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WO2025056453A1 - Composition détergente pour lave-vaisselle comprenant de l'acide polyaspartique et/ou ses sels de métaux alcalins correspondants - Google Patents

Composition détergente pour lave-vaisselle comprenant de l'acide polyaspartique et/ou ses sels de métaux alcalins correspondants Download PDF

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Publication number
WO2025056453A1
WO2025056453A1 PCT/EP2024/075094 EP2024075094W WO2025056453A1 WO 2025056453 A1 WO2025056453 A1 WO 2025056453A1 EP 2024075094 W EP2024075094 W EP 2024075094W WO 2025056453 A1 WO2025056453 A1 WO 2025056453A1
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WIPO (PCT)
Prior art keywords
weight
acid
composition
alkali metal
mol
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PCT/EP2024/075094
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English (en)
Inventor
Oliver Jonathan Deane
Peter William Wills
Original Assignee
Unilever Ip Holdings B.V.
Unilever Global Ip Limited
Conopco, Inc., D/B/A Unilever
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Application filed by Unilever Ip Holdings B.V., Unilever Global Ip Limited, Conopco, Inc., D/B/A Unilever filed Critical Unilever Ip Holdings B.V.
Publication of WO2025056453A1 publication Critical patent/WO2025056453A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/10—Alpha-amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/04—Polyamides derived from alpha-amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the present invention relates to a detergent composition for use in machine dishwashing, containing polyaspartic acid and/or its corresponding alkali metal salts, having a weight average molecular weight of at least 20,000 g/mol. Moreover, the invention relates to a method for cleaning articles in a dishwashing machine, comprising the step of provision of a composition according to the invention to the dishwashing machine. Further aspects of the invention relate to the use of a composition according to the invention to improve the shiny surface of metal products which have been treated in a machine dishwashing process; to decrease spotting on surfaces of products which have been treated in a machine dishwashing process, and to improve the overall aesthetic appearances of articles which have been treated in a machine dishwashing process.
  • Polyaspartic acid is known to be used as a builder material or anti-redeposition agent in detergents, and as anti-scaling agent in cooling water systems, water desalination processes, and waste water treatment operations.
  • US 2021/0130740 A1 (Mitsui) relates to a detergent composition, comprising an antiredeposition agent that includes a polyaspartic acid alkali metal having a polydispersity, represented by the ratio (Mw/Mn) of the weight-average molecular weight (Mw) to the numberaverage molecular weight (Mn) of 1.4 or more, and being selected from the group consisting of lithium polyaspartate, potassium polyaspartate and sodium polyaspartate.
  • the polyaspartic acid alkali metal salt preferably has a weight-average molecular weight (Mw) of from 1 ,000 to 120,000, more preferred from 4,000 to 80,000.
  • the polyaspartic acid alkali metal salt preferably has a number-average molecular weight ranging from 1 ,000 to 80,000, more preferred from 4,000 to 50,000.
  • the detergent composition may be used for clothing, for tableware, for washing machines, or for a house. Preferably the composition is used for clothing, considering that the detergent composition works well due to the anti-redeposition agent; even in a range of from weak acidity to weak alkalinity, in which clothing material is not damaged.
  • US 2016/0229956 A1 relates to methods for producing polyaspartic acids with a weight-average molecular weight (Mw) of 6,000 to 15,000 g/mol, and polyaspartic acids obtainable from the method, compositions comprising the polyaspartic acids, and also the use thereof as scale inhibitors, dispersants and as additive in dishwashing agents, detergents or cleaning agents.
  • Automatic dishwasher compositions have been prepared, containing polyaspartic acids with molecular weights Mw ranging from 5,450 to 10,630 g/mol. These compositions show that a higher molecular weight of polyaspartic acid leads to an improved combination of scale formation and spotting on knives and glasses.
  • US 2012/0125374 A1 (Reckitt Benckiser) relates to detergent compositions for machine dishwashing comprising a combination of polyaspartic acid, a solid non-ionic surfactant and a liquid non-ionic surfactant.
  • the polyaspartic acid tested in machine dishwashing compositions (at a concentration of 25% by weight of the composition) has a molecular weight of 5,000 or 15,000 g/mol. Change of the molecular weight of polyaspartic acid has no influence on cleaning performance in a machine dishwashing test. The increase of the molecular weight of polyaspartic acid results in less spotting on long drink glasses. The filming on long drink glasses is also improved.
  • WO 2007/141145 A1 (Unilever) relates to a laundry detergent composition containing polyaspartate derivatives.
  • Such polyaspartate derivatives may have any molecular weight, though preferably the molecular weight is 50,000 or lower, more preferably the molecular weight is 20,000 or lower, even more preferably from 1 ,000 to 20,000.
  • the polyaspartate derivative is present at a level of from 0.001 to 20% by weight of the total composition.
  • US 2003/0069153 A1 (Procter & Gamble) relates to polyaspartate derivatives, especially hydrophobically modified and/or hydrophilically modified polyaspartate derivatives, most especially polyaspartate derivatives that are both hydrophilically and hydrophobically modified, for use in detergent compositions, specifically laundry detergent compositions for providing cleaning, dispersancy, especially soil dispersion, builder properties and/or improved whitening of fabrics contacted by such detergent compositions.
  • WO 2010/030323 A1 (Nanochem) relates to a method of making graft co-polymers and the resulting graft co-polymer, and more particularly to a method of making graft co-polymers from sodium poly(aspartate) and the resulting graft co-polymer.
  • the sodium poly(aspartate) is used as the backbone of the co-polymer, and preferably has a weight average molecular weight ranging from 1 ,000 to 50,000.
  • the co-polymer may be used in detergents.
  • IN 333315 (BASF) relates to the use of modified polyaspartic acids in dishwashing detergents, in particular as dispersants, film inhibitors and spot inhibitors.
  • the molecular weights fluctuate between 2,000-3,000 g/mol or between 5,000-6,000 g/mol depending on the preparation process. Adaptation of the polymer structure or of the molecular weight to specific application requirements through targeted process changes is only possible to a very limited extent, if at all.
  • the molecular weight of the polymers here can ideally be adjusted between 1 ,000 and 10,000 g/mol.
  • WO 2009/095645 A1 (Reckitt) relates to compositions comprising polyaspartic acid derivatives and the use of said compositions in washing processes, especially in automatic dishwashing.
  • the film of surfactant molecules covering the surface of the tableware and the dishwasher is believed to be stabilized by the polyaspartic acid derivatives; this prevents the deposition of calcium carbonate on the surfaces.
  • a second and unexpected beneficial effect is an increased "carry over" of surfactant from the main washing cycle into the rinse cycle due to the stabilized films of surfactant. This is important for multi-benefit detergents, because they are used without adding extra rinse aid into reservoir provided in the dishwasher.
  • WO 92/16462 and WO 95/20617 both relate to a method of using polyaspartic acid to inhibit the precipitation of calcium carbonate or calcium phosphate.
  • the polyaspartic acid with more than 50% beta-linkages, and less than 50% alpha-linkages, has a weight average molecular weight ranging from 1 ,000 to 5,000.
  • US 2009/0326165 A1 (Patil et al.) relates to a method of making graft co-polymers and the resulting graft co-polymer, and more particularly to a method of making graft co-polymers from sodium poly(aspartate) and the resulting graft co-polymer.
  • the sodium poly(aspartate) used has weight average molecular weight from 1 ,000 to 50,000.
  • the resulting graft co-polymer can have a molecular weight up to the millions.
  • US 2017/0321008 A1 (BASF) relates to methods for preparing polyaspartic acid by means of a pre-condensate of aspartic acid and polyaspartimide, to compositions comprising polyaspartic acid thus obtained, and to the use of such a pre-condensate for preparing polyaspartic acid.
  • Objective of the present invention is to provide a detergent composition for machine dishwashing which upon cleaning and treating articles like dishes, cutlery, glasses, and plastic products, provides the benefit that it inhibits the deposition of substances like soils and salts on the surface of those articles.
  • an objective is to provide a machine dishwash detergent composition which upon use reduces the number of spots left on the surface of articles after having been cleaned and dried in a dishwashing machine.
  • Another objective is to provide detergent compositions that improve the shiny surface of metal surfaces of treated articles, in particular stainless steel surfaces, in particular after a multitude of washes.
  • Another objective is to provide a machine dishwash detergent composition that not only improves the shiny appearance of treated articles, but also that of the internal metal surfaces in the dishwashing machine itself.
  • Another objective is to provide a machine dishwash detergent composition which leads to an improved aesthetic appearance of the articles that have been cleaned and dried in a dishwashing machine.
  • Such aesthetic appearance is an important attribute for the general consumer, as the aesthetic appearance is the first impression that the consumer gets when opening the dishwasher after running. The aesthetic appearance immediately gives the consumer to the impression whether the treated articles are clean, dry, and shiny, and without any residues from salts or soils left on the surfaces.
  • a machine dishwash detergent composition containing polyaspartic acid and/or its corresponding alkali metal salts, having a weight average molecular weight of at least 20,000 g/mol.
  • the presence of the polyaspartic acid and/or its corresponding alkali metal salts leads to an improved shiny surface of metal surfaces of treated articles and the machine itself, in particular in case such metal surfaces have been subjected to multiple washes with that detergent composition.
  • the use of such polyaspartic acid and/or its corresponding alkali metal salts leads to less spots left on the articles after having been washed and dried in a dishwashing machine.
  • composition of the invention improves the overall aesthetic appearance of the articles, due to good cleaning and drying, leading to improved shiny surface and reduction of spots left on the surfaces.
  • polyaspartic acid and/or its corresponding alkali metal salts are readily biodegradable.
  • the invention provides a composition for use in machine dishwashing, containing polyaspartic acid and/or its corresponding alkali metal salts, having a weight average molecular weight of at least 20,000 g/mol, and at a concentration ranging from 0.5% by weight to 5% by weight of the composition.
  • the invention provides in a second aspect a method for cleaning articles in a dishwashing machine, comprising the step of provision of a composition according to the first aspect of the invention to the dishwashing machine.
  • the invention provides the use of a composition according to the first aspect of the invention to improve the shiny surface of metal articles which have been treated in a machine dishwashing process. Further the invention provides the use of a composition according to the first aspect of the invention to decrease spotting on surfaces of articles which have been treated in a machine dishwashing process. Moreover, the invention provides the use of a composition according to the first aspect of the invention to improve the aesthetic appearance of articles which have been treated in a machine dishwashing process.
  • the concentration of compounds is generally provided by weight% (wt%) based on the total weight of the composition.
  • the first aspect the invention provides a composition for use in machine dishwashing, containing polyaspartic acid and/or its corresponding alkali metal salts, having a weight average molecular weight of at least 20,000 g/mol.
  • the polyaspartic acid most likely will be present in the salt form.
  • the composition comprises an alkali metal salt of polyaspartic acid.
  • the alkali metal comprises sodium, potassium, or lithium, or combinations thereof.
  • the composition comprises the sodium salt of polyaspartic acid, in other words sodium polyaspartate. Therefore, most preferred the composition of the invention comprises polyaspartic acid and/or sodium polyaspartate, having a weight average molecular weight of at least 20,000 g/mol.
  • the composition comprises the polyaspartic acid and/or its corresponding alkali metal salts at a concentration ranging from 0.5% by weight to 5% by weight of the composition, preferably from 1 % by weight to 5% by weight, preferably from 2% by weight to 5% by weight, preferably from 3% by weight to 5% by weight.
  • the composition comprises less than 5% by weight of polyaspartic acid and/or its corresponding alkali metal salts.
  • the composition comprises polyaspartic acid and/or its corresponding alkali metal salts at a concentration ranging from 0.5% by weight to 4.9% by weight, preferably from 1% by weight to 4.5 % by weight, preferably from 1 % by weight to 4% by weight of the composition, preferably from 2.5% by weight to 3.5 % by weight of the composition. More preferred, the composition comprises the polyaspartic acid and/or its corresponding alkali metal salts at a concentration ranging from 2% by weight to 4% by weight of the composition.
  • the weight average molecular weight of the polyaspartic acid and/or its corresponding alkali metal salts as used in the present invention is relatively high: at least 20,000 g/mol.
  • the polyaspartic acid and/or its corresponding alkali metal salts have a weight average molecular weight of at least 24,000 g/mol. A higher molecular weight leads to an improved benefit.
  • the polyaspartic acid and/or its corresponding alkali metal salts have a weight average molecular weight of at least 25,000 g/mol, preferably at least 30,000 g/mol, preferably at least 31 ,000 g/mol, preferably at least 32,000 g/mol, preferably at least 33,000 g/mol, preferably at least 34,000 g/mol.
  • the polyaspartic acid and/or its corresponding alkali metal salts have a weight average molecular weight of at least 35,000 g/mol, preferably at least 37,000 g/mol.
  • the maximum weight average molecular weight of the polyaspartic acid and/or its corresponding alkali metal salts preferably is 200,000 g/mol, preferably maximally 100,000 g/mol, preferably maximally 80,000 g/mol. More preferably, the polyaspartic acid and/or its corresponding alkali metal salts have a weight average molecular weight of maximally 60,000 g/mol, preferably maximally 50,000 g/mol, or preferably maximally 45,000 g/mol, preferably maximally 44,000 g/mol.
  • the weight average molecular weight of the polyaspartic acid can be determined using a method as described in one of the following standards:
  • TD-SEC Triple Detection Size Exclusion Chromatography
  • TM-SEC Triple Detection Size Exclusion Chromatography
  • the complete OMNISEC system consists of OMNISEC RESOLVE (chromatography module) and OMNISEC REVEAL (detectors module).
  • OMNISEC RESOLVE chromatography module
  • OMNISEC REVEAL detector module
  • the columns used for the analysis of polyaspartatic acid are 2 x A6000 columns plus the corresponding guard column.
  • the exclusion limit for these columns is 20 MDa with respect to Pullulan.
  • Typical sample solutions are prepared at 10 mg/ml and then filtered using 0.45 micrometer nylon filters prior to dispensing into sample vials using an eluent of demineralised water containing 0.02wt% sodium azide. The eluent is filtered using a 0.2 micrometer nylon filter.
  • the flow rate throughout all runs is 1 ml/min; the detector and column oven temperature is set to be at 40°C.
  • the detector calibration is carried out using a narrow molecular weight standard to calculate the detector offsets, the detector constants for all detectors and the band broadening and tailing corrections.
  • the calibration is performed using a standard of known concentration, molecular weight, dispersity and intrinsic viscosity; the narrow molecular weight standard of choice usually is a Pullulan standard material.
  • a verification standard is also run with every sequence. This standard is usually a broad (polydisperse) standard, whose properties are known and can be measured. This independently verifies that the calculation method has been correctly calibrated. For this analysis, a Dextran 73 kDa material is chosen.
  • the polyaspartic acid and/or its corresponding alkali metal salts may contain both the D-aspartic acid isomer, and the L-aspartic acid isomer as monomers.
  • the polymer may contain the aspartic acid monomers linked to each other by either alpha- or beta-peptide bonds. Therefore, the repeating unit of synthetically prepared polyaspartic acid, can exist in four isomeric forms, depending on the stereochemistry of the starting material (D- and L-aspartic acid) and the synthesis process leading to a and links (alpha and beta links).
  • the polyaspartic acid comprises poly(a, -D, L-aspartic acid) (poly(alpha,beta-D, L-aspartic acid)).
  • poly(a, -D, L-aspartic acid) poly(alpha,beta-D, L-aspartic acid)
  • the weight average molecular weight does not influence the handling of the polyaspartic acid.
  • the polyaspartic acid and/or its corresponding alkali metal salts are available as solution or dispersion in water.
  • a potential supplier of the materials is NanoChem Solutions Inc. (Naperville, IL, USA), and the materials are available with various average molecular weights.
  • composition of the invention may contain other ingredients which are commonly used in detergent compositions for machine dishwashing.
  • Builder Compounds and Sequestrants are commonly used in detergent compositions for machine dishwashing.
  • builder compound refers to a material that is capable of removing calcium and/or magnesium ion from aqueous solution by ion exchange, complexation, sequestration and/or precipitation.
  • the composition of the invention preferably contains builder compounds.
  • the alkali metal salts of citric acid comprise the sodium salt, the potassium salt, and lithium salt of citric acid, and mixtures thereof. More preferred the alkali metal salt of citric acid comprises the sodium salt of citric acid, also known as sodium citrate.
  • the sodium citrate may be present as the dihydrate salt, or the anhydrous salt. Most preferred the alkali metal salt of citric acid comprises trisodium citrate dihydrate.
  • composition of the invention comprises trisodium citrate dihydrate at a total concentration ranging from 5% to 15% by weight of the composition, preferably from 6% to 14% by weight, more preferred from 8% to 12% by weight.
  • citrate will dissolve in water and may (partly) be present as an acid rather than in an ionic form, with a single, double or triple negative charge, depending on the pH of the wash or rinse liquor in the dishwashing machine.
  • the citric acid and citrate ions act as builder material during the dishwashing process, and can bind calcium present in tap water and in the washing liquor.
  • the composition of the invention may contain other builder materials.
  • the composition comprises one or more aminocarboxylic acids and their corresponding alkali metal salts at a concentration ranging from 7% to 20% by weight of the composition.
  • aminocarboxylic acids and their alkali metal salts are selected from tetrasodium salt of glutamic acid, N,N-diacetic acid (GLDA) and trisodium salt of methylglycinediacetic acid (MGDA), and combinations thereof.
  • aminocarboxylic acids and their alkali metal salts are selected from tetrasodium salt of glutamic acid, N,N-diacetic acid (GLDA) and trisodium salt of methylglycinediacetic acid (MGDA).
  • MGDA and GLDA are well-known builder compounds in machine dishwash compositions.
  • a preferred source of GLDA is Dissolvine GL ex Nouryon (Arnhem, Netherlands), more in particular Dissolvine GL 47-S.
  • the latter is a liquid form of GLDA with a concentration of about 47% GLDA-Na4.
  • a preferred source of MGDA is Trilon M ex BASF (Ludwigshafen, Germany). Trilon M is available as liquid (approx. 40% MGDA-Na 3 ), as powder (approx. 84% MGDA-Na 3 ), and as granules (approx. 78% MGDA- Na 3 ).
  • Another preferred source for MGDA is Britesil ex PQ Corporation (Malvern, PA, USA), which are granules containing MGDA-Na 3 .
  • the aminocarboxylic acids and their alkali metal salts are included in the composition at a concentration ranging from 6% to 20% by weight of the composition, more preferred from 8% to 15% by weight, more preferred from 9% to 12% by weight of the composition.
  • the builder compounds tetrasodium salt of glutamic acid, N,N-diacetic acid (GLDA) and trisodium salt of methylglycinediacetic acid (MGDA) are included at a concentration ranging from 6% to 20% by weight of the composition, preferably from 8% to 15%, more preferred from 9% to 12% by weight of the composition.
  • Builder compounds or sequestrant material used in the present invention are preferably fully soluble so as to eliminate the possibility of unwanted and unsightly residues on substrates. For that reason alkali metal aluminosilicates are not favoured, and preferably absent from the product of the invention.
  • the composition comprises one or more aminocarboxylic acids and their alkali metal salts and citric acid and alkali metal salts of citric acid, at a total concentration ranging from 12% to 35% by weight of the composition.
  • the composition comprises one or more aminocarboxylic acids and their alkali metal salts on the one hand and citric acid and alkali metal salts of citric acid on the other hand in a weight ratio ranging from 3:1 to 1 :3.
  • the composition additionally comprises an alkali metal carbonate salt at a concentration ranging from 25% to 45% by weight of the composition, preferably ranging from 30% to 40% by weight of the composition. More preferred the composition comprises sodium carbonate at a concentration ranging from 25% to 45% by weight of the composition more preferred from 30% to 40% by weight of the composition.
  • the composition may comprise sodium silicate and/or sodium disilicate. If present, its concentration preferably ranges from 2% to 10% by weight, preferably from 3% to 8% by weight, more preferably from 4% to 7% by weight. More preferred the composition comprises hydrous sodium silicate at a concentration ranging from 2% to 10% by weight.
  • the hydrous sodium silicate preferably has the molecular formula HNaOsSi, and the mole ratio between SiC>2 and Na2O preferably ranges from 2.6 to 2.7.
  • the silicate serves as builder compound, and additionally has other benefits.
  • Such benefits include corrosion inhibitor for glass, and as a compound necessary to obtain the correct pH when the composition has been dissolved in water.
  • the weight ratio between alkali metal carbonate on the one hand and sodium silicate and/or sodium disilicate on the other hand ranges from 3 to 12, preferably from 4 to 1 1 . More preferred the ratio ranges from 5 to 10, more preferred from 6 to 9. Within this ratio, the cleaning performance of a product of the invention, in particular bleach performance, is optimal.
  • the product of the invention is preferably free from inorganic builder compounds based on phosphates.
  • This includes the water-soluble salts of phosphates, especially alkali metal pyrophosphates, orthophosphates and polyphosphates.
  • inorganic phosphate builder compounds which are preferably absent from the product include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates.
  • the composition may contain a phosphonate.
  • phosphonate preferably 1 -hydroxyl ethylidene-1 ,1 -diphosphonic acid (HEDP) is present.
  • HEDP 1 -hydroxyl ethylidene-1 ,1 -diphosphonic acid
  • the maximum concentration of HEDP in the composition is less than 2% by weight, more preferably less than 1.5% by weight, and at least 1% by weight.
  • the phosphonate serves to inhibit the growth of calcite crystals during the washing process in the dishwasher.
  • non-phosphorus water-soluble builder compounds may be present, such as alkali metal carbonates other than sodium carbonate, bicarbonates, sesquicarbonates, borates, and crystalline and amorphous aluminosilicates, and organic builders as polycarboxylate polymers, such as polyacrylates, acrylic/maleic co-polymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates other than sodium citrate, gluconates, oxydisuccinates, glycerol mono- di and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxy- malonates, dipicolinates and hydroxyethyliminodiacetates.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic co-polymers, and acrylic phosphonates
  • monomeric polycarboxylates such as citrates other than sodium citrate, gluconates, oxydisuccinates, glycerol mono- di and trisuccinates
  • the product of the invention does not comprise other builder compounds in addition to the polyaspartic acid and/or its corresponding alkali metal salts of the invention, and the preferred citric acid and citrates, carbonate salt, aminocarboxylic acids and their corresponding alkali metal salts, and silicates.
  • Builder compounds or sequestrant material used in the present invention are preferably fully soluble so as to eliminate the possibility of unwanted and unsightly residues on substrates. For that reason alkali metal aluminosilicates are not favoured, and preferably absent from the product of the invention.
  • the composition of the invention may contain one or more other polymers, preferably dispersant polymers.
  • Such polymers, preferably dispersant polymers may aid in dispersing soils and other compounds.
  • Such dispersant polymers may be used to improve drying of articles treated in the dishwashing machine, to prevent spotting and formation of stripes on the articles, and may have other benefits as well.
  • the total concentration of dispersant polymers preferably ranges from 0.5 to 10% by weight, which includes the polyaspartic acid and its corresponding alkali metal salts.
  • the concentration of the other dispersant polymers, if present, preferably ranges from 0.01% to 9.5% by weight of the composition. More preferred the concentration of the other dispersant polymers, if present, ranges from 0.1% to 8% by weight of the composition, more preferred from 0.5% to 5% by weight of the composition.
  • the ratio between on the one hand the polyaspartic acid and its corresponding alkali metal salts and on the other hand the other dispersant polymers (if present), preferably ranges from 2:1 to 1 :15 by weight, more preferred from 1 :1 to 1 :10 by weight.
  • Preferred dispersant polymers to be added in combination with the polyaspartic acid and its corresponding alkali metal salts of the invention are selected from polycarboxylates, polyacrylates, polymethacrylates, sulphonated polymers, copolymers of carboxylates and sulphonates, and mixtures thereof.
  • Such dispersant polymers to be added in combination with the polyaspartic acid and its corresponding alkali metal salts of the invention are selected from polyacrylates, sulphonated polymers, and mixtures thereof.
  • Preferred polyacrylates include anionic carboxylic polymers. They can either be homopolymers or co-polymers, and preferably have a weight average molecular weight of maximally 200,000 g/mol, preferably maximally 75,000 g/mol, and preferably at least 3,000 g/mol, preferably at least 5,000 g/mol.
  • the additional dispersant polymer preferably is a homopolymer of polyacrylate, having a weight average molecular weight ranging from 1 ,000 to 20,000 g/mol, preferably from 2,000 to 10,000 g/mol.
  • the polyacrylate may be a co-polymer of acrylic with methacrylic acid, acrylic and/or methacrylic with maleic acid, and acrylic and/or methacrylic with fumaric acid, preferably with a molecular weight of less than 70,000 g/mol.
  • Preferred polyacrylates which may be present in the composition of the inventions includes polyacrylate homopolymers, such as Sokalan PA15 or Sokalan PA25 (ex BASF), which are polyacrylic acids; polyacrylate co-polymers, such as Sokalan CP5 (ex BASF), which is a maleic acid-acrylic acid co-polymer.
  • Preferred sulphonated polymers if present, have a weight average molecular weight of maximally 100,000 g/mol, preferably maximally 75,000 g/mol, and preferably at least 3,000 g/mol, preferably at least 5,000 g/mol.
  • a range of sulphonated monomers can be used to prepare the sulphonated polymers, and these include 1 -acrylamido-1 -propanesulphonic acid, 2-acrylamido-2-propanesulphonic acid, 2-acrylamido-2-methyl-1 -propane sulphonic acid (AMPS), 2-methacrylamido-2-methyl-1 -propanesulphonic acid, 3-methacrylamido-2-hydroxy- propane-sulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzene- sulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3-(2-propenyloxy) propane- sulphonic acid, 2-methyl-2-propen-1 -sulphonic acid, styrenesulphonic acid, vinylsulphonic acid, 3-sulphopropyl, 3-sulpho-propylmethacrylate, sulphomethacrylamide, sulphomethylmethacrylamide and mixtures
  • the sulphonated polymer may in addition to the sulphonated monomer, additionally contain a carboxylated monomer.
  • the sulphonated polymer comprises 70% to 80% by weight of the polymer of at least one carboxylic acid monomer and from 20% to 30% by weight of the polymer of at least one sulphonic acid monomer.
  • Preferred carboxylic acid monomer are acrylic acid and methacrylic acid, and the sulphonated monomer preferably comprises AMPS.
  • Preferred sulphonated polymers for use in the present invention are Sokalan CP50 (ex BASF), a sulphonated co-polymer of AMPS and acrylic acid; or Acusol 588 (ex Dow), a co-polymer of AMPS and acrylic acid; or Alcosperse 240 and Aquatreat AR 540 (ex Nouryon); or Acumer 3100, Acumer 2000, and Acusol 587 (ex Dow)
  • sulphonated polymers are the itaconic/sulphonic co-polymers, which contains a monomer derived from itaconic acid, and as sulphonated monomer preferably comprises styrene-sulphonic acid and/or AMPS.
  • sulphonated monomer preferably comprises styrene-sulphonic acid and/or AMPS.
  • such polymer comprises from 5% to 20% by weight thereof of monomer units derived from styrene-sulphonic acid.
  • the polymer comprises from 15% to 40% by weight thereof of monomer units derived from AMPS.
  • such polymer has a weight average molecular weight of from about 500 g/mol to 10,000 g/mol.
  • co-polymer are Itaconix TSI 122 and Itaconix TSI 322 ex Itaconix Corporation. These polymers are co-polymers of itaconic acid and AMPS.
  • PESA polyepoxysuccinic acid
  • This polymer is also known as epoxysuccinic acid homopolymer, polyoxirane-2,3-dicarboxylic acid, 2,3-oxiranedicarboxylic acid homopolymer, or poly(1 -oxacyclopropane-2, 3-dicarboxylic acid); and has the general structure: where R may be hydrogen or any organic chain (but preferably an ester such as C1-4 alkyl) and where M may be any cation (preferably such as Na + , H + , K + , and/or NH4T
  • M w molecular weight
  • PESA and their derivatives have a molecular weight (M w ) ranging from 100 to 10,000 g/mol.
  • amphoteric polymers such as Mirapol Surf S (ex Solvay).
  • graft copolymers having a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units.
  • the graft co-polymer contains one or more side chains of two or more, even more preferably of three or more synthetic monomeric units.
  • the preferred graft co-polymer preferably has a molecular weight of at least 4,000 g/mol, more preferably of at least 8,000 g/mol and most preferably at least 15,000 g/mol.
  • the one or more synthetic monomeric units are preferably selected from olefinically unsaturated carboxylate monomers; sulphonate monomers; phosphonate monomers and combinations thereof.
  • the one or more synthetic monomeric units are selected from olefinically unsaturated carboxylate monomers; sulphonate monomers and combinations thereof. Most preferably, the synthetic monomeric units are olefinically unsaturated carboxylate monomers.
  • the olefinically unsaturated carboxylate monomers include, for example, aliphatic, branched or cyclic, mono- or dicarboxylic acids, the alkali or alkaline earth metal or ammonium salts thereof, and the anhydrides thereof.
  • Examples of such olefinically unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, ethacrylic acid, a-chloro-acrylic acid, a-cyano acrylic acid, p-methyl-acrylic acid (crotonic acid), a-phenyl acrylic acid, p-acryloxy propionic acid, sorbic acid, a-chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, p- styryl acrylic acid (1 -carboxy-4-phenyl butadiene-1 ,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, and 2- acryloxypropionic acid.
  • Moieties such as maleic anhydride or acrylamide that can be derivatized to an acid containing group can also be used.
  • combinations of olefinically unsaturated carboxylic acid monomers may be used.
  • the olefinically unsaturated carboxylic acid monomer is selected from acrylic acid, maleic acid, itaconic acid, or methacrylic acid and combinations thereof.
  • sulphonate monomers examples include AMPS, as well as styrene-sulphonic acid, (meth-)acrylic acid sulpho-alkyl esters, itaconic acid-sulpho-alkyl esters, preferably in each case as Ci-Ce-alkyl esters, vinyl sulphonic acid and the alkali, alkaline earth and/or ammonium salts thereof.
  • AMPS styrene sulphonic acid
  • acrylic acid-sulpho-propyl ester acrylic acid-sulpho-propyl ester
  • itaconic acid-sulpho-propyl ester itaconic acid-sulpho-propyl ester
  • vinyl sulphonic acid as well as in each case the ammonium, sodium, potassium and/or calcium salts.
  • the polysaccharide that forms the backbone of the graft co-polymer is preferably selected from starch, maltodextrin, cellulose, gums (e.g., gum arabic, guar and xanthan), alginates, pectin and gellan. More preferably, the polysaccharide is selected from starch and maltodextrin.
  • the polysaccharides employed in the graft co-polymer can be modified or derivatised by etherification (e.g., via treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyl trimethyl ammonium chloride), esterification (e.g., via reaction with acetic anhydride, octenyl succinic anhydride (“OSA”)), acid hydrolysis, dextrinization, oxidation (e.g. oxidized starch) or enzyme treatment, or various combinations of these treatments.
  • etherification e.g., via treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyl trimethyl ammonium chloride
  • esterification e.g., via reaction with acetic anhydride, octenyl succinic anhydride (“OSA”)
  • OSA octenyl succinic anhydride
  • acid hydrolysis e.g., dextrinization, oxidation (e.g. oxid
  • the polysaccharide of the co-polymer is maltodextrin.
  • Maltodextrins are polymers that can be produced by starch hydrolysis and that have D-glucose units linked primarily by a-1 ,4 bonds and a dextrose equivalent of less than about 20.
  • Dextrose equivalent (DE) is a measure of the extent of starch hydrolysis. It is determined by measuring the amount of reducing sugars in a sample relative to dextrose (glucose). The DE of dextrose is 100, representing 100% hydrolysis.
  • the polysaccharide in the backbone of the graft co-polymer preferably contains a chain of at least 8, more preferably of at least 10 monosaccharide units bound together by glycosidic linkages.
  • the graft copolymer preferably has a high degree of polysaccharide. Typically, the polysaccharide represents at least 50 wt.%, more preferably at least 60 wt.%, even more preferably at least 70 wt.% and most preferably at least 80 wt.% of the graft co-polymer.
  • graft co-polymer that may suitably be employed in accordance with the present invention is Alcoguard H 5240, which is commercially available from Nouryon.
  • the term "bleach component" as used herein refers to substances that are capable of removing coloured stains by oxidizing or reducing the colour components of the stain.
  • the bleach component preferably employed in the present detergent composition preferably is an oxidizing bleach component.
  • the oxidizing bleach component may suitably comprise a chlorine-, or bromine-releasing agent or a peroxygen compound.
  • the bleach component is selected from peroxides (including peroxide salts such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleach component is a peroxide. Examples of peroxides are acids and corresponding salts of monopersulphate, perborate monohydrate, perborate tetrahydrate, and percarbonate. More preferably, the bleach component is a percarbonate, most preferably sodium percarbonate.
  • Organic peracids useful herein include alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring substituted peroxybenzoic acids (e.g. peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid), and phthaloyl amido peroxy caproic acid (PAP).
  • alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring substituted peroxybenzoic acids (e.g. peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid), and phthaloyl amido peroxy caproic acid (PAP).
  • peroxybenzoic acid and ring substituted peroxybenzoic acids e.g. peroxy-alpha-n
  • bleach activators suitable for use in the cleaning compositions of this invention include one or more activators such as peroxyacid bleach precursors.
  • Peroxyacid bleach precursors are well known in the art.
  • TAED tetraacetylethylenediamine
  • SNOBS sodium nonanoyloxybenzene sulphonate
  • SBOBS sodium benzoyloxybenzene sulphonate
  • SPCC cationic peroxyacid precursor
  • a bleach activator may suitably be present in the composition in the form of a encapsulate, notably an encapsulate that is separate from the bleach particles in order to avoid premature bleach activation.
  • the composition preferably contains tetraacetylethylenediamine (TAED), at a concentration ranging from 2% to 4% by weight.
  • concentration of TAED is maximally 3%, preferably maximally 2.7% by weight of the composition.
  • the composition is free from other bleach activators than TAED, like peroxyacid bleach precursors.
  • the composition is free from sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC).
  • SNOBS sodium nonanoyloxybenzene sulphonate
  • SBOBS sodium benzoyloxybenzene sulphonate
  • SPCC cationic peroxyacid precursor
  • a “bleach catalyst” is a compound that also activates the bleaching process. Bleaching catalysts are also known in the art.
  • the composition of the invention preferably comprises a bleach catalyst at a concentration ranging from 0.005% to 0.1 % by weight of the composition.
  • Such bleach catalyst preferably comprises a manganese-containing bleach catalyst, preferably at a concentration ranging from 0.005% to 0.1% by weight of the composition.
  • concentration of the bleach catalyst in the composition ranges from 0.006% to 0.08% by weight, more preferred from 0.008% to 0.07% by weight of the composition.
  • Preferred manganese-containing bleach catalysts include a manganese complex as described in EP 0 458 397 A2.
  • the composition comprises a complex of the following formula:
  • Preferred ligands are 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane (coded as Me-TACN); 1 ,4,7- triazacyclononane (coded as TACN); 1 ,5,9-trimethyl-1 ,5,9-triazacyclododecane (coded as Me- TACO); 2-methyl-1 ,4,7-trimethyl-1 ,4,7-triazacyclononane (coded as Me/Me-TACN); and 2- methyl-1 ,4,7-triazacyclononane (coded as Me/TACN).
  • Ligands Me-TACN and Me/Me-TACN are particularly preferred for use as bleach catalyst.
  • the composition comprises Me-TACN at a concentration ranging from 0.005% to 0.1% by weight of the composition, preferably 0.006% to 0.08% by weight, more preferred from 0.008% to 0.07% by weight.
  • the composition comprises Me/Me-TACN at a concentration ranging from 0.04% to 0.1% by weight of the composition, preferably 0.04% to 0.09% by weight, more preferred from 0.008% to 0.07% by weight.
  • the composition comprises a combination of Me-TACN and Me/Me-TACN at a concentration ranging from ranging from 0.04% to 0.1% by weight of the composition, preferably 0.04% to 0.09% by weight, more preferred from 0.008% to 0.07% by weight.
  • one or more non-coordinating counterions are selected from acetate, chloride, sulphate, nitrate and hexafluorophosphate.
  • the product of the invention preferably comprises a non-ionic surfactant.
  • the composition comprises non-ionic surfactant at a concentration ranging from 0.5% to 4% by weight of the composition. Preferably the concentration ranges from 1% to 4%, more preferred from 1% to 3% by weight.
  • the non-ionic surfactant preferably is a low-foaming non-ionic surfactant.
  • Preferred non-ionic surfactants include the alkyl ethoxylates and the alkyl ethoxylates propoxylates.
  • a preferred non-ionic surfactant for use in the composition is a modified fatty alcohol polyglycol ether, such as Dehypon E127 (ex BASF, Ludwigshafen, Germany).
  • Other useful non-ionic surfactants include for example Dehypon WET (ex BASF), Lutensol AT80 (ex BASF), Ecosurf Bright 12 (ex Dow), and Genapol EC50 M90 (ex Clariant).
  • the composition of the invention preferably comprises one or more enzymes; preferably selected from proteases and/or amylases. Such enzymes are commonly known to be used in machine dishwash compositions.
  • the enzymes may be immobilised on a carrier, or in a liquid.
  • Optional ingredients are, for example, buffering agents, reducing agents, e. g., borates, alkali metal hydroxide and the well-known enzyme stabilisers such as the polyalcohols, e. g. glycerol and borax; crystal -growth inhibitors, threshold agents; perfumes and dyestuffs and the like.
  • Glass corrosion inhibitors can prevent the irreversible corrosion and iridescence of glass surfaces in automatic dishwash detergents.
  • the claimed composition may suitably contain glass corrosion inhibitors.
  • Suitable glass corrosion inhibitors can be selected from the group the group consisting of salts of zinc, bismuth, aluminum, tin, magnesium, calcium, strontium, titanium, zirconium, manganese, lanthanum, mixtures thereof and precursors thereof. More preferred are salts of bismuth, magnesium or zinc or combinations thereof.
  • the most prefered glass corrosion inhibitors are silicate, disilicate or combinations thereof. Using silicates helps on reducing the glass corrosion as well as aluminium corrosion over time.
  • Anti-tarnishing agents may prevent or reduce the tarnishing, corrosion or oxidation of metals such as silver, copper, aluminium and stainless steel.
  • Anti-tarnishing agents such as benzotriazole, methyl benzotriazole or bis-benzotriazole and substituted or substituted derivatives thereof and those described in EP 0 723 577 may also be included in the composition.
  • the composition may comprise monoethanolamine, and if present preferably at a concentration ranging from 4% to 8% by weight of the composition, preferably ranging from 5% to 7% by weight.
  • the composition preferably is a solid composition, for example a powdered composition, or a tabletted composition.
  • the composition is present as a unit-dose composition, meaning that a consumer can take a single unit-dose, and provide it to a household dishwasher, without the risk of overdosing or underdosing the detergent.
  • the unit-dose composition is present as a powder, then the powder composition may be packed in a capsule of water-soluble polyvinylalcohol film.
  • a unit-dose tablet may be packed in a water-soluble polyvinylalcohol film. This prevents that the consumer touches the detergent composition with bare hand or fingers.
  • the amount of the unit-dose product preferably ranges from 10 to 25 gram, preferably from 15 to 20 gram.
  • the moisture level of the preferred solid composition preferably ranges from about 0.5% to about 8% by weight of the composition.
  • the moisture may be present as dissolved water, which may naturally be present in the ingredients.
  • the pH of the composition when dissolved in water preferably ranges from 8 to 12, more preferred from 9 to 1 1 , more preferred from 9.5 to 10.5, more preferred from 9.8 to 10.5.
  • the pH that results upon dissolution is easily adapted such that it falls in the required range by variation of the amounts of components of differing acidity and basicity, the composition typically including components of well-known acidity and basicity. This pH requirement ensures that the pH of the wash liquor upon use is optimal for the functioning of the ingredients.
  • the composition of the invention is a solid product
  • the composition can be prepared by a standard process for making powdered detergents: dry mixing the various dry ingredients into a homogeneous mixture, and subsequently spraying the optional liquid nonionic surfactant (if present in the composition) on the dry powder. Such powder with optional absorbed non-ionic surfactant is then again mixed into a homogeneous mixture.
  • the preferred powder is free-flowing, such that the many granules of the powder do not stick to each other.
  • the diameter of the individual granules generally ranges from about 0.01 millimeter up to about 2 millimeter.
  • the powder may be packed in individual pouches preferably made from polyvinyl alcohol. The consumer can dose such pouch directly into the dishwasher, as a unit-dose composition. The polyvinylalcohol will rapidly dissolve in the water in the dishwashing process.
  • the powder may be compressed into a tablet, which aids the consumer to dose the correct amount of detergent composition to the dishwasher.
  • a preferred tablet is prepared by compressing a defined amount of powder into a tablet, by adding the powder into a recess, and compressing the powder in that recess with a solid weight with the exertion of force, such that no individual granules from the powders are identifiable anymore.
  • the tablet may be covered by a film made from polyvinyl alcohol, and the polyvinylalcohol will rapidly dissolve in the water in the dishwashing process.
  • the invention provides a method for cleaning articles in a dishwashing machine, comprising the step of provision of a composition according to the first aspect of the invention to the dishwashing machine.
  • the method includes placing the correct amount of the composition in the drum or dosing drawer or any dosing device of a dishwashing machine prior to commencement of a wash cycle.
  • that correct amount is a unit-dose product of the invention, as described herein before.
  • the temperature of the dishwashing process preferably ranges from 30°C to 95°C, more preferred from 30°C to 70°C, more preferred from 30°C to 55°C.
  • the third aspect of the invention provides the use of a composition according to the first aspect of the invention to improve the shiny surface of metal articles which have been treated in a machine dishwashing process. Additionally, this is not only an advantage obtained when cleaning dishes in the machine, but also the internal metal surfaces of the machine have a stronger shiny surface than when using compositions that do not contain the polyaspartic acid of the invention.
  • the invention provides a method to improve the shiny surface of metal articles which have been treated in a machine dishwashing process, by using a composition according to the first aspect of the invention.
  • a composition according to the first aspect of the invention Preferably such metal surface is a stainless steel surface.
  • the invention provides the use of a composition according to the first aspect of the invention to decrease spotting on surfaces of articles which have been treated in a machine dishwashing process.
  • the invention provides a method to decrease spotting on surfaces of articles which have been treated in a machine dishwashing process, by using a composition according to the first aspect of the invention. Also this effect is obtained more clearly after multiple cleaning rounds.
  • Reduced spotting, and improved shiny surface of metal means that the aesthetic appearance of the cleaned dishes and internal machine walls has improved.
  • the consumer emptying a machine after a cleaning round will notice immediately this positive effect on the dishes and the internal wall of the machine. This will give the consumer a positive impression on the quality of the detergent composition of the invention.
  • the invention provides the use of a composition according to the first aspect of the invention to improve the aesthetic appearance of articles which have been treated in a machine dishwashing process. Or in other words, the invention provides a method for improving the aesthetic appearance of articles which have been treated in a machine dishwashing process, by using a composition according to the first aspect of the invention.
  • Any preferred aspect disclosed herein in relation to the first aspect of the invention can be applied to the third aspect of the invention, mutatis mutandis. While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention.
  • Example 1 Machine dishwash compositions were prepared, with different types of polyaspartic acid.
  • MGDA granules contain 80.5% MGDA-Nas salt
  • formulations were prepared by mixing the dry materials excluding the polyaspartic acid preparations to make a dry granular powder composition, in a conventional manner as known in the art. These granular powders were dosed in dry form to the dispensing drawer of a machine dishwashing machine, to perform the tests described below.
  • the liquid polyaspartic acid solutions were added separately to the machine, at the same time as the dosing of the powder. This means that the polyaspartic acid solution can be regarded to be an ingredient of the compositions as described in the table above.
  • Table 2 pH of machine dishwash detergents, formulations as in Table 1 .
  • the pH was determined by taking aliquots of the washing liquor after it had run for 15 minutes in the main wash program. The samples were kept at a temperature of 20°C, and subsequently the pH was measured with calibrated pH meter.
  • Table 3 Information about polyaspartic acid and its corresponding salts in the formulations as in Table 1 , as supplied by NanoChem Solutions Inc. (Naperville, IL, USA).
  • the weight average molecular weights were provided by the supplier of the materials. These can be determined using the method in the description, using a T riple Detection Size Exclusion Chromatography (TD-SEC) system. Such analysis is conducted using a Malvern OMNISEC system (ex Malvern Panalytical Ltd., Malvern, United Kingdom).
  • TD-SEC T riple Detection Size Exclusion Chromatography
  • Table 1 The formulations as in Table 1 were used in machine dishwash tests, under the following conditions: Table 4: Washing conditions for washes in machine dishwasher.
  • SGS spotting soil (used in 6 washes experiments): tomato ketchup 2.5%, potato starch 0.5%, benzoic acid 0.1%, margarine 10.1%, milk (1.5%) 5.1%, egg yolk (30 count) 5.8%, tap water 75.9%.
  • STIWA soil used in 30 washes experiments: tomato ketchup 2.5%, potato starch 0.5%, mustard 2.5%, gravy 2.5%, benzoic acid 0.1%, margarine 10.1%, milk (1.5%) 5.1%, egg yolk (30 count) 5.8%, tap water 70.9%. These soils are intended to simulate the presence of easily removable food residues.
  • the unit dose weight of the detergent composition was 18 gram per wash. This 18 gram dose includes the liquid polyaspartic acid solution which was added separately from the dry compounds to the wash, and which is included/mentioned in the formulations in Table 1 .
  • “Spots” are formed through water not completely running off dishes in the end of the wash cycle and the drying up of these drops that remain.
  • the water may contain calcium and magnesium salts, which may originate from the tap water which is used to clean, or from the soils.
  • “Filming” means that a moderate and uniform coating from salts is left behind on the articles and that, subsequently, may produce a dull outer appearance.
  • “Aesthetic appearance” means that the visual appearance of overall cleanliness of the article is determined; without focussing on any one attribute alone.
  • the articles from the dishwasher are illuminated from above with normal light versus a grey wall to mimic an average consumer kitchen background, using the naked eye.
  • the objective is to evaluate the overall appearance of articles from the dishwasher, in an objective and reproducible manner. It focuses more on looking good or bad, rather than the exact number of spots or presence of filming.
  • the shininess of the article’s surface is an important attribute for aesthetic appearance.
  • a viewing cabinet For determination of spots and filming, a viewing cabinet is used. In this cabinet, articles having been treated in the dishwasher are either illuminated from beneath (glasses) or from above (other articles). Under standardised light conditions, a comparison can be made between articles which have been treated as described above, or which are new and/or clean (meaning without spots).
  • the score is about the number of spots or streaks. The score does not measure density, size or colour of spots or streaks.
  • the spotting score is highly correlated to the amount of visible clear glass, i.e. when the score for spotting is low (there are lots of spots), the amount of visible clear glass is also very low.
  • Table 5 Scores for spotting for the formulations in Table 1 , after 6 washes under the conditions as in Table 4, column ‘For 6 washes experiments’ . These results show that composition F4, containing polyaspartate with a molecular weight of 40,000 g/mol, has the best results after 6 washes (meaning least spots after drying). In particular the effect is strong on plastic and earthenware dishes. Also F3, containing polyaspartate with a molecular weight of 10,000 g/mol, has a better scoring on spotting, as compared to the two compositions F1 and F2 containing lower molecular weight polyaspartate. Table 6: Scores for filming for the formulations in Table 1 , after 6 washes under the conditions as in Table 4, column ‘For 6 washes experiments’ .
  • Table 7 Scores for aesthetic appearance for the formulations in Table 1 , after 6 washes under the conditions as in Table 4, column ‘For 6 washes experiments’.
  • Composition F4 containing polyaspartate with a molecular weight of 40,000 g/mol, scores best on general aesthetic appearance of the dishes after 6 washes.
  • aesthetics relates to the visual appearance of the dishes after washing, this parameter has a strong effect on the evaluation of the results by the average consumer who empties the dishwasher after cleaning. It shows that the reduction in spotting of the compositions with higher molecular weight polyaspartic acid leads to better spotting results (meaning less spotting). Filming score are more or less similar for the compositions, so the improved spotting compensates strongly for the flat filming results on determining overall aesthetic appearance. The even scores on filming do not counteract the improved spotting results and overall aesthetic appearance. In particular the metal surfaces of the articles cleaned with composition F4, have a more shiny surface than the articles cleaned with the other compositions.
  • Table 8 Scores for spotting for the formulations as in Table 1 , after 30 washes under the conditions as in Table 4, column ‘For 30 washes experiments’ .
  • composition F4 containing polyaspartate with a molecular weight of 40,000 g/mol, shows the best results (meaning least spots after drying).
  • the effect is strong on metal and glass surfaces. It seems that a lasting effect is obtained on these surfaces, that the high molecular weight polyaspartate leads to a surface which is less prone to spotting on the long term.
  • F3 containing polyaspartate with a molecular weight of 10,000 g/mol, has a better scoring on spotting, as compared to the articles cleaned with compositions F1 and F2 containing lower molecular weight polyaspartate.
  • Table 9 Scores for filming for the formulations as in Table 1 , after 30 washes under the conditions as in Table 4, column ‘For 30 washes experiments’ .
  • Table 10 Scores for aesthetics for the formulations as in Table 1 , after 30 washes under the conditions as in Table 4, column ‘For 30 washes experiments’ .
  • composition F4 containing polyaspartic acid with a molecular weight of 40,000 g/mol, scores best on general aesthetic appearance of the treated articles after 30 washes.
  • aesthetics relates to the immediately observed visual appearance of the articles after washing, this parameter has a strong effect on the evaluation of the results by the average consumer who empties the dishwasher after washing.
  • compositions containing polyaspartate having a molecular weight of 40,000 g/mol are the compositions which yield the best results with regard to spotting, and overall aesthetic appearance of the dishes.
  • shininess of metal surfaces which have been treated improved by using the composition containing polyaspartic acid having a molecular weight of 40,000 g/mol.
  • composition F4 leads to least spots on the metal surface of the door of the machine.
  • Table 11 Scores for spotting and filming on inside of metal machine door, for the formulations as in Table 1 , after 30 washes under the conditions as in Table 4. Also in this case, the effect of the molecular weight of polyaspartic acid on filming was flat. There is a very pronounced effect on spotting: a higher molecular weight of polyaspartic acid leads to a strong reduction of spots on the internal metal (steel) was of the dishwasher after 30 washes. Also the aesthetic appearance of the internal door had improved, although it was not possible to quantify this in the same manner as with the treated articles. The shiny surface of the internal metal wall of the door was clearly visible when using the composition containing polyaspartic acid having a molecular weight of 40,000 g/mol. A reduction of spots leads to a more shiny surface.
  • Example 2 Example 2
  • a machine dishwash composition was prepared, with the following type of polyaspartic acid: Polyaspartic acid A-43D, as supplied by NanoChem Solutions Inc. (Naperville, IL, USA).
  • the weight average molecular weight was 43,000 g/mol. This weight average molecular weight was provided by the supplier of the material. This can be determined using the method as described in example 1 .
  • MGDA granules contain 80.5% MGDA-Nas salt
  • This formulation was prepared in a similar manner as described in example 1.
  • the pH of this composition at a concentration in water of 3.6 gram per litre, and measured at a temperature of 20°C (similar as in example 1 ), was 10.4.

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  • Detergent Compositions (AREA)

Abstract

L'objectif de la présente invention est de fournir une composition détergente pour le lavage de la vaisselle en machine qui, lors du nettoyage et du traitement d'articles tels que des plats, des couverts, des verres et des produits plastiques, offre l'avantage qu'elle empêche le dépôt de substances telles que des salissures et des sels sur la surface de ces articles. Cet objectif a été atteint par une composition détergente destinée à être utilisée dans le lavage de la vaisselle en machine, contenant de l'acide polyaspartique et/ou ses sels de métaux alcalins correspondants, présentant une masse moléculaire moyenne en poids spécifique, afin de diminuer les taches sur des surfaces de produits qui ont été traités dans un procédé de lavage de la vaisselle en machine et d'améliorer les aspects esthétiques globaux d'articles qui ont été traités dans un processus de lavage de la vaisselle en machine. Ceci conduit à moins de taches sur des articles, une brillance améliorée et un aspect esthétique amélioré des articles traités et séchés.
PCT/EP2024/075094 2023-09-15 2024-09-09 Composition détergente pour lave-vaisselle comprenant de l'acide polyaspartique et/ou ses sels de métaux alcalins correspondants WO2025056453A1 (fr)

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