Patent Description:
The automatic dishwashing detergent formulator is continuously looking for ways to improve the performance of automatic dishwashing, in terms of cleaning, finishing and also reducing the amount of water and energy consumed during the process.

<CIT> relates to a method of automatic dishwashing of dishware using wash water, wherein:.

The object of the present invention is to provide an automatic dishwashing method that provides improved cleaning and in particular, baked and burnt-on items and a more efficient use of water and energy than conventional dishwashing methods.

<CIT> relates to a method of automatic dishwashing of dishware.

<CIT> relates to a chemical cleaning system for multi-tank mechanical warewashing machine.

According to a first aspect of the invention, there is provided a method of washing dishware in a dishwasher. The method comprises the step of delivering two different compositions into the dishwasher. The first composition comprises bleach and it is substantially free of enzymes. The second composition comprises enzymes and it is preferably substantially free of bleach. The pH of the first composition is at least <NUM> and it is at least <NUM> pH unit higher than the pH of the second composition. The pH is measured in tap water at the wash concentration at <NUM>.

The method provides very good cleaning across most of the soils found on dishware and allows for shorter washing times.

Preferably, the method comprises the delivery of an intermediate composition between the first and second composition. The intermediate composition helps to lower the pH without draining the water. It allows the first and the second composition to use the same water, thereby saving water and energy. The intermediate composition comprises a pH buffering composition. Preferably the pH buffering composition also has calcium binding properties. Improved cleaning results are obtained when the pH buffering composition has calcium binding properties.

An automatic dishwashing operation typically comprises three or more phases: a pre-wash cycle, a main-wash cycle and one or more rinse cycles, these phases are usually followed by a drying step. The first and second compositions of the present invention are preferably delivered into the main wash without the need for a pre-wash. The method of the invention does not require the drainage of the wash liquor before the second composition is delivered. Both compositions can use the same wash water.

The present invention encompasses a method of washing dishware in a dishwasher and the use of the method to reduce the length of an automatic dishwashing process and a dishwasher. The method provides superior cleaning, potentially utilising less energy and/or water and/or chemicals.

"Dishware" herein means all items related to cooking and eating that are usually washed in a dishwasher.

The composition of the method and product of the invention are referred herein as "the composition of the invention".

As used herein, the articles including "a" and "an" are understood to mean one or more of what is claimed or described. Unless specifically stated or the context otherwise requires, embodiments described herein apply equally to all aspects of the invention. Percentages quoted are by weight, unless otherwise stated or the context otherwise requires.

The invention provides a method of washing soiled dishware in a dishwasher. The method comprises the step of firstly delivering a first composition followed by a second composition. The first composition has time to act before the second composition is added. The first composition comprises oxygen bleach but substantially no enzyme, and the second composition comprises enzyme. Preferably, the second composition is substantially free of bleach (whether oxygen bleach, halogen bleach or any other type of bleach). Preferably, the first composition contains no more than <NUM> wt % enzymes, preferably no more than <NUM> wt % enzymes, preferably no more than <NUM> wt % enzymes, preferably no more than <NUM> wt % enzymes, preferably no more than trace amounts of enzymes, preferably no enzymes. Preferably, the second composition contains no more than <NUM> wt % bleach, preferably no more than <NUM> wt % bleach, preferably no more than <NUM> wt % bleach, preferably no more than <NUM> wt % bleach, preferably no more than trace amounts of bleach, preferably no bleach.

The delivery of the second composition is preferably at least <NUM> minutes, more preferably at least <NUM> minutes and especially <NUM> minutes after the delivery of the first composition. The second composition is preferably delivered after approximately one third of the duration of the cycle and before two thirds of the duration of the cycle. The delivery time of the first and second compositions can be optimised depending on the type of soils that the dishware has, for example if the dishware load contains enzymatic soils then it might be preferred to give the second composition more acting time than the first composition. But if the load contains baked or burnt soils, it might be preferred to increase the proportion of time spent with the first chemistry. Preferably, the first and the second composition are delivered into the main wash cycle. If for example, the duration of the main wash is <NUM> mins, the first composition can be added when the cycle starts and let it act from approximately <NUM> minutes and then optionally adding the intermediate composition and let it act for approximately <NUM> minutes and then <NUM> minutes after the first composition is added, the second composition is added.

The pH of the first composition is at least <NUM>, preferably at least greater than <NUM>, more preferably at least about <NUM> and especially about <NUM>. The pH of the second composition is at least <NUM> pH unit, more preferably at least <NUM> and especially at least <NUM> units lower than the pH of the first composition. Especially preferred is when the first composition has a pH greater than <NUM> and the second composition has a pH <NUM> units less. The pH is measured at the wash concentration in tap water and at <NUM>. The method optionally but preferably comprises the step of delivering an intermediate composition after the first composition and before the second composition. The intermediate composition allows the pH of the wash liquor to decrease at least <NUM> unit, preferably at least <NUM> units, more preferably at least <NUM> units.

Although in the method of the invention it is possible to use an oxygen bleach scavenger in the intermediate or in the second composition, this is not essential. The wash water does not need to be removed from the interior of the dishwasher and fresh wash water does not need to be used in the second step, thereby saving water.

In one embodiment, the main wash cycle can be thought of as <NUM> phases which correspond to the dosing of the compositions. In a first phase of the main wash cycle, the first composition is delivered and dosed at the beginning of the main wash cycle after filling the dishwasher with water. As time is among the important factors for removing soils such as baked-on soils, the time with this first composition is preferably at least <NUM> minutes. This time can be shortened for quick cycles, but minimum time of <NUM> minutes is preferred be used even for short cycles. Also, the temperature for this first phase is important as well. Higher temperatures are associated with better baked-on cleaning. A target of <NUM>° C is most preferred, with <NUM>° C as a trade-off for a quicker cycle or to reduce energy with <NUM>° C as the least temperature to achieve cleaning performance.

In a second phase of the main wash cycle, the second phase begins with the addition of a buffering chemistry, which can include the second composition to reduce the pH of the main wash liquid according to the needs of the third composition which will be added in the third phase of the main wash cycle. Typically, there is no heat added during this phase. Time spent in this phase should be preferably about <NUM> minutes following the dosing of the second composition to allow the dishwasher to cycle through all the wash zones within the dishwasher and for the dilution of all the wash liquid inside the dishwasher.

In a third phase of the main wash, the third phase begins with the addition of the enzymes corresponding to the third composition of the chemistry. While non-burnt-on foods respond to longer cleaning times in this phase, a shorter time is desirable as a trade-off for energy consumption and overall cleaning performance. This third phase has a preferred time of about <NUM> minutes, although longer times in this phase would benefit cleaning performance if energy and time are not considered as important. The temperature in this third phase is a byproduct of the temperature desired for the first phase. For example, if the temperature of the first phase is most significant, it is possible to either (<NUM>) maintain temperature through this third phase, (<NUM>) allow the temperature to decrease towards ambient temperature, or to (<NUM>) continue towards the desired temperature (if it was not achieved in the first phase) since temperature in this phase in this example is not considered a factor for cleaning.

Further in this embodiment, following the main wash cycle, there is a complete drain of the dishwasher tub and refill for an intermediate rinse cycle. The purpose of this intermediate rinse cycle is to remove bulk soils from the wash bath, neutralize pH, and remove chemistry that could cause spotting and filming on dishes if not diluted. The time and temperature of this intermediate rinse cycle are not critical. Typically, there is no heat added during this phase. Time spent in this phase should be ideally at least about <NUM> minutes to allow the machine to cycle through all the zones.

The last cycle segment in this embodiment is the final rinse cycle. This cycle begins with a fill of the dishwasher tub following the drain of the dishwasher tub at the end of the intermediate rinse cycle. The temperature of the liquid in the tub of this final rinse cycle is a significant factor for cleaning of soils such as standard cheese soil, although other soils tested did not respond to higher temperature or longer time in the final rinse cycle. So, the final rinse temperature is most desired to be <NUM>° C for overall cleaning performance, but a range of about <NUM>° C to about <NUM>° C will allow for cleaning performance. The time for the final rinse cycle is preferably at least about <NUM> minutes. This time optimizes energy performance and allows dilution and rinsing of the dishware in each rack of the dishwasher. In testing, longer times in this final rinse cycle did not result in significantly better cleaning performance. During this final rinse phase, standard rinse aid can be optionally dispensed to improve drying.

It is understood that the dosing of the compositions described herein can include dosing by several methods such as unit dosing of a tablet, powder or liquid or bulk dosing a portion of the compositions from a certain volume stored in the dishwasher. In the case of a unit-dose chemistry, the dishwasher user would refill the composition dispenser before each cycle with an amount of each composition for one cycle. For bulk dosing, the dishwasher user would need to refill a container inside the dishwasher for each composition at some frequency where the stored composition can be dosed over at least one cycle.

The first composition comprises an oxygen bleach, preferably percarbonate. It may further comprise an alkalinity source, preferably a hydroxide, more preferably sodium hydroxide. It may further comprise complexing agent, polymer, bleach catalyst, bleach activator, surfactant and mixtures thereof. Preferably, the first composition comprises oxygen bleach, alkalinity source, complexing agent, dispersant polymer, bleach catalyst and/or bleach activator and surfactant. The weight of the first composition delivered to the dishwasher is preferably from about <NUM> to <NUM> grams, more preferably from <NUM> to <NUM> grams.

The role of the intermediate composition is to reduce the pH of the wash liquor comprising the first composition before the second composition is added. The intermediate composition comprises a pH buffering system. Preferably the buffering system comprises an organic acid, more preferably a carboxylic acid and more preferably the buffer is selected from a polycarboxylic acid, its salt and mixtures thereof. Preferably the intermediate composition has also calcium binding properties. Preferably the pH buffering system comprises citric acid and more preferably citric acid and bicarbonate. More preferably, the intermediate composition comprises from <NUM> to <NUM>, more preferably from <NUM> to <NUM> grams of citric acid and optionally sodium bicarbonate. If sodium bicarbonate is present in the second composition, it is preferably present in an amount of from <NUM> to <NUM>, more preferably from <NUM> to <NUM> grams.

The second composition comprises enzymes, preferably selected from the group consisting of amylases, proteases, lipases, cellulases, beta-glucanases and mixtures thereof, preferably amylases and proteases. The level of active enzymes delivered into the wash is from about <NUM> to <NUM>, more preferably from about <NUM> to <NUM>, more preferably from about <NUM> to <NUM> of protease and from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM> of amylase per wash.

The product comprises three independent compositions: first, intermediate and second composition. The first composition is to be added first, followed by the intermediate composition and then the second composition. The first composition comprises oxygen bleach, preferably sodium percarbonate, and is substantially free of enzymes and is capable of providing a wash pH of at least <NUM>. The intermediate composition is capable of lowering the pH of the first composition by at least <NUM> pH unit, preferably at least <NUM> pH units and more preferably at least <NUM> units. The second composition comprises enzymes.

The first composition should be designed with an excess pH, i. e, a pH well above <NUM> so it can provides a pH of at least <NUM> at the wash concentration.

The product of the invention can be provided in a single reservoir either external or as part of the dishwasher wherein the three compositions are separated and adapted to be delivered separately. Alternatively, the three compositions can be stored in different reservoirs.

The compositions of the invention can be in any physical form. It can be a loose powder, a liquid or gel or presented in unit dose form, unit dose forms include pressed tablets and water-soluble packs. The compositions can be added from the dispenser of the dishwasher at different times or the dishwasher can have a dosing system adapted to take a plurality of doses that can be delivering in a plurality of dishwashing processes.

The compositions are preferably phosphate free. By "phosphate-free" is herein understood that a composition comprises less than <NUM>%, preferably less than <NUM>% by weight of the composition of phosphate.

The alkalinity source is preferably selected from the group consisting of carbonate, hydroxide, silicate and mixtures thereof. Preferably the alkalinity source comprises sodium hydroxide. The amount of alkalinity source present in the first composition of the invention is such that the pH at the wash liquor composition and <NUM> is at least <NUM> pH units.

For the purpose of this invention a "complexing agent" is a compound capable of binding polyvalent ions such as calcium, magnesium, lead, copper, zinc, cadmium, mercury, manganese, iron, aluminium and other cationic polyvalent ions to form a water-soluble complex. The complexing agent has a logarithmic stability constant ([log K]) for Ca2+ of at least <NUM>. The stability constant, log K, is measured in a solution of ionic strength of <NUM>, at a temperature of <NUM>° C.

Any composition of the invention can comprise a complexing agent. Preferably the first composition of the invention comprises from <NUM>% to <NUM>% by weight of the composition of a complexing agent. Preferably, the composition comprises a complexing agent selected from the group consisting of citric acid, methyl glycine diacetic acid (MGDA), glutamic-N,N-diacetic acid (GLDA), iminodisuccinic acid (IDS), carboxy methyl inulin, L-Aspartic acid N, N-diacetic acid tetrasodium salt (ASDA) and mixtures thereof. For the purpose of this invention, the term "acid", when referring to complexing agents, includes the acid and salts thereof.

In a preferred embodiment, the first composition comprises from <NUM>% to <NUM>% by weight of the composition of MGDA, more preferably the tri-sodium salt of MGDA. Compositions comprising this high level of MGDA perform well in the presence of hard water and also in long and/or hot cycles. Preferably the first composition comprises from <NUM> to <NUM> grams of MGDA, more preferably from <NUM> to <NUM>.

A dispersant polymer can be used in any suitable amount from about <NUM> to about <NUM>%, preferably from <NUM> to about <NUM>%, more preferably from <NUM> to % by weight of any of the compositions. It is preferably present in the first composition.

The dispersant polymer is capable to suspend calcium or calcium carbonate in an automatic dishwashing process.

The dispersant polymer has a calcium binding capacity within the range between <NUM> to <NUM> of Ca/g of dispersant polymer, preferably between <NUM> to <NUM> of Ca/g of dispersant polymer, more preferably <NUM> to <NUM> of Ca/g of dispersant polymer at <NUM>. In order to determine if a polymer is a dispersant polymer within the meaning of the invention, the following calcium binding-capacity determination is conducted in accordance with the following instructions:.

The calcium binding capacity referred to herein is determined via titration using a pH/ion meter, such as the Mettler Toledo SevenMulti™ bench top meter and a PerfectION™ comb Ca combination electrode. To measure the binding capacity a heating and stirring device suitable for beakers or tergotometer pots is set to <NUM>, and the ion electrode with meter are calibrated according to the manufacturer's instructions. The standard concentrations for the electrode calibration should bracket the test concentration and should be measured at <NUM>. A stock solution of <NUM>/g of Ca is prepared by adding <NUM> of CaCl<NUM>-<NUM><NUM>O into <NUM> of deionised water, then dilutions are carried out to prepare three working solutions of <NUM> each, respectively comprising <NUM>/g, <NUM>/g, and <NUM>/g concentrations of Calcium. The <NUM> Ca/g working solution is used as the initial concentration during the titration, which is conducted at <NUM>. The ionic strength of each working solution is adjusted by adding <NUM>/L of NaCl to each. The <NUM> of <NUM> Ca/g working solution is heated and stirred until it reaches <NUM>. The initial reading of Calcium ion concentration is conducted at when the solution reaches <NUM> using the ion electrode. Then the test polymer is added incrementally to the calcium working solution (at <NUM>/L intervals) and measured after <NUM> minutes of agitation following each incremental addition. The titration is stopped when the solution reaches <NUM>/g of Calcium. The titration procedure is repeated using the remaining two calcium concentration working solutions. The binding capacity of the test polymer is calculated as the linear slope of the calcium concentrations measured against the grams/L of test polymer that was added.

The dispersant polymer preferably bears a negative net charge when dissolved in an aqueous solution with a pH greater than <NUM>.

The dispersant polymer can bear also sulfonated carboxylic esters or amides, in order to increase the negative charge at lower pH and improve their dispersing properties in hard water. The preferred dispersant polymers are sulfonated / carboxylated polymers, i.e., polymer comprising both sulfonated and carboxylated monomers.

Preferably, the dispersant polymers are sulfonated derivatives of polycarboxylic acids and may comprise two, three, four or more different monomer units. The preferred copolymers contain:.

At least one structural unit derived from a carboxylic acid monomer having the general formula (III):
<CHM>
wherein R<NUM> to R<NUM> are independently selected from hydrogen, methyl, linear or branched saturated alkyl groups having from <NUM> to <NUM> carbon atoms, linear or branched mono or polyunsaturated alkenyl groups having from <NUM> to <NUM> carbon atoms, alkyl or alkenyl groups as aforementioned substituted with -NH2 or -OH, or -COOH, or COOR<NUM>, where R<NUM> is selected from hydrogen, alkali metal, or a linear or branched, saturated or unsaturated alkyl or alkenyl group with <NUM> to <NUM> carbons;.

Preferred carboxylic acid monomers include one or more of the following: acrylic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, <NUM>-phenylacrylic acid, cinnamic acid, crotonic acid, fumaric acid, methacrylic acid, <NUM>-ethylacrylic acid, methylenemalonic acid, or sorbic acid. Acrylic and methacrylic acids being more preferred.

Optionally, one or more structural units derived from at least one nonionic monomer having the general formula (IV):
<CHM>.

Wherein R<NUM> to R<NUM> are independently selected from hydrogen, methyl, phenyl or hydroxyalkyl groups containing <NUM> to <NUM> carbon atoms, and can be part of a cyclic structure, X is an optionally present spacer group which is selected from -CH<NUM>-, -COO-, -CONH- or -CONR<NUM>-, and R<NUM> is selected from linear or branched, saturated alkyl radicals having <NUM> to <NUM> carbon atoms or unsaturated, preferably aromatic, radicals having from <NUM> to <NUM> carbon atoms.

Preferred non-ionic monomers include one or more of the following: butene, isobutene, pentene, <NUM>-methylpent-<NUM>-ene, <NUM>-methylpent-<NUM>-ene, <NUM>,<NUM>,<NUM>-trimethylpent-<NUM>-ene, <NUM>,<NUM>,<NUM>-trimethylpent-<NUM>-ene, cyclopentene, methylcyclopentene, <NUM>-methyl-<NUM>-methyl-cyclopentene, hexene, <NUM>,<NUM>-dimethylhex-<NUM>-ene, <NUM>,<NUM>-dimethylhex-<NUM>-ene, <NUM>,<NUM>-dimethylhex-<NUM>-ene, <NUM>,<NUM>-dimethylhex-<NUM>-ene, <NUM>,<NUM>-dimethylhex-<NUM>-ene, cyclohexene, methylcyclohexene, cycloheptene, alpha olefins having <NUM> or more carbon atoms such as, dec-<NUM>-ene, dodec-<NUM>-ene, hexadec-<NUM>-ene, octadec-<NUM>-ene and docos-<NUM>-ene, preferred aromatic monomers are styrene, alpha methylstyrene, <NUM>-methylstyrene, <NUM>-dodecylstyrene, <NUM>-ethyl-<NUM>-bezylstyrene, <NUM>-cyclohexylstyrene, <NUM>-propylstyrol, <NUM>-vinylnaphtalene, <NUM>-vinylnaphtalene; preferred carboxylic ester monomers are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, <NUM>-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate and behenyl (meth)acrylate; preferred amides are N-methyl acrylamide, N-ethyl acrylamide, N-t-butyl acrylamide, N-<NUM>-ethylhexyl acrylamide, N-octyl acrylamide, N-lauryl acrylamide, N-stearyl acrylamide, N-behenyl acrylamide. and at least one structural unit derived from at least one sulfonic acid monomer having the general formula (V) and (VI):
<CHM>
<CHM>
wherein R<NUM> is a group comprising at least one sp2 bond, A is O, N, P, S, an amido or ester linkage, B is a mono- or polycyclic aromatic group or an aliphatic group, each t is independently <NUM> or <NUM>, and M+ is a cation. In one aspect, R<NUM> is a C2 to C6 alkene. In another aspect, R7 is ethene, butene or propene.

Preferred sulfonated monomers include one or more of the following: <NUM>-acrylamido-<NUM>-propanesulfonic acid, <NUM>-acrylamido-<NUM>-propanesulfonic acid, <NUM>-acrylamido-<NUM>-methyl-<NUM>-propanesulfonic acid, <NUM>-methacrylamido-<NUM>-methyl-<NUM>-propanesulfonic acid, <NUM>-methacrylamido-<NUM>-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, <NUM>-hydroxy-<NUM>- (<NUM>-propenyloxy) propanesulfonic acid, <NUM>-methyl-<NUM>-propen-<NUM>-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, <NUM>-sulfopropyl, <NUM>-sulfo-propylmethacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

Preferably, the polymer comprises the following levels of monomers: from about <NUM> to about <NUM>%, preferably from about <NUM> to about <NUM>% by weight of the polymer of one or more carboxylic acid monomer; from about <NUM> to about <NUM>%, preferably from about <NUM> to about <NUM>% by weight of the polymer of one or more sulfonic acid monomer; and optionally from about <NUM>% to about <NUM>%, preferably from about <NUM> to about <NUM>% by weight of the polymer of one or more non-ionic monomer. An especially preferred polymer comprises about <NUM>% to about <NUM>% by weight of the polymer of at least one carboxylic acid monomer and from about <NUM>% to about <NUM>% by weight of the polymer of at least one sulfonic acid monomer.

Preferred commercially available polymers include: Alcosperse <NUM>, Aquatreat AR <NUM> and Aquatreat MPS supplied by Alco Chemical; Acumer <NUM>, Acumer <NUM>, Acusol <NUM> and Acusol <NUM> supplied by Rohm & Haas; Goodrich K-<NUM>, K-<NUM> and K-<NUM> supplied by BF Goodrich; and ACP <NUM> supplied by ISP technologies Inc. Particularly preferred polymers are Acusol <NUM> and Acusol <NUM> supplied by Rohm & Haas.

Suitable dispersant polymers include anionic carboxylic polymer of low molecular weight. They can be homopolymers or copolymers with a weight average molecular weight of less than or equal to about <NUM>,<NUM>/mol, or less than or equal to about <NUM>,<NUM>/mol, or less than or equal to about <NUM>,<NUM>/mol, or from about <NUM>,<NUM> to about <NUM>,<NUM>/mol, preferably from about <NUM>,<NUM> to about <NUM>,<NUM>/mol. The dispersant polymer may be a low molecular weight homopolymer of polyacrylate, with an average molecular weight of from <NUM>,<NUM> to <NUM>,<NUM>, particularly from <NUM>,<NUM> to <NUM>,<NUM>, and particularly preferably from <NUM>,<NUM> to <NUM>,<NUM>.

The dispersant polymer may be a copolymer of acrylic with methacrylic acid, acrylic and/or methacrylic with maleic acid, and acrylic and/or methacrylic with fumaric acid, with a molecular weight of less than <NUM>,<NUM>. Their molecular weight ranges from <NUM>,<NUM> to <NUM>,<NUM> and more preferably from <NUM>,<NUM> to <NUM>,<NUM> and in particular <NUM>,<NUM> to <NUM>,<NUM>/mol. and a ratio of (meth)acrylate to maleate or fumarate segments of from <NUM>:<NUM> to <NUM>:<NUM>.

The dispersant polymer may be a copolymer of acrylamide and acrylate having a molecular weight of from <NUM>,<NUM> to <NUM>,<NUM>, alternatively from <NUM>,<NUM> to <NUM>,<NUM>, and an acrylamide content of less than <NUM>%, alternatively less than <NUM>%, by weight of the dispersant polymer can also be used. Alternatively, such dispersant polymer may have a molecular weight of from <NUM>,<NUM> to <NUM>,<NUM> and an acrylamide content of from <NUM>% to <NUM>%, by weight of the polymer.

Dispersant polymers suitable herein also include itaconic acid homopolymers and copolymers.

Alternatively, the dispersant polymer can be selected from the group consisting of alkoxylated polyalkyleneimines, alkoxylated polycarboxylates, polyethylene glycols, styrene co-polymers, cellulose sulfate esters, carboxylated polysaccharides, amphiphilic graft copolymers and mixtures thereof. Preferably the first composition comprises from <NUM> to <NUM>, more preferably from <NUM> to <NUM> grams of dispersant polymer, more preferably sulfonate carboxylate polymer.

The first composition of the invention comprises oxygen bleach, preferably percarbonate in combination with a bleach activator or a bleach catalyst or both. Preferably the bleach activator is TAED and the bleach catalyst is a manganese bleach catalyst.

The first composition of the invention preferably comprises from about <NUM> to about <NUM>%, more preferably from about <NUM> to about <NUM>% of bleach, preferably percarbonate, by weight of the composition.

Alkali metal percarbonates, particularly sodium percarbonate is the preferred bleach for use herein. The percarbonate is most preferably incorporated into the products in a coated form which provides in-product stability. The first composition of the invention can comprise other bleaches in addition to percarbonate. Inorganic and organic bleaches that can be used in addition to percarbonate include perhydrate salts such as perborate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. Alternatively, the salt can be coated. Suitable coatings include sodium sulphate, sodium carbonate, sodium silicate and mixtures thereof. Said coatings can be applied as a mixture applied to the surface or sequentially in layers.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility herein. Typical organic bleaches are organic peroxyacids, especially dodecanediperoxoic acid, tetradecanediperoxoic acid, and hexadecanediperoxoic acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid are also suitable herein. Diacyl and Tetraacylperoxides, for instance dibenzoyl peroxide and dilauroyl peroxide, are other organic peroxides that can be used in the context of this invention.

Further typical organic bleaches include the peroxyacids, particular examples being the alkylperoxy acids and the arylperoxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as <NUM>,<NUM>-diperoxycarboxylic acid, <NUM>,<NUM>-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, <NUM>-decyldiperoxybutane-<NUM>,<NUM>-dioic acid, N,N-terephthaloyldi(<NUM>-aminopercaproic acid). Preferably the first composition comprises from <NUM> to <NUM>, more preferably from <NUM> to <NUM> grams of percarbonate.

Bleach activators are typically organic peracid precursors that enhance the bleaching action in the course of cleaning at temperatures of <NUM>° C and below. Bleach activators suitable for use herein include compounds which, under perhydrolysis conditions, give aliphatic peroxoycarboxylic acids having preferably from <NUM> to <NUM> carbon atoms, in particular from <NUM> to <NUM> carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances bear O-acyl and/or N-acyl groups of the number of carbon atoms specified and/or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular <NUM>,<NUM>-diacetyl-<NUM>,<NUM>-dioxohexahydro-<NUM>,<NUM>,<NUM>-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (nor iso-NOBS), decanoyloxybenzoic acid (DOBA), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and <NUM>,<NUM>-diacetoxy-<NUM>,<NUM>-dihydrofuran and also triethylacetyl citrate (TEAC). If present the first composition of the method of the invention comprises from <NUM> to <NUM>, preferably from <NUM> to <NUM>% by weight of the composition of bleach activator, preferably TAED.

The first composition herein preferably comprises a bleach catalyst, preferably a metal containing bleach catalyst. More preferably the metal containing bleach catalyst is a transition metal containing bleach catalyst, especially a manganese or cobalt-containing bleach catalyst. Bleach catalysts preferred for use herein include manganese triazacyclononane and related complexes; Co, Cu, Mn and Fe bispyridylamine and related complexes; and pentamine acetate cobalt(III) and related complexes. Especially preferred bleach catalyst for use herein are <NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>-triazacyclononane (Me-TACN) and <NUM>,<NUM>, <NUM>,<NUM>- tetramethyl-<NUM>,<NUM>,<NUM>-triazacyclononane (Me/Me-TACN).

Preferably the first composition of the method of the invention comprises from <NUM> to <NUM>, more preferably from <NUM> to <NUM>%, more preferably from <NUM> to <NUM>% of bleach catalyst by weight of the composition. Preferably the bleach catalyst is a manganese bleach catalyst. Preferably the first composition comprises from <NUM> to <NUM>, more preferably from <NUM> to <NUM> of manganese bleach catalyst.

The compositions of the invention preferably comprises an inorganic builder, more preferably, the first composition comprises an inorganic builder. Suitable inorganic builders are selected from the group consisting of carbonate, silicate and mixtures thereof. Especially preferred for use herein is sodium carbonate. Preferably the first composition of the method of the invention comprises from <NUM> to <NUM>%, more preferably from <NUM> to <NUM>% and especially from <NUM> to <NUM>% of sodium carbonate by weight of the composition.

Surfactants suitable for use herein include non-ionic surfactants, preferably the compositions are free of any other surfactants. Traditionally, non-ionic surfactants have been used in automatic dishwashing for surface modification purposes in particular for sheeting to avoid filming and spotting and to improve shine. It has been found that non-ionic surfactants can also contribute to prevent redeposition of soils.

Preferably the first composition of the invention comprises a non-ionic surfactant or a non-ionic surfactant system, more preferably the non-ionic surfactant or a non-ionic surfactant system has a phase inversion temperature, as measured at a concentration of <NUM>% in distilled water, between <NUM> and <NUM>, preferably between <NUM> and <NUM>. By a "non-ionic surfactant system" is meant herein a mixture of two or more non-ionic surfactants. Preferred for use herein are non-ionic surfactant systems. They seem to have improved cleaning and finishing properties and better stability in product than single non-ionic surfactants.

Phase inversion temperature is the temperature below which a surfactant, or a mixture thereof, partitions preferentially into the water phase as oil-swollen micelles and above which it partitions preferentially into the oil phase as water swollen inverted micelles. Phase inversion temperature can be determined visually by identifying at which temperature cloudiness occurs.

The phase inversion temperature of a non-ionic surfactant or system can be determined as follows: a solution containing <NUM>% of the corresponding surfactant or mixture by weight of the solution in distilled water is prepared. The solution is stirred gently before phase inversion temperature analysis to ensure that the process occurs in chemical equilibrium. The phase inversion temperature is taken in a thermostable bath by immersing the solutions in <NUM> sealed glass test tube. To ensure the absence of leakage, the test tube is weighed before and after phase inversion temperature measurement. The temperature is gradually increased at a rate of less than <NUM> per minute, until the temperature reaches a few degrees below the preestimated phase inversion temperature. Phase inversion temperature is determined visually at the first sign of turbidity.

Suitable nonionic surfactants include: i) ethoxylated non-ionic surfactants prepared by the reaction of a monohydroxy alkanol or alkyphenol with <NUM> to <NUM> carbon atoms with preferably at least <NUM> moles particularly preferred at least <NUM> moles, and still more preferred at least <NUM> moles of ethylene oxide per mole of alcohol or alkylphenol; ii) alcohol alkoxylated surfactants having a from <NUM> to <NUM> carbon atoms and at least one ethoxy and propoxy group. Preferred for use herein are mixtures of surfactants i) and ii).

Another suitable non-ionic surfactants are epoxy-capped poly(oxyalkylated) alcohols represented by the formula:.

R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2]     (I).

wherein R1 is a linear or branched, aliphatic hydrocarbon radical having from <NUM> to <NUM> carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from <NUM> to <NUM> carbon atoms; x is an integer having an average value of from <NUM> to <NUM>, more preferably about <NUM>; and y is an integer having a value of at least <NUM>, more preferably at least <NUM>.

Preferably, the surfactant of formula I, at least about <NUM> carbon atoms in the terminal epoxide unit [CH2CH(OH)R2]. Suitable surfactants of formula I, according to the present invention, are Olin Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as described, for example, in <CIT>. Preferably the first composition comprises from <NUM> to <NUM>, more preferably from <NUM> to <NUM> grams of surfactant, preferably non-ionic surfactant.

The second composition of the invention comprises enzymes. The enzymes are preferably selected from amylase, proteases, lipases, cellulases, beta-glucanases and mixtures thereof. Preferably the second composition comprises amylase and protease.

The second composition of the invention may comprise a protease or a mixture of proteases. A mixture of two or more proteases can contribute to an enhanced cleaning across a broader temperature, cycle duration, and/or substrate range, and provide superior shine benefits, especially when used in conjunction with the first composition.

Suitable proteases for use in the second composition include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC <NUM>. Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable protease may be of microbial origin. The suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one aspect, the suitable protease may be a serine protease, such as an alkaline microbial protease or/and a trypsin-type protease. Examples of suitable neutral or alkaline proteases include:.

Preferred proteases for the second composition of the method of the invention are polypeptides demonstrating at least <NUM>%, preferably at least <NUM>%, more preferably at least <NUM>%, even more preferably at least <NUM>% and especially <NUM>% identity with the wild-type enzyme from Bacillus lentus, comprising mutations at one or more, preferably two or more and more preferably three or more of the following positions, using the BPN' numbering system: <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, X101, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. Most preferably the protease comprises one or more, preferably two or more and more preferably three or more of the following mutations using the BPN' numbering system and amino acid abbreviations as illustrated in <CIT>: S9R, A15T, V68A, N76D, N87S, S99D, S99E, S99SD, S99A, S101G, S101M, S103A, V104N/I, G118V, G118R, S128L, P129Q, S130A, Y167A, R170S, A194P, V205I, Q206L/D/E, Y209W, M222S, and/or Q245R.

Preferably the protease is selected from the group of proteases comprising the below mutations (BPN' numbering system) versus either the PB92 wild-type (SEQ ID NO:<NUM> in <CIT>) or the subtilisin <NUM> wild-type (sequence as per PB92 backbone, except comprising a natural variation of N87S).

Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase®, Coronase®, Blaze®, Blaze Ultra® and Esperase® by Novozymes A/S (Denmark); those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase®, Ultimase® and Purafect OXP® by Dupont; those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes; and those available from Henkel/Kemira, namely BLAP (sequence shown in Figure29 of <CIT> with the following mutations S99D + S101 R + S103A + V104I + G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D); and KAP (Bacillus alkalophilus subtilisin with mutations A230V + S256G + S259N) from Kao.

Especially preferred for use herein is a combination of two or more proteases selected from the group consisting of Properase®, Blaze®, Ultimase®, Everlase®, Savinase®, Excellase®, Blaze Ultra®, BLAP and BLAP variants.

Preferably, the second composition comprises from <NUM> to <NUM>, more preferably from <NUM> to <NUM> of active protease.

Preferably the composition of the invention may comprise an amylase. Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp. , such as Bacillus sp. NCBI <NUM>, NCBI <NUM>, NCBI <NUM>, DSM <NUM> (<CIT>) DSM <NUM>, DSMZ no. <NUM>, KSM AP1378 (<CIT>), KSM K36 or KSM K38 (<CIT>). Preferred amylases include:.

Preferably the amylase is an engineered enzyme, wherein one or more of the amino acids prone to bleach oxidation have been substituted by an amino acid less prone to oxidation. In particular it is preferred that methionine residues are substituted with any other amino acid. In particular it is preferred that the methionine most prone to oxidation is substituted. Preferably the methionine in a position equivalent to <NUM> in SEQ ID NO:<NUM> is substituted. Preferably, the methionine at this position is substituted with threonine or leucine, preferably leucine.

Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL®, ATLANTIC®, ACHIEVE ALPHA®,AMPLIFY® PRIME, INTENSA® and BAN® (Novozymes A/S, Bagsvaerd, Denmark), KEMZYM® AT <NUM> Biozym Biotech Trading GmbH Wehlistrasse 27b A-<NUM> Wien Austria, RAPIDASE® , PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE®, PREFERENZ S® series (including PREFERENZ S1000® and PREFERENZ S2000® and PURASTAR OXAM® (DuPont. , Palo Alto, California) and KAM® (Kao, <NUM>-<NUM> Nihonbashi Kayabacho, <NUM>-chome, Chuo-ku Tokyo <NUM>-<NUM>, Japan). In one aspect, suitable amylases include ATLANTIC®, STAINZYME®, POWERASE®, INTENSA® and STAINZYME PLUS® and mixtures thereof.

Preferably, the second composition comprises at least <NUM>, preferably from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, mg of active amylase.

Preferably, the enzymes of the second composition of the method of the invention are in the form of granulates, the granulates comprise more than <NUM>% of sodium sulfate by weight of the granulate and/or the sodium sulfate and the active enzyme (protease and/or amylase) are in a weight ratio of between <NUM>:<NUM> and <NUM>:<NUM> or preferably between <NUM>:<NUM> and <NUM>:<NUM> or more preferably between <NUM>:<NUM> and <NUM>:<NUM>.

The second composition may comprise polypeptides of glycoside hydrolase family <NUM> (GH <NUM>) having beta-glucanase activity (e.g. comprising or consisting of licheninase EC <NUM>. <NUM>, β-<NUM>,<NUM>-<NUM>,<NUM>-endoglucanase EC <NUM>. <NUM> and/or β-<NUM>,<NUM>-endoglucanases; β-<NUM>,<NUM>-endoglucanase EC <NUM>. <NUM> activity) which are highly active in degrading different types of beta-glucans (e.g. beta-D-glucans, beta-<NUM> ,<NUM>-<NUM> ,<NUM> glucans, mix-linkage beta-glucans, barley beta-glucans and oatmeal beta-glucans).

The cleaning provided by different methods is evaluated: Method A, outside the scope of the invention, delivers a single composition into the main wash. Method B, outside the scope of the invention, delivers the first composition (comprising bleach) and the second composition (comprising enzyme) having the same pH (<NUM>). Method C, according to the invention, delivers the first composition at pH <NUM>, the intermediate composition, and the second composition at pH <NUM>. Method D, according to the invention, delivers the first composition at pH <NUM>, the intermediate composition, and the second composition at pH <NUM>. Method E, outside the scope of the invention, delivers the first composition at pH <NUM>, the intermediate composition, and the second composition at pH <NUM>.

The method evaluates the removal of triple corn starch, baked cheese and double egg yolk on CFT tiles and the removal of baked-on macaroni cheese (Mac & Cheese) from copper saucepans.

The baked-on Mac & Cheese is representative of baked and burnt soiled items that do not get cleaned in a typical wash.

CFT tiles (Center For Testmaterials BV. Stoomloggerweg <NUM>, <NUM> KT Vlaardingen, the Netherlands), which are stained melamine dishwasher monitors that discriminate the performance of the product to remove enzyme sensitive stains among others, were tested.

All tiles were cut in half and two tiles per wash of each stain were placed in the upper rack of the dishwasher.

After subjecting the tiles to the dishwashing process the tiles were evaluated using a computer aided image analysis to assign a stain removal index, having a continuous scale from <NUM> to a <NUM>, where <NUM>% is unwashed and <NUM>% is a complete removal of the stain.

Revere <NUM> quart copper bottom saucepans with handle removed were used.

The soiled substrates were prepared the day before the test was run and allowed to air dry overnight.

Kraft Macaroni & Cheese Dinner (<NUM> oz. box) was used following the below recipe.

Two saucepans are placed in the dishwasher and are visually graded by <NUM> independent panelists: the higher the number the cleaner the saucepan.

<NUM> of ballast soil is added per dishwasher. The composition is as follows:.

As it can be seen from the table above the best cleaning results are obtained when the first composition is delivered first at a pH of at least <NUM> and the second composition is delivered after the second composition at a lower pH (Methods C and D).

Claim 1:
A method of washing dishware in a dishwasher comprising the step of delivering into the dishwasher:
a) a first composition comprising oxygen bleach and substantially free of enzymes; followed by
b) a second composition comprising enzymes,
wherein the first composition has a pH of at least <NUM> and the pH of the first composition is at least <NUM> pH unit greater than the pH of the second composition wherein the pH is measured at wash concentration at <NUM>.