 emulsifier / surfactant / dispersant polymers for use in, for example, automatic dishwashing formulations. In particular, there remains a need for new emulsifier / surfactant / dispersant polymers for use in automatic dishwashing formulations, wherein the emulsifier / surfactant / dispersant polymers provide effective low filming performance; are biosourced and biodegradable.

[0007] The present invention provides an emulsifier / surfactant / dispersant polymer comprising: structural units of malic acid; and structural units of hydroxystearic acid.

[0008] The present invention provides an emulsifier / surfactant / dispersant polymer comprising: structural units of malic acid; and structural units of hydroxystearic acid;wherein the emulsifier / surfactant / dispersant polymer has a number average molecular weight of 1,000 to 5,000 Daltons; and wherein 90 to 100 mol% of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid.

[0009] The present invention provides an emulsifier / surfactant / dispersant polymer comprising: 60 to 99.9 mol% of structural units of malic acid; and 0.1 to 40 mol% of structural units of hydroxystearic acid.

[0010] The present invention provides an emulsifier / surfactant / dispersant polymer comprising: 60 to 99.9 mol% of structural units of malic acid; and 0.1 to 40 mol% of structural units of hydroxystearic acid; wherein the emulsifier / surfactant / dispersant polymer has a number average molecular weight of 1,000 to 5,000 Daltons.

[0011] The present invention provides an emulsifier / surfactant / dispersant polymer comprising: 60 to 99.9 mol% of structural units of malic acid; and 0.1 to 40 mol% of structural units of hydroxystearic acid; wherein the emulsifier / surfactant / dispersant polymer has a number average molecular weight of 1,000 to 5,000 Daltons; and wherein 90 to 100 mol% of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid.

[0012] The present invention provides an emulsifier / surfactant / dispersant polymer comprising: 75 to 99.25 mol% of structural units of malic acid; and 0.75 to 25 mol% of structural units of hydroxystearic acid; wherein the emulsifier / surfactant / dispersant polymer has a number average molecular weight of 1,000 to 5,000 Daltons; and wherein 90 to 100 mol% of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid.

[0013] The present invention provides an emulsifier / surfactant / dispersant polymer comprising: 75 to 99.25 mol% of structural units of malic acid; and 0.75 to 25 mol% of structural units of hydroxystearic acid, wherein the structural units of hydroxystearic acid are selected from structural units of secondary hydroxystearic acid; wherein the emulsifier / surfactant / dispersant polymer has a number average molecular weight of 1,000 to 5,000 Daltons; and wherein 90 to 100 mol% of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid.

[0014] The present invention provides an emulsifier / surfactant / dispersant polymer comprising: 75 to 99.25 mol% of structural units of malic acid; and 0.75 to 25 mol% of structural units of hydroxy stearic acid selected from the group consisting of 3 -hydroxy stearicacid, 4-hydroxystearic acid, 5-hydroxystearic acid, 6-hydroxystearic acid, 7-hydroxy stearic acid; 8-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxy stearic acid, 11-hydroxystearic acid; 12-hydroxy stearic acid, 13-hydroxystearic acid, 14-hydroxystearic acid, 15-hydroxystearic acid, 16-hydroxystearic acid and mixtures thereof; wherein the emulsifier / surfactant / dispersant polymer has a number average molecular weight of 1,000 to 5,000 Daltons; and wherein 90 to 100 mol% of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid.

[0015] The present invention provides an emulsifier / surfactant / dispersant polymer comprising: 75 to 99.25 mol% of structural units of malic acid; and 0.75 to 25 mol% of structural units of 12-hydroxystearic acid; wherein the emulsifier / surfactant / dispersant polymer has a number average molecular weight of 1,000 to 5,000 Daltons; and wherein 90 to 100 mol% of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid.

[0016] 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 an emulsifier / surfactant / dispersant polymer of the present invention.DETAILED DESCRIPTION

[0017] Surprisingly, it has been found that, an emulsifier / surfactant / dispersant polymer comprising: structural units of malic acid and structural units of hydroxystearic acid exhibits properties of an emulsifier, a surfactant and a dispersant and provides 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.

[0019] Preferably, the emulsifier / surfactant / dispersant polymer of the present invention, comprises: structural units of malic acid and structural units of hydroxystearic acid (preferably, secondary hydroxystearic acid; more preferably, secondary hydroxystearic acidselected from the group consisting of 3-hydroxystearic acid, 4-hydroxystearic acid; 5-hydroxystearic acid; 6-hydroxystearic acid; 7-hydroxy stearic acid; 8-hydroxystearic acid; 9-hydroxystearic acid; 10-hydroxystearic acid; 11 -hydroxystearic acid; 12-hydroxy stearic acid; 13 -hydroxy stearic acid; 14-hydroxystearic acid; 15-hydroxystearic acid;16-hydroxystearic acid and mixtures thereof; most preferably, 12-hydroxy stearic acid)(preferably, wherein the emulsifier / surfactant / dispersant 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)))(preferably, wherein 90 to 100 mol% (preferably, 92 to 100 mol%; more preferably, 95 to 100 mol%; most preferably, 98 to 100 mol%) of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid). More preferably, the emulsifier / surfactant / dispersant polymer of the present invention, comprises: 60 to 99.9 mol% (preferably, 70 to 99.5 mol%; more preferably, 75 to 99.25 mol%; still more preferably, 80 to 99 mol%; yet more preferably, 85 to 98 mol%; still yet more preferably, 90 to 97.5 mol%; most preferably, 92.5 to 97 mol%) of structural units of malic acid; and 0.1 to 40 mol% (preferably, 0.5 to 30 mol%; more preferably, 0.75 to 25 mol%; still more preferably, 1 to 20 mol%; yet more preferably, 2 to 15 mol%; still yet more preferably, 2.5 to 10 mol%; most preferably, 3 to 7.5 mol%) of structural units of hydroxystearic acid (preferably, secondary hydroxystearic acid; more preferably, secondary hydroxystearic acid selected from the group consisting of 3-hydroxystearic acid, 4-hydroxystearic acid; 5-hydroxystearic acid; 6-hydroxystearic acid; 7-hydroxystearic acid; 8-hydroxystearic acid; 9-hydroxystearic acid; 10-hydroxystearic acid;11 -hydroxy stearic acid; 12-hydroxy stearic acid; 13-hydroxystearic acid; 14-hydroxystearic acid; 15 -hydroxy stearic acid; 16-hydroxystearic acid and mixtures thereof; most preferably,12-hydroxy stearic acid). Still more preferably, the emulsifier / surfactant / dispersant polymer of the present invention, comprises: 60 to 99.9 mol% (preferably, 70 to 99.5 mol%; more preferably, 75 to 99.25 mol%; still more preferably, 80 to 99 mol%; yet more preferably, 85 to 98 mol%; still yet more preferably, 90 to 97.5 mol%; most preferably, 92.5 to 97 mol%) of structural units of malic acid; and 0.1 to 40 mol% (preferably, 0.5 to 30 mol%; more preferably, 0.75 to 25 mol%; still more preferably, 1 to 20 mol%; yet more preferably, 2 to 15 mol%; still yet more preferably, 2.5 to 10 mol%; most preferably, 3 to 7.5 mol%) of structural units of hydroxystearic acid (preferably, secondary hydroxystearic acid; more preferably, secondary hydroxystearic acid selected from the group consisting of3-hydroxystearic acid, 4-hydroxystearic acid; 5-hydroxystearic acid; 6-hydroxystearic acid;7-hydroxystearic acid; 8-hydroxystearic acid; 9-hydroxystearic acid; 10-hydroxy stearic acid;1 1 -hydroxy stearic acid; 12-hydroxy stearic acid; 13-hydroxystearic acid; 14-hydroxystearic acid; 15 -hydroxy stearic acid; 16-hydroxystearic acid and mixtures thereof; most preferably,12-hydroxy stearic acid); wherein the emulsifier / surfactant / dispersant 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 (MALDLMS). Most more preferably, the emulsifier / surfactant / dispersant polymer of the present invention, comprises: 60 to 99.9 mol% (preferably, 70 to 99.5 mol%; more preferably, 75 to 99.25 mol%; still more preferably, 80 to 99 mol%; yet more preferably, 85 to 98 mol%; still yet more preferably, 90 to 97.5 mol%; most preferably, 92.5 to 97 mol%) of structural units of malic acid; and 0.1 to 40 mol% (preferably, 0.5 to 30 mol%; more preferably, 0.75 to 25 mol%; still more preferably, 1 to 20 mol%; yet more preferably, 2 to 15 mol%; still yet more preferably, 2.5 to 10 mol%; most preferably, 3 to 7.5 mol%) of structural units of hydroxystearic acid (preferably, secondary hydroxystearic acid; more preferably, secondary hydroxystearic acid selected from the group consisting of 3-hydroxystearic acid,4-hydroxystearic acid; 5-hydroxystearic acid; 6-hydroxystearic acid; 7-hydroxystearic acid;8-hydroxystearic acid; 9-hydroxystearic acid; 10-hydroxystearic acid; 11 -hydroxystearic acid; 12-hydroxy stearic acid; 13 -hydroxy stearic acid; 14-hydroxystearic acid;15-hydroxystearic acid; 16-hydroxystearic acid and mixtures thereof; most preferably, 12-hydroxy stearic acid); wherein the emulsifier / surfactant / dispersant 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); and wherein 90 to 100 mol% (preferably, 92 to 100 mol%; more preferably, 95 to 100 mol%; most preferably, 98 to 100 mol%) of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid.

[0020] Preferably, the emulsifier / surfactant / dispersant 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 emulsifier / surfactant / dispersant polymer, of structural units of sulfonated monomer. More preferably, the emulsifier / surfactant / dispersant polymer comprises < 1 wt% (preferably, < 0.5wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, < the detectable limit), based on weight of the emulsifier / surfactant / dispersant 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-l -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 emulsifier / surfactant / dispersant 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 emulsifier / surfactant / dispersant polymer, of structural units of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) monomer.

[0021] Preferably, the automatic dishwashing detergent formulation of the present invention, comprises: a builder (preferably, 1 to 99.6 wt% (more preferably 10 to 98.5 wt%; still more preferably, 20 to 96.5 wt%; most preferably, 25 to 93 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 detersive surfactant (preferably, 0.2 to 15 wt% (more preferably, 0.5 to 10 wt%; still more preferably, 1.5 to 8.5 wt%; most preferably, 4 to 8 wt%), based on dry weight of the automatic dishwashing detergent formulation, of the nonionic detersive surfactant); and an emulsifier / surfactant / dispersant polymer of the present invention as described above (preferably, 0.2 to 15 wt% (more preferably, 1 to 10 wt%; still more preferably, 2 to 8 wt%; most preferably, 3 to 7 wt%), based on dry weight of the automatic dishwashing detergent formulation, of the emulsifier / surfactant / dispersant polymer).

[0022] 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.

[0023] Preferably, the automatic dishwashing detergent formulation of the present invention, comprises: 1 to 99.6 wt% (preferably 10 to 98.5 wt%; more preferably, 20 to 96.5 wt%; most preferably, 25 to 93 wt%), based on dry weight of the automatic dishwashing detergent formulation, of the builder; wherein the builder comprises at least one of a carbonate, asilicate and an organophosphonate. Preferably, the automatic dishwashing detergent formulation of the present invention, comprises: > 1 wt% (preferably, > 10 wt%; more preferably, > 20 wt%; most preferably, > 25 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: < 99.6 wt% (preferably, < 98.5 wt%; more preferably, < 96.5 wt%; most preferably, < 93 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.

[0024] 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.

[0025] 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).

[0026] The term "organophosphonate(s)" as used herein and in the appended claims refers to a phosphonate; wherein the phosphonate comprises at least one of l-hydroxyethylidene-l,l-diphosphonic acid (HEDP) and a salt of l-hydroxyethylidene-l,l-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 is selected from the group consisting of l-hydroxyethylidene-l , l-diphosphonic acid (HEDP) and salts thereof.

[0027] Preferably, the automatic dishwashing formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; more preferably, 1.5 to 8.5 wt%; most preferably, 4 to 8 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a nonionic detersive surfactant 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. More preferably, the automatic dishwashing detergent formulation of the present invention, comprises: 0.2 to 15 wt% (preferably, 0.5 to 10 wt%; more preferably, 1.5 to 8.5 wt%; most preferably, 4 to 8 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a nonionic detersive surfactant; wherein the nonionic detersive 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%; more preferably, 1.5 to 8.5 wt%; most preferably, 4 to 8 wt%), based on dry weight of the automatic dishwashing detergent formulation, of a nonionic detersive surfactant; wherein the nonionic detersive surfactant is a fatty alcohol alkoxylate according to formula Iwherein w is an average of 5 to 100 (preferably, 6 to 75; more preferably, 7 to 60; most preferably, 8 to 50); wherein R1is selected from the group consisting of a hydrogen and a linear or branched C1-20 alkyl group (preferably, a hydrogen, and a linear or branched C1-20 alkyl group; more preferably, a hydrogen and a linear Ci-20 alkyl group); wherein R2isselected from the group consisting of a linear or branched C1-20 alkyl group and a linear or branched C1-4 hydroxyalkyl group (preferably, a linear or branched C1-20 alkyl group; more preferably, a linear C1-20 alkyl group); wherein each R3is independently selected from the group consisting of a hydrogen, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-butyl group and a 2-methyl-2-butyl group (preferably, a hydrogen, a methyl group and an ethyl group); and with the proviso that sum of the total number of carbon atoms in R1and R2is 5 to 21 (preferably, 6 to 20 carbon atoms; more preferably, 7 to 20 carbon atoms).

[0028] 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 of 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), polypropylene 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.

[0029] 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 aretypically 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.

[0030] 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.

[0031] 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 least 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.

[0032] 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.

[0033] 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.

[0034] 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).

[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 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 disuccinic acid; iminodisuccinic acid; aspartic acid; aspartic acid-N,N-diacetic acid; beta- alaninediacetic acid; polyaspartic acid; salts thereof and mixtures thereof.

[0036] 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).

[0037] 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).

[0038] 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.

[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 sodium alginate.

[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 depentane oil.

[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 polymer comprising structural units of 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-l -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.

[0042] 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.

[0043] Preferably, the automatic dishwashing detergent formulation of the present invention contains less than 6 wt% (preferably, < 5 wt%; more preferably, < 2.5 wt%; still morepreferably, 2 wt%; yet more preferably, < 1 wt%), based on weight of the automatic dishwashing detergent formulation, of water).

[0044] 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.

[0045] Preferably, the automatic dishwashing detergent formulation of the present invention are suitable for use under typical operating conditions. For example, when used in an automatic dishwashing machine, typical water temperatures during the washing process preferably are from 20 °C to 85 °C, preferably 30 °C to 70 °C. 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.

[0046] 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.

[0047] Some embodiments of the present invention will now be described in detail in the following Examples.Synthesis SI; Poly(malic acid co-hydroxystearic acid)

[0048] A 4CV Helicone reactor (from Design Integrated Technology, Inc.) was charged through the side port with L-(-)-Malic acid (130 g; from MilliporeSigma) and 12-hydroxy stearic acid (14.57 g; from TCI Chemicals). The reactor was then sealed under nitrogen and heated to 120 °C. 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 20 hours. 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 poly(malic acid co-hydroxystearic acid) was measured by Matrix Assisted Laser Desorption / Ionization Mass Spectrometry (MALDLMS) as MN= 1,300 Daltons and Mw= 1,700 Daltons.Comparative Examples CF1-CF2 and Example Fl: Dishwashing detergents

[0049] Dishwashing compositions were prepared in each of Comparative Examples CF1-CF2 and Example Fl having the component formulations identified in TABLE 1. TABLE 1Dishwashing Test Conditions

[0050] 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 TABLE 2.Filming Evaluation

[0051] 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 methodranging from 1 (no film) to 5 (heavily filmed). An average value of 1 to 5 for filming was determined as reported in TABLE 2. 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.TABLE 2Emulsification / surfactant property observation

[0052] A 1 wt% mixture of poly(malic acid co-hydroxystearic acid) prepared according to Synthesis SI in distilled water was prepared. The resulting mixture (pH 2) was observed to be a stable milky white emulsion / dispersion, indicating the poly(malic acid co-hydroxystearic acid) exhibits emulsifier / dispersant properties. The pH of the stable emulsion / dispersion was then adjusted to a pH of 8 with the addition of aqueous sodium hydroxide. The pH 8 mixture was observed to be a clear, translucent solution which generated a stable foam layer when shaken, indicating the poly(malic acid co-hydroxystearic acid) exhibits surfactant like properties.

Claims

We claim:

1. An emulsifier / surfactant / dispersant polymer comprising : structural units of malic acid; and structural units of hydroxystearic acid.

2. The emulsifier / surfactant / dispersant polymer of claim 1 , wherein the emulsifier / surfactant / dispersant polymer has a number average molecular weight of 1,000 to 5,000 Daltons.

3. The emulsifier / surfactant / dispersant polymer of claim 1 , wherein 90 to 100 mol% of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid.

4. The emulsifier / surfactant / dispersant polymer of claim 1 , wherein the emulsifier / surfactant / dispersant polymer comprises:60 to 99.9 mol% of structural units of malic acid; and0.1 to 40 mol% of structural units of hydroxystearic acid.

5. The emulsifier / surfactant / dispersant polymer of claim 4, wherein the emulsifier / surfactant / dispersant polymer has a number average molecular weight of 1,000 to 5,000 Daltons.

6. The emulsifier / surfactant / dispersant polymer of claim 5, wherein 90 to 100 mol% of the structural units in the emulsifier / surfactant / dispersant polymer are either structural units of malic acid or structural units of hydroxystearic acid.

7. The emulsifier / surfactant / dispersant polymer of claim 6, wherein the structural units of hydroxystearic acid are selected from structural units of secondary hydroxystearic acid.

8. The emulsifier / surfactant / dispersant polymer of claim 7, wherein the structural units of secondary hydroxystearic acid are selected from the group consisting of 3-hydroxystearic acid, 4-hydroxystearic acid; 5-hydroxystearic acid; 6-hydroxystearic acid; 7-hydroxystearic acid; 8-hydroxystearic acid; 9-hydroxystearic acid; 10-hydroxy stearic acid;11 -hydroxy stearic acid; 12-hydroxy stearic acid; 13-hydroxystearic acid; 14-hydroxystearic acid; 15 -hydroxy stearic acid; 16-hydroxystearic acid and mixtures thereof.

9. The emulsifier / surfactant / dispersant polymer of claim 8, wherein the structural units of secondary hydroxystearic acid are structural units of 12-hydroxy stearic acid.

10. 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 an emulsifier / surfactant / dispersant polymer according to claim 9.

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