Automatic dishwashing method with alkaline rinse

Abstract

A method for washing dishes in a domestic dishwasher using a program including a wash cycle and a rinse cycle, the method comprising: a) placing dishes in the dishwasher; b) supplying a cleaning composition including an enzyme to the wash cycle to form a wash liquor and subjecting the dishes to the wash liquor; and c) supplying a rinse composition that does not include an enzyme, and preferably does not include a bleach, to the rinse cycle to form a rinse liquor having a pH greater than 9 and subjecting the dishes to the rinse liquor.

Description

[Technical field]

[0001] The present invention is in the field of automatic dishwashing. In particular, the present invention relates to a method for providing improved cleaning, more particularly enzymatic cleaning, while simultaneously providing grit prevention and providing shine. The method also allows for improved energy efficiency of the dishwashing process. [Background technology]

[0002] Automatic dishwashing detergent formulators are continually looking for ways to improve automatic dishwashing performance in terms of cleaning and finish.

[0003] A frequent problem in automatic dishwashing is the presence of grit on the washed items. Grit can be found on the dishes / tableware after the automatic dishwashing process even if it was not present before the items entered the dishwasher. Grit appears to form during the dishwashing process. The mechanism of grit formation is not well understood. This may be due to the high temperatures during the dishwashing process and the combination of different soils, including oily soils, that are lifted from the soiled items. It seems that somehow the different soils recombine to produce grit, which are tiny particles that deposit on the surface of the washed items. Once grit is formed and deposited, it is very difficult to remove it.

[0004] There is a constant drive to make automatic dishwashing more environmentally friendly by reducing the amount of water, time, and / or energy required by the automatic dishwashing process. Summary of the Invention [Problem to be solved by the invention]

[0005] It is an object of the present invention to provide a method of dishwashing that provides improved cleaning, particularly improved removal of proteinaceous soils such as meat, egg, and dairy, while at the same time providing good shine and grit prevention.

[0006] It is another object of the present invention to provide a more energy efficient automatic dishwashing method. [Means for solving the problem]

[0007] According to a first aspect of the present invention, there is provided a method for washing dishes in a domestic dishwasher, the method using a dishwashing program comprising a wash cycle and a rinse cycle, the method comprising the following steps: a) loading dishes into a dishwasher; b) providing a cleaning composition comprising an enzyme in a wash cycle to form a wash liquor and subjecting the dishware to the wash liquor; c) providing an enzyme-free, and preferably bleach-free, alkaline rinse composition to a rinse cycle to form a rinse liquor having a pH greater than 9 and subjecting the dishes to the rinse liquor.

[0008] The method of the present invention provides improved enzymatic cleaning, particularly proteinaceous soil removal, while simultaneously providing improved shine and preventing grit formation.

[0009] According to a second aspect of the present invention, there is provided a rinse composition suitable for use in the method of the present invention. According to a third aspect of the present invention, there is provided an automatic dishwashing pack suitable for use in the method of the present invention. According to further aspects of the present invention, there is provided the use of the method of the present invention to provide proteinaceous soil removal, and also the use of the rinse composition of the present invention to provide shine and grit prevention in low temperature rinse programs.

[0010] The elements of the first aspect of the invention apply mutatis mutandis to subsequent aspects of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention encompasses a method of cleaning dishes in a dishwashing machine, compositions suitable for use in the method of the invention, packs containing the cleaning and rinsing compositions for use in the method of the invention, the use of the compositions to improve proteinaceous soil removal, and the use of the compositions in a low temperature rinse program to provide grit prevention and shine. The method of the present invention is carried out in a domestic dishwashing machine.

[0012] Automatic dishwashing machines may be domestic or commercial / institutional machine types. Generally, the differences are in terms of size, throughput, and duration of the dishwashing process. This may mean that the machines are designed in a completely different way. Industrial / institutional machines often have much shorter but more energy intensive (e.g., higher temperature) cycles compared to domestic machines, and / or use much more aggressive chemistry. Typically, they do not use enzymes, because enzymes require a certain contact time with the treated soil to function effectively, and commercial cycle times are too short. In the case of commercial dishwashing machines, the machine may be based on a conveyor system where the dishes move through a single or multiple tanks of the dishwasher, while in domestic machines, the dishes generally always remain stationary in one tank inside the dishwasher, and all the washing steps are carried out in that single tank. In domestic dishwashing, it is conventional to include bleach and enzymes in the detergent.

[0013] By "dishware" herein is meant cookware, dishes and tableware, i.e. all items associated with the preparation and serving of food and beverages that are normally washed in a dishwasher.

[0014] As used herein, articles including "a" and "an" are understood to mean one or more of what is claimed or described. Unless otherwise noted, all component or composition levels refer to the active portion of that component or composition and exclude impurities, such as residual solvents or by-products, that may be present in commercial sources of such components or compositions. Unless specifically stated or otherwise required by context, the embodiments described herein apply equally to all aspects of the invention. Percentages listed are by weight unless specifically stated or otherwise required by context.

[0015] Unless otherwise stated, all measurements are performed at 25°C.

[0016] Method of the invention The method of the present invention comprises the following steps carried out in a domestic dishwashing machine: a) loading dishes into a dishwasher; b) delivering the cleaning composition to a wash cycle to form a wash liquor and subjecting the dishware to the resulting wash liquor; and c) delivering the alkaline rinse composition to a rinse cycle to form a rinse liquor and subjecting the dishes to the resulting alkaline rinse liquor.

[0017] The wash cycle is performed before the rinse cycle. The wash liquor may be drained before introducing fresh water to form the rinse liquor. Alternatively, the rinse liquor may be formed by adding a rinse composition to the wash liquor.

[0018] The method of the present invention may optionally comprise an intermediate rinse between steps b) and c) and / or a final rinse after step c), the liquid of the intermediate rinse may be drained or left for a subsequent rinse.

[0019] The cleaning composition comprises an enzyme and is preferably alkaline. Without wishing to be bound by theory, it is believed that the enzyme from the cleaning composition is carried over from the wash cycle to the rinse cycle, and some of the components of the cleaning liquor remain on the dishes even when the water is drained at the end of the wash cycle. The alkaline rinse liquor promotes enzyme cleaning in the rinse with the enzyme carried over from the wash cycle. The cleaning composition preferably comprises a builder, a complexing agent, a non-ionic surfactant, a dispersion polymer, and optionally a bleaching agent.

[0020] Rinse aids in automatic dishwashing are usually used for finishing, not for cleaning of dishes. Rinse aids are usually used to promote sheeting of the rinse liquid to prevent filming and spotting on the washed dishes, and for shine. In the present application, it has surprisingly been found that a method comprising treating dishes with an enzymatic cleaning composition in the main wash followed by an alkaline rinse provides improved cleaning over a method not including an alkaline rinse step. The method of the present invention provides improved enzymatic cleaning, more specifically improved removal of proteinaceous soils, while providing good shine and grit prevention. Shine is further improved when the rinse composition comprises a complexing agent, more specifically when the complexing agent comprises a salt of methylglycine diacetate. The rinse composition is preferably free of citric acid.

[0021] Surprisingly, it has been found that filming and spotting on glass and plastics is reduced compared to methods using conventional rinse aid compositions containing acids when the maximum rinse liquor temperature is less than 50° C., preferably about 45° C. It has also been found surprisingly that grit prevention on glass and plastics is increased compared to methods using conventional rinse aid compositions containing acids when the maximum rinse liquor temperature is less than 50° C., preferably about 45° C.

[0022] In the context of the present application, a "dishwashing program" is a complete washing process, including a washing cycle and a rinsing cycle, and optionally a pre-wash, pre-rinse and / or post-rinse cycle, which can be selected and activated by a program switch of the dishwasher. The duration of these separate dishwashing programs is advantageously at least 15 minutes, advantageously between 20 and 360 minutes, preferably between 20 and 90 minutes. Within the meaning of the present application, a "short washing program" lasts less than 60 minutes and a "long washing program" lasts more than 60 minutes.

[0023] Domestic dishwashers can usually provide several programs, such as a basic wash program for normal washing of soiled dishes that have dried to a certain extent, an intensive wash program for washing very soiled dishes, or an economical wash program for cases where food has become stuck and is particularly difficult to remove (very dry or burnt spots). Each program includes several successive steps, usually one or two low-temperature pre-wash cycles, a wash cycle (also known as a main wash), a low-temperature rinse cycle, a high-temperature rinse cycle, and optionally a drying cycle. During different cycles of the program, different compositions can be added to the dishwasher water to aid in cleaning.

[0024] In the course of a selected dishwashing program, a domestic dishwasher generally executes two or more cycles, such as a prewash, a wash cycle, an intermediate rinse cycle, a rinse cycle, and then a drying cycle, to finish the program. During each cycle, the washing liquid is distributed, in particular sprayed, by a rotating spray arm, a fixed spray nozzle, e.g. a top spray head, a movable spray nozzle, e.g. a top spin unit, and / or some other liquid dispensing device, into a processing chamber of the dishwasher cavity, where the washing liquid is applied to the articles to be washed, such as dishes and / or cutlery, preferably supported in and / or on at least one loading unit, e.g. a pull-out rack or a cutlery drawer, which can be removed or withdrawn. For this purpose, the dishwasher is preferably replenished with washing liquid via at least one supply line by a working circulation pump, which washing liquid collects at the bottom of the dishwasher cavity, preferably in a recess, in particular in a sump. If the washing and / or rinsing liquid has to be heated during the respective cycle, the washing and / or rinsing liquid is heated by a heating facility, which may be part of the circulation pump. At the end of each cycle, some or all of the liquid present in the processing chamber of each instance of the dishwasher cavity is pumped out by the drain pump.

[0025] Cleaning Composition The cleaning composition is provided to the wash water of a wash cycle to form a wash liquor. The cleaning composition comprises enzymes, preferably proteases and amylases. The wash liquor is preferably alkaline, more preferably the wash liquor has a pH greater than 9, preferably greater than 10. Preferably, the cleaning composition is phosphate-free. By "phosphate-free" herein is meant that the composition comprises less than 0.1% phosphate by weight of the composition.

[0026] The cleaning composition includes enzymes, and optionally, but preferably, complexing agents, polymers, inorganic builders (preferably carbonates and silicates), non-ionic surfactants, etc. The composition may include bleaching agents, bleach catalysts, and / or bleach activators. In some embodiments, the cleaning composition may be free of bleaching agents, bleach catalysts, and bleach activators, and preferably free of anionic surfactants.

[0027] enzyme The cleaning composition comprises enzymes, preferably amylases and proteases.

[0028] In describing the enzyme variants herein, the following nomenclature is used for ease of reference: original amino acid:position:substitute amino acid. Standard enzyme IUPAC one-letter codes for amino acids are used.

[0029] Proteases The cleaning composition preferably includes a protease. A mixture of two or more proteases can also contribute to enhanced cleaning over a broader temperature, cycle duration, and / or substrate range, especially when used with an anti-redeposition agent and / or a sulfonated polymer, and can provide superior shine benefits.

[0030] Suitable proteases include metalloproteases and serine proteases, including, for example, neutral or alkaline microbial serine proteases, such as subtilisin (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable proteases may be of microbial origin. Suitable proteases include chemically or genetically modified variants of the aforementioned suitable proteases. In one aspect, suitable proteases may be serine proteases, such as alkaline microbial proteases or / and trypsin-type proteases. Examples of suitable neutral or alkaline proteases include: (a) Subtilisin (EC 3.4.21.62), in particular WO2004 / 067737, WO 2015 / 091989, WO2015 / 091990, WO 2015 / 024739, WO 2015 / 143360, U.S. Pat. Nos. 6,312,936, 5,679,630, 4,760,025, German Patent Publication No. 10 / 200602 Bacillus species, as described in WO 2015 / 089447, WO 2015 / 089441, WO 2016 / 066756, WO 2016 / 066757, WO 2016 / 069557, WO 2016 / 069563, and WO 2016 / 069569, sp.), Bacillus derived from Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, B. pumilus, B. gibsonii and B. akibaii. (b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g., of porcine or bovine origin), including the Fusarium proteases described in WO 89 / 06270, and the chymotrypsin proteases from Cellulomonas described in WO 05 / 052161 and WO 05 / 052146. (c) metalloproteases, in particular those derived from Bacillus amyloliquefaciens, as described in WO 07 / 044993(A2). Bacillus, Brevibacillus, Thermoactinomyces, Geobacillus, Paenibacillus, Lysinibacillus or Streptomyces spp. as described in WO 2014 / 194032, WO 2014 / 194054 and WO 2014 / 194117, those derived from Kribella alluminosa as described in WO 2015 / 193488, and those derived from Streptomyces and Lysobacter as described in WO2016075078. (d) proteases having at least 90% identity to the subtilase from Bacillus sp. TY145, NCIMB40339, described in WO92 / 17577 (Novozymes A / S), such as proteases including variants of this Bacillus sp. TY145 subtilase described in WO 2015 / 024739 and WO 2016 / 066757. (e) including the variants found in WO 2016 / 205755 and WO 2018 / 118950, including 1, 4, 9, 21, 24, 27, 36, 37, 39, 42, 43, 44, 47, 54, 55, 56, 74, 80, 85, 87, 99, 102, 114, 117, 119, 121, 126, 127, 128, 131, 143, 144, 158, 159, 160, 169, 182, 188, A protease comprising at least one amino acid substitution selected from the group consisting of 190, 197, 198, 212, 224, 231, 232, 237, 242, 245, 246, 254, 255, 256, and 257 (using the numbering of SEQ ID NO: 85), and having at least 90%, preferably at least 92%, identity to the amino acid sequence of SEQ ID NO: 85 from WO 2016 / 205755. (f) A protease having at least 90%, preferably at least 92%, more preferably at least 98% identity with the amino acid sequence of SEQ ID NO: 1 from U.S. Patent No. 10,655,090(B2). A preferred protease has 100% identity with SEQ ID NO: 1 from U.S. Patent No. 10,655,090(B2). Another preferred protease has 1 to 4 modifications with respect to SEQ ID NO: 1 from U.S. Patent No. 10,655,090(B2).

[0031] Particularly preferred proteases for the detergent of the present invention are the following: (a) Bacillus lentus and / or, (b) a protease having at least 95%, more preferably at least 98%, even more preferably at least 99%, in particular 100% identity to the amino acid sequence of SEQ ID NO: 85 from WO 2016 / 205755, and comprising at least one amino acid substitution (using the numbering of SEQ ID NO: 85) selected from the group comprising: P54E / G / I / L / Q / S / T / V;S99A / E / H / I / K / M / N / Q / R / T / V;S126A / D / E / F / G / H / I / L / M / N / Q / R / T / V / Y;D127A / E / F / G / H / I / L / M / N / P / Q / S / T / V / W / Y;F128A / C / D / E / G / H / I / K / L / M / N / P / Q / R / S / T / W, A37T, S39E, A47V, T56Y, I80V, N85S, E87D, T114Q, N242D; Most preferably, the additional protease is selected from the group of proteases that contain the following mutations (BPN numbering system) relative to either the PB92 wild type (SEQ ID NO: 2 of WO 08 / 010925) or the subtilisin 309 wild type (sequence according to the PB92 backbone but containing the naturally occurring N87S mutation): (i) G118V+S128L+P129Q+S130A (ii)S101M+G118V+S128L+P129Q+S130A (iii)N76D+N87R+G118R+S128L+P129Q+S130A+S188D+N248R (iv)N76D+N87R+G118R+S128L+P129Q+S130A+S188D+V244R (v)N76D+N87R+G118R+S128L+P129Q+S130A (vi) V68A+N87S+S101G+V104N (vii) S99AD or from the group of proteases comprising one or more, preferably two or more, preferably three or more, preferably four or more of the following mutations relative to SEQ ID NO: 1 of WO 2018 / 118950: P54T, S99M, S126A / G, D127E, F128C / D / E / G, A37T, S39E, A47V, T56Y, I80V, N85S, E87D, T114Q, and N242D.

[0032] Most preferred for use herein is a protease having at least 60% identity with the amino acid sequence of SEQ ID NO: 1 of WO 2019 / 125894(A1) and a variant comprising at least one amino acid substitution selected from the group consisting of (using the numbering of SEQ ID NO: 1) X54T; X126A, D, G, V, E, K, I; X127E, S, T, A, P, G, C; and X128E, C, T, D, P, G, L, Y, N and X211L. Preferably, a variant having at least 90% identity with the amino acid sequence of SEQ ID NO: 1, the variant comprising at least one amino acid substitution selected from the group consisting of (using the numbering of SEQ ID NO: 1) P54T, S126A, D127E, F128G, and M211L.

[0033] Other preferred proteases for use herein are variants of proteases having at least 90% identity to the amino acid sequence of SEQ ID NO: 1 of WO 2019 / 245839(A1), wherein the variant is 1C / D / E / M / N, 21L, 37A, 54A, 73V, 76D / H / N / T, 83G, 84D / E / F, 85I / M, 86I / S / T / V, 87T, 88M / V, 89F / W, 91I, 95A / N / S, 96M / Q, 97E, 98M , 99A / F / H / I / K / L / Q / T / W / Y, 102L, 104E, 105L, 106I / V, 108A, 109I, 112C, 114M / N, 115A / E / H / Q, 116A / E / G / H / Q, 118A / D / N, 122C, 1 and wherein the protease comprises one or more amino acid substitutions at one or more positions corresponding to a position in SEQ ID NO:1 selected from among 24E / Q, 126I / Q / V, 128H / I / L / M / N / Q / S / T / V / Y, 129D / H, 130N, 131D / E / N / P / Q, 135A / D / H / K / L / M / N / Q / T / V / W / Y, 138D / E, 139E / L, 141A / E / F / H / Y, 142A / D / E, 143E / H / K / M / S / V, 156E, and 157C / D / E. An automatic dishwashing composition, wherein the amino acid positions of the variants are numbered corresponding to the amino acid sequence of SEQ ID NO:1.

[0034] Suitable commercially available additional protease enzymes include those sold by Novozymes A / S (Denmark) under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Savinase Evity®, Ovozyme®, Neutrase®, Everlase®, Coronase®, Blaze®, Blaze Ultra®, Blaze Evity® and Esperase®; those sold by Dupont under the trade names Ox®, FN3®, FN4®, Excellase®, Ultimase®, Extremase®, and Purafect OXP®; those sold by Solvay Enzymes under the trade names Opticlean® and Optimase®; and those available from Henkel / Kemira, namely, BLAP (the sequence of which is shown in FIG. 29 of U.S. Pat. No. 5,352,604 and which has the mutations S99D+S101R+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 from Kao (Bacillus alkalophilus subtilisin with the mutations A230V+S256G+S259N).

[0035] Particularly preferred for use herein are commercially available proteases selected from the group consisting of Properase®, Blaze®, Blaze Evity®, Savinase Evity®, Extremase®, Ultimase®, Everlase®, Savinase®, Excellase®, Blaze Ultra®, BLAP and BLAP variants.

[0036] Preferred levels of protease in the compositions of the present invention include from about 0.05 to about 20, more preferably from about 0.5 to about 15, especially from about 2 to about 12 mg of active protease / g of composition.

[0037] amylase Preferably, the cleaning composition comprises an amylase. Suitable α-amylases include those of bacterial or fungal origin, including chemically or genetically modified variants. Preferred alkaline α-amylases are derived from Bacillus strains, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus species, such as Bacillus species NCBI12289, NCBI12512, NCBI12513, DSM9375 (U.S. Pat. No. 7,153,818), DSM12368, DSMZ no. 12649, KSM AP1378 (WO 97 / 00324), KSM K36 or KSM K38 (EP 1,022,334). (a) variants described in WO 96 / 23873, WO 00 / 60060, W006 / 002643 and WO 2017 / 192657, in particular variants having one or more substitutions at the following positions relative to SEQ ID NO: 12 of WO 06 / 002643: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 202, 214, 231, 246, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, preferably D183 * and G184 * Mutants that also contain deletions of (b) SEQ ID NO: 4 of WO06 / 002643, variants exhibiting at least 90% identity to the wild-type enzyme from Bacillus sp. 722, in particular variants having deletions at positions 183 and 184, and variants described in WO 00 / 60060, WO 2011 / 100410, and WO2013 / 003659, which are incorporated herein by reference. (c) variants exhibiting at least 95% identity with the wild-type enzyme from Bacillus sp. 707 (SEQ ID NO: 7 in U.S. Pat. No. 6,093,562), in particular those comprising one or more mutations at the following positions: M202, M208, S255, R172 and / or M261. Preferably, the amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and / or R172Q. Particularly preferred are those comprising the M202L or M202T mutations. (d) a variant described in WO 09 / 149130, preferably SEQ ID NO: 1 or SEQ ID NO: 2 of WO 09 / 149130, which shows at least 90% identity to the wild-type enzyme from Geobacillus Stearophermophilus or a truncated version thereof. (e) a variant exhibiting at least 89% identity to SEQ ID NO: 1 of WO 2016 / 091688, in particular comprising a deletion at positions H183+G184 and one or more mutations at positions 405, 421, 422 and / or 428. (f) A variant showing at least 60% amino acid sequence identity with “PcuAmyl α-amylase” derived from Paenibacillus curdlanolyticus YK9 (SEQ ID NO: 3 in WO 2014 / 099523). (g) A variant showing at least 60% amino acid sequence identity with "CspAmy2 amylase" derived from Cytophaga sp. (SEQ ID NO: 1 of WO 2014 / 164777). (h) a variant showing at least 85% identity to AmyE from Bacillus subtilis (SEQ ID NO: 1 of WO 2009 / 149271). (i) A variant that exhibits at least 90% identity with the wild-type amylase derived from Bacillus sp. KSM-K38 having accession number AB051102. (j) A variant exhibiting at least 80% identity to the mature amino acid sequence of AAI10 from Bacillus species (SEQ ID NO: 7 in WO 2016 / 180748), preferably containing one or more mutations at one or more of the following positional modifications: 1, 54, 56, 72, 109, 113, 116, 134, 140, 159, 167, 169, 172, 173, 174, 181, 182, 183, 184, 189, 194, 195, 206, 255, 260, 262, 265, 284, 289, 304, 305, 347, 391, 395, 439, 469, 444, 473, 476, or 477. (k) a variant exhibiting at least 80% identity with the mature amino acid sequence of the fusion peptide (SEQ ID NO: 14 of US Patent Application Publication No. 2019 / 0169546), preferably a mutant H1 * , N54S+V56T, A60V, G109A, R116Q / H+W167F, L173V, A174S, Q172N, G182 * , D183 * , N195F, V206L / Y, V208L, K391A, K393A, I405L, A421H, A422P, A428T, G476K and / or G478K. Preferred amylases include those with the deletion G182 *and G183 * and optionally one or more of the following sets of mutations: 1.Hl * +G109A+N195F+V206Y+K391A; 2.H1 * +N54S+V56T+G109A+A1745+N195F+V206L+K391A+G476K) 3.H1 * +N54S+V56T+A60V+G109A+R116Q+W167F+Q172N+L173V+A1745+N195F+V206L+I405L+A421H+A422P+A428T 4.H1 * +N545+V56T+G109A+R116Q+A1745+N195F+V206L+I405L+A421H+A422P+A428T; 5.H1 * +N545+V56T+G109A+R116H+A1745+N195F+V208L+K393A+G478K; (l) A variant that shows at least 80% identity to the mature amino acid sequence of Alicyclobacillus amylase (SEQ ID NO: 8 in WO 2016 / 180748).

[0038] The amylase may be a genetically engineered enzyme, in which one or more of the amino acids susceptible to bleaching oxidation are replaced by amino acids less susceptible to oxidation. In particular, it is preferred that the methionine residue is replaced by any other amino acid. In particular, it is preferred that the methionine most susceptible to oxidation is replaced. Preferably, the methionine at position corresponding to 202 in SEQ ID NO: 2 is replaced. Preferably, the methionine at this position is replaced by threonine or leucine, preferably leucine.

[0039] Suitable commercially available α-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL®, ATLANTIC®, INTENSA® and BAN® (Novozymes A / S, Bagsvaerd, Denmark), KEMZYM® AT9000 (Biozym Biotech Trading GmbH, Wehlistrasse 27b A-1200 Wien Austria), RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE®, PREFERENZ S® series (PREFERENZ S1000® and PREFERENZ S2000®, as well as PURASTAR OXAM® (DuPont., Palo Alto, California) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitable amylases include ATLANTIC®, STAINZYME®, POWERASE®, INTENSA® and STAINZYME PLUS®, ACHIEVE ALPHA®, and mixtures thereof.

[0040] Preferably, the composition of the present invention contains at least 0.01 mg, preferably from about 0.05 to about 10, more preferably from about 0.1 to about 6, especially from about 0.2 to about 5 mg of active amylase / g of composition.

[0041] Preferably, the protease and / or amylase of the composition of the present invention is in the form of a granule, the granule containing more than 29% sodium sulfate by weight of the granule, and / or the sodium sulfate and the active enzyme (protease and / or amylase) are in a weight ratio of 3:1 to 100:1, or preferably 4:1 to 30:1, or more preferably 5:1 to 20:1.

[0042] Complexing Agent Complexing agents are substances capable of sequestering hardness ions, especially calcium and / or magnesium. The cleaning composition can contain high levels of complexing agents, but the levels should not be too high or the enzymes may be adversely affected. Too high a concentration of complexing agent may also adversely affect glass care. Complexing agents provide improved shine. Preferably, both the cleaning composition and the rinsing composition contain a complexing agent, especially a salt of methylglycine diacetate.

[0043] The cleaning composition may comprise from 15% to 50%, preferably from 20% to 40%, more preferably from 20% to 35%, by weight of the composition, of a complexing agent selected from the group consisting of methylglycine-N,N-diacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), iminodisuccinic acid (IDS), citric acid, aspartic acid-N,N-diacetic acid (ASDA), salts thereof, and mixtures thereof. Particularly preferred complexing agents for use herein are salts of MGDA, specifically the trisodium salt of MGDA. Mixtures of the citrate salt and the trisodium salt of MGDA are also preferred for use herein. Preferably, the cleaning composition of the present invention comprises from 15% to 40% of the trisodium salt of MGDA, by weight of the composition.

[0044] Inorganic Builders The cleaning composition preferably comprises an inorganic builder. Suitable inorganic builders are selected from the group consisting of carbonates, silicates and mixtures thereof. Sodium carbonate and sodium silicate are particularly preferred for use herein. Preferably, the cleaning composition comprises from 5 to 50%, more preferably from 10 to 40%, especially from 15 to 30% sodium carbonate by weight of the composition.

[0045] polymer When present, the polymers are used in any suitable amount from about 0.1% to about 30%, preferably 0.5% to about 15%, more preferably 1% to 10% by weight of the composition. Sulfonated / carboxylated polymers are particularly suitable for the composition.

[0046] Suitable sulfonated / carboxylated polymers described herein may have a weight average molecular weight of about 100,000 Da or less, or about 75,000 Da or less, or about 50,000 Da or less, or from about 3,000 Da to about 50,000, preferably from about 5,000 Da to about 45,000 Da.

[0047] Preferred sulfonated monomers include one or more of 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallyl sulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl, 3-sulfo-propyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and mixtures of the aforementioned acids or water-soluble salts thereof.

[0048] Preferably, the polymer comprises the following concentrations of monomers: from about 40 to about 90%, preferably from about 60 to about 90%, by weight of the polymer of one or more carboxylic acid monomers, from about 5 to about 50%, preferably from about 10 to about 40%, by weight of the polymer of one or more sulfonic acid monomers, and optionally from about 1% to about 30%, preferably from about 2 to about 20%, by weight of the polymer of one or more non-ionic monomers. Particularly preferred polymers comprise from about 70% to about 80% by weight of the polymer of at least one carboxylic acid monomer and from about 20% to about 30% by weight of the polymer of at least one sulfonic acid monomer.

[0049] In the polymer, all or some of the carboxylic or sulfonic acid groups may be present in neutralized form, i.e. the acidic hydrogen atoms of the carboxylic and / or sulfonic acid groups in some or all of the acidic groups may be replaced by metal ions, preferably alkali metal ions, in particular sodium ions.

[0050] The carboxylic acid is preferably (meth)acrylic acid. The sulfonic acid monomer is preferably 2-acrylamido-2-propanesulfonic acid (AMPS).

[0051] Preferred commercially available polymers include Alcosperse 240 and Aquatreat AR540 supplied by Nouryon, Acumer 3100, Acumer 2000, Acusol 587G and Acusol 588G supplied by Dow. Particularly preferred polymers are Acusol 587G and Acusol 588G supplied by Dow.

[0052] Suitable polymers include low molecular weight anionic carboxylic acid polymers. They may be homopolymers or copolymers having a weight average molecular weight of about 200,000 g / mol or less, or about 75,000 g / mol or less, or about 50,000 g / mol or less, or about 3,000 to about 50,000 g / mol, preferably about 5,000 to about 45,000 g / mol. The dispersant polymer may be a low molecular weight homopolymer of polyacrylate having an average molecular weight of 1,000 to 20,000, in particular 2,000 to 10,000, and particularly preferably 3,000 to 5,000.

[0053] The polymers may be copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and / or methacrylic acid and maleic acid, and copolymers of acrylic acid and / or methacrylic acid and fumaric acid, having a molecular weight of less than 70,000, with a molecular weight in the range of 2,000 to 80,000, more preferably 20,000 to 50,000, specifically 30,000 to 40,000 g / mol, and with a ratio of (meth)acrylate to maleate or fumarate segments of 30:1 to 1:2.

[0054] The polymer may be a copolymer of acrylamide and acrylate having a molecular weight of 3,000 to 100,000, alternatively 4,000 to 20,000, and an acrylamide content of less than 50%, alternatively less than 20%, by weight of the dispersant polymer may also be used. Alternatively, such polymers may have a molecular weight of 4,000 to 20,000, and an acrylamide content of 0% to 15% by weight of the polymer.

[0055] Suitable polymers herein also include itaconic acid homopolymers and copolymers.

[0056] Alternatively, the polymer may be selected from the group consisting of alkoxylated polyalkyleneimines, alkoxylated polycarboxylates, polyethylene glycols, styrene copolymers, cellulose sulfate esters, carboxylated polysaccharides, amphiphilic graft copolymers, and mixtures thereof.

[0057] Nonionic Surfactants Suitable surfactants for use herein include nonionic surfactants, preferably the composition does not contain other surfactants, more preferably the composition does not contain anionic cleaning surfactants.Anionic cleaning surfactants are typically cleaning grades with chain lengths of more than 10 carbon atoms.Anionic cleaning surfactants include alkyl sulfates, alkyl / aryl sulfonates, and alkyl ethoxy sulfates.Traditionally, nonionic surfactants have been used in automatic dishwashing for surface modification purposes, specifically for sheeting purposes to avoid filming and spotting and improve gloss.It has been found that nonionic surfactants can also contribute to preventing soil redeposition.

[0058] Preferably, the cleaning composition comprises a nonionic surfactant or nonionic surfactant system, more preferably the nonionic surfactant or nonionic surfactant system has a cloud point of 20-70°C, preferably 35-65°C, when measured at a concentration of 1% in distilled water. By "nonionic surfactant system" herein is meant a mixture of two or more nonionic surfactants. Nonionic surfactant systems are preferred for use herein. They are believed to have improved cleaning and finishing properties and better stability in the product than a single nonionic surfactant.

[0059] The cloud point is the temperature at which the nonionic surfactant solution phase separates into a water-rich phase and a surfactant-rich phase and becomes cloudy. The cloud point temperature can be determined visually by identifying the temperature at which clouding occurs.

[0060] The cloud point temperature of a nonionic surfactant may be determined as follows: Prepare a solution containing 1% of the corresponding nonionic surfactant by weight of the solution in distilled water. The solution is briefly stirred and then analyzed to ensure that the process occurs at chemical equilibrium. The cloud point temperature is measured in a thermostable bath by immersing the surfactant solution in a 75 mm sealed glass test tube. To ensure there are no leaks, weigh the test tube before and after measuring the cloud point temperature. The temperature is gradually increased at a rate of less than 1° C. / min until it reaches a few degrees below the pre-estimated cloud point. The cloud point temperature is determined visually at the first sign of turbidity.

[0061] Suitable nonionic surfactants include i) ethoxylated nonionic surfactants prepared by reaction of monohydroxyalkanols or alkyphenols having 6 to 20 carbon atoms with, preferably, at least 3 moles, particularly preferably at least 5 moles, and even more preferably at least 7 moles of ethylene oxide per mole of alcohol or alkylphenol, ii) alcohol alkoxylated surfactants having 6 to 20 carbon atoms and at least one ethoxy and propoxy group. Mixtures of surfactants i) and ii) are preferred for use herein.

[0062] Other suitable nonionic surfactants are the epoxy-capped poly(oxyalkylated) alcohols represented by the formula: R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2] (I) In the formula, R1 is a linear or branched aliphatic hydrocarbon group having 4 to 18 carbon atoms, R2 is a linear or branched aliphatic hydrocarbon group having 2 to 26 carbon atoms, x is an integer having an average value of 0.5 to 1.5, more preferably about 1, and y is an integer having a value of at least 15, more preferably at least 20.

[0063] Preferably, the surfactant of formula I has at least about 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2]. In accordance with the present invention, a suitable surfactant of formula I is, for example, POLY-TERGENT® SLF-18B nonionic surfactant of Olin Corporation, as described in WO 94 / 22800, published October 13, 1994 by Olin Corporation.

[0064] Amine oxide surfactants are useful for use in the cleaning compositions of the present invention. C10-C18 alkyl dimethyl amine oxides, and C10-18 acylamido alkyl dimethyl amine oxides are preferred.

[0065] Preferably, the cleaning composition comprises from about 0.1 to about 30% by weight of the composition, more preferably from about 0.5 to about 20% by weight of the composition of a nonionic surfactant.

[0066] Crystal Growth Inhibitors Crystal growth inhibitors are materials that can bind to calcium carbonate crystals and prevent the further growth of species such as aragonite and calcite.

[0067] A particularly preferred crystal growth inhibitor for use herein is the sodium salt of HEDP (1-hydroxyethylidene 1,1-diphosphonic acid). Preferably the cleaning composition comprises from 0.01 to 10%, more preferably from 0.1 to 8%, especially from 0.5 to 6% by weight of the composition of the crystal growth inhibitor, preferably the sodium salt of HEDP.

[0068] Metal Care Agent The metal care agent can prevent or reduce tarnishing, corrosion or oxidation of metals including aluminum, stainless steel, and non-ferrous metals such as silver and copper. Preferably, the cleaning composition comprises 0.1-5%, more preferably 0.2-4%, especially 0.3-3% by weight of the composition of the metal care agent, and preferably the metal care agent is benzo triazole (BTA).

[0069] Glass care products Glasscare agents protect the appearance of glassware during the dishwashing process. Preferably the cleaning composition comprises 0.1 to 5%, more preferably 0.2 to 4%, especially 0.3 to 3% by weight of the composition of a glasscare agent, preferably the glasscare agent is a zinc salt.

[0070] Bleach In some embodiments, the composition may preferably comprise from about 8 to about 30%, more preferably from about 9 to about 25%, and even more preferably from about 9 to about 20% bleaching agent by weight of the composition.

[0071] Inorganic and organic bleaching agents are suitable for use herein. Inorganic bleaching agents include perhydrated salts such as perborates, percarbonates, persulfates and persilicates. Inorganic perhydrated salts are usually alkali metal salts. Inorganic perhydrated salts can be included as crystalline solids without additional protection. Alternatively, the salts can be coated. Suitable coatings include sodium sulfate, sodium carbonate, sodium silicate and mixtures thereof. The coatings can be applied as a mixture applied to the surface or applied in sequential layers.

[0072] Alkali metal percarbonates, especially sodium percarbonate, are the preferred bleaching agents for use herein. The percarbonate is most preferably incorporated into the product in a coated form which provides in-product stability.

[0073] Potassium monopersulfate peroxide is another inorganic perhydrate salt useful herein.

[0074] Typical organic bleaching agents are organic peroxyacids, especially dodecane diperoxyacid, tetradecane diperoxyacid, and hexadecanediperoxyacid. Mono- and diperazelaic acid, mono- and diperbrassylic acid are also suitable herein. Diacyl and tetraacyl peroxides, such as dibenzoyl peroxide and dilauroyl peroxide, are other organic peroxides that can be used in the context of the present invention.

[0075] Further typical organic bleaching agents include peroxyacids, specific examples being the alkylperoxyacids and arylperoxyacids. Preferred representatives are: (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, as well as peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, diperoxyphthalic acid, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyldi(6-aminopercaproic acid).

[0076] bleach activator Bleach activators are typically organic peracid precursors that enhance bleaching action during washing at temperatures up to 60° C. Suitable bleach activators for some embodiments include compounds that, under perhydrolysis conditions, give aliphatic peroxoycarboxylic acids, preferably having 1-12 carbon atoms, specifically 2-10 carbon atoms, and / or optionally substituted perbenzoic acids. Suitable materials have O-acyl and / or N-acyl groups with the number of carbon atoms specified, and / or optionally substituted benzoyl groups. Also preferred are polyacylated alkylenediamines, specifically tetraacetylethylenediamine (TAED), acylated triazine derivatives, specifically 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, specifically tetraacetylglycoluril (TAGU), N-acylimides, specifically N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, specifically n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), decanoyloxybenzoic acid (DOBA), carboxylic anhydrides, specifically phthalic anhydride, acylated polyhydric alcohols, specifically triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and triethylacetyl citrate (TEAC). When present, the cleaning composition comprises from 0.01 to 5, preferably from 0.2 to 2% by weight of the composition of a bleach activator, preferably TAED.

[0077] Bleaching catalyst The cleaning composition may comprise 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.

[0078] Preferred bleach catalysts for use herein include manganese triazacyclononane and related complexes; Co, Cu, Mn and Fe bispyridylamines and related complexes; and cobalt(III) pentamine acetate and related complexes.

[0079] The cleaning composition may contain from 0.001 to 0.5, more preferably from 0.002 to 0.05% by weight of the composition of a bleach catalyst. Preferably the bleach catalyst is a manganese bleach catalyst.

[0080] Preferably, the cleaning composition of the present invention comprises: i) 5 to 50% by weight of the composition of a builder; ii) 0.5 to 20% by weight of the composition of a nonionic surfactant; iii) 5 to 50% by weight of the composition of a complexing agent, preferably a complexing agent comprising a salt of MGDA; iv) enzymes, preferably amylases and proteases; v) optionally, 0.5 to 10% by weight of the composition of a dispersant polymer, preferably a carboxylate / sulfonate polymer; vi) optionally, 5 to 20% by weight of the composition of a bleaching agent, more preferably a bleach catalyst.

[0081] Rinse Composition The rinse composition is provided to the water of the rinse cycle to form a rinse liquor. The rinse liquor has a pH greater than 9, preferably greater than 10, more preferably greater than about 10.2. The rinse composition is enzyme-free. By "free" herein is meant that the composition contains less than 0.1% enzyme, preferably less than 0.001% enzyme, by weight of the composition.

[0082] The rinse composition may contain any of the ingredients listed in the description of the cleaning composition at the same levels, except for enzymes, unless otherwise specified.

[0083] The rinse composition preferably comprises an alkaline source. The alkaline source includes carbonates, silicates, and alkali metal hydroxides. Preferably, the alkaline source comprises an alkali metal hydroxide, more preferably sodium hydroxide. Other alkaline sources may have a detrimental effect on the gloss of the dishware, especially the gloss of glass.

[0084] The rinse composition may also contain a complexing agent. Improved shine and improved removal of bleachable stains are obtained when the rinse composition contains a complexing agent, particularly when the rinse composition contains a salt of methylglycine diacetate. Preferably, the rinse composition contains 5-50% complexing agent by weight of the composition, more preferably 10-35%. The rinse composition is preferably free of citric acid.

[0085] The rinse composition preferably comprises a crystal growth inhibitor, in particular the sodium salt of HEDP. Preferably, the rinse composition comprises 0.1 to 30% by weight of the composition, more preferably 0.5 to 25% by weight, especially 1 to 20% by weight of a crystal growth inhibitor, preferably the sodium salt of HEDP.

[0086] The rinse composition preferably comprises 5-50% by weight of the composition, more preferably 10-40% by weight of the composition of nonionic surfactant. The rinse composition preferably does not comprise anionic cleansing surfactant. As used herein, "anionic cleansing surfactant" means an anionic surfactant having a chain length of more than 10 carbon atoms. Examples of anionic cleansing surfactants include long chain length (i.e., more than 10 carbon atoms) alkyl sulfates, alkyl / aryl sulfonates, and alkyl ethoxy sulfates.

[0087] Hydrotropes The rinse aid composition of the present invention may include a hydrotrope. The hydrotrope increases the water solubility of the hydrophobic material and ensures the physical stability of the composition. In some embodiments, the hydrotrope is a low molecular weight aromatic sulfonate material, such as cumene sulfonate, xylene sulfonate, and dialkyldiphenyloxide sulfonate materials. In other embodiments, the hydrotrope is a short chain length alkyl sulfate having less than 10 carbon atoms in the alkyl chain.

[0088] The hydrotrope or combination of hydrotropes may be present in the composition in an amount of from about 1% to about 50% by weight of the composition, hi other embodiments, the hydrotrope or combination of hydrotropes may be present in an amount of from about 10% to about 30% by weight of the composition.

[0089] Carrier The rinse composition of the present invention can be formulated as a liquid composition.Carrier can be included in such liquid formulation.Any carrier suitable for use in rinse aid compositions can be used in the present invention.For example, in some embodiments, the composition comprises water as carrier.

[0090] In some embodiments, liquid rinse aid compositions according to the present invention will contain up to about 98% water by weight of the composition, typically up to about 90% water by weight of the composition, hi other embodiments, liquid rinse aid compositions will contain at least 50% water by weight of the composition, or at least 60% water by weight of the composition, as a carrier.

[0091] The rinse composition may include glass care agents and / or metal care agents.

[0092] Preferably, the rinse composition of the method of the present invention comprises: i) 0 to 40% by weight of the composition of the present invention, ii) 10 to 40% by weight of the composition of the present invention of a nonionic surfactant; iii) 10-35% by weight of the composition of a complexing agent, preferably the complexing agent comprises a salt of MGDA; and iv) 0 to 20% by weight of the composition of a sodium salt of HEDP; v) optionally a glass care agent and / or a metal care agent; vi) water, Packaging to contain cleaning and rinsing compositions.

[0093] The cleaning and rinsing compositions may be contained in a pack with at least two separate compartments. The pack may have three or more compartments. The pack may be inserted directly into the dishwasher or its contents may be used to fill an existing storage reservoir in the dishwasher.

[0094] The pack or reservoir containing the composition of the method of the present invention can be placed inside or outside the dishwasher. If placed inside the dishwasher, the pack or storage reservoir can be integrated into the automatic dishwasher (i.e., a storage reservoir that is permanently fixed (built-in) to the automatic dishwasher) or can be freestanding (i.e., a separate storage reservoir that can be inserted inside the automatic dishwasher).

[0095] An example of an integrated storage reservoir is a container built into the door of an automatic dishwasher and connected to the interior of the dishwasher by a refill line.

[0096] The pack can be used as a removable dosing device. The dosing device can be, for example, an automated unit comprising a pack and a dispensing unit capable of releasing controlled amounts of different compositions at different times, for example, into the main wash and into the rinse. Different types of hardware can be part of the dosing device for controlling the dispensing of the wash and rinse compositions or for communicating with external devices, such as a data processing unit, a dishwasher, or a mobile device or server that can be operated by a user.

[0097] The pack has very good thermal stability, especially when it is placed inside a dishwasher.

[0098] Preferably, 1 to 25, more preferably 2 to 20 grams of the cleaning composition is dispensed first, followed by 1 to 15, more preferably 2 to 8 grams of the rinse composition thereafter.

[0099] A preferred method according to the present invention is such that the composition remains in a storage reservoir located outside (e.g. WO 2019 / 81910 A1) or inside the dishwasher for at least 2, preferably at least 4, particularly preferably at least 8, in particular at least 12 separate dishwashing programs before being metered inside the dishwasher.

[0100] The dosing system can be linked to sensors that can determine the amount of composition needed based on the sensor input. Sensors that can be used include pH, turbidity, temperature, humidity, conductivity, etc. The dishwasher may require data processing capabilities to achieve this. The dishwasher preferably has connectivity with other devices. This can be in the form of wi-fi, mobile data, Blue tooth, etc. This allows the dishwasher to be monitored and / or controlled remotely. Preferably, this also allows the machine to connect with the internet.

[0101] The preferred storage reservoir, comprising one or more chambers, has a volume of 10-1000 ml, preferably 20-800 ml, in particular 50-500 ml. EXAMPLES

[0102] An automatic dishwashing composition was made as detailed herein below.

[0103] I. Preparation of Test Compositions Cleaning composition: 13.34 grams of automatic dishwashing detergent (based on active ingredients) containing MGDA, bleach, bleach catalyst, carbonate, HEDP, sulfonated polymer, protease, amylase, and non-ionic surfactant.

[0104] Four rinse compositions were prepared as detailed below.

[0105] [Table 1]

[0106] II. Test Articles The following items were procured and added to each automatic dishwasher:

[0107] [Table 2]

[0108] The dishwasher monitor was purchased from the Center for Test materials BVNetherlands. The following stains were used:

[0109] [Table 3]

[0110] III. Additional ballast soiling I To add additional soils to the test, a soil blend, prepared according to the procedure described below, is added to the dishwasher.

[0111] [Table 4]

[0112] Stain preparation 1. Combine the vegetable oil and whole eggs and mix thoroughly (about 30 minutes). 2. Continue to add ketchup and mustard while stirring vigorously. 3. Melt the fat and cool to about 40°C then add to the mixture and blend thoroughly. 4. Add cream and milk and stir. 5. Add the powdered solid ingredients and mix everything into a smooth paste. 6. Place 50 g of the soil mixture into plastic pots and freeze.

[0113] IV. Additional Ballast Fouling II To add additional soils to the test, a soil blend, prepared according to the procedure described below, is added to the dishwasher.

[0114] [Table 5]

[0115] Stain preparation 1. Mix the Carrefour Matere grass vegetale (Cuir et Rotir) and Carrefour Graisse a frire in a Thermomixer at speed 2, 55°C for 30 minutes, melting the fat while mixing. After 2.30 minutes, add Solvent Red 26 dye to the mixture and continue mixing at the same settings for an additional 15 minutes. 3. Place 10 g of the dirt mixture into a plastic pot and refrigerate.

[0116] V. Test Cleaning Procedure Automatic dishwasher: Miele, model GSL2 Wash volume: 5000ml Main wash water temperature: 45℃ Main wash length 22 minutes (8 minute hold) Rinse water temperature: 45℃, 55℃, or 70℃ Water hardness: 21gpg Adding cleaning composition: Add to bottom of automatic dishwasher when detergent dispenser opens at start of main wash. Add Rinse Composition: Add to bottom of automatic dishwasher at start of second (heated) rinse. Additional Soil Stress: Add 1 x 50 g pot of additional ballast soil I and 1 x 10 g pot of additional ballast soil II to the bottom rack.

[0117] Examples 1 to 3 13.34 grams of the cleaning composition was added to the main wash and the amounts detailed in the table below were added to the rinse.

[0118] [Table 6]

[0119] The dishwasher was loaded with the dishwasher monitor detailed above which was washed using methods 1-4. This method was repeated four times resulting in four replicates for each stain tested. Stains were analyzed via an Image Analysis System before and during washing to determine the % stain removed and a stain removal index (SRI) was calculated. SRI is a scale of 0-100 where 0=no stain removal and 100=complete removal of the stain. Means were calculated and are presented herein. Significance was calculated using a statistics package at the 95% confidence level.

[0120] [Table 7]

[0121] [Table 8]

[0122] [Table 9]

[0123] Example 4 13.34 grams of the cleaning composition was added to the main wash and the amounts detailed in the table below were added to the rinse.

[0124] [Table 10]

[0125] The dishwasher was loaded with the above detailed articles washed using method 2 and method 3, respectively. After four consecutive cycles were run, the plastic tumblers were then photographed against a black background and the images were analyzed using computer-aided software. The images generated were analyzed against a grey scale and assigned a numerical value indicating the average transmission of light through the same. The whiter the image, the lower the transmission of light through the sample and the darker the image, the higher the transmission of light through the sample. The numerical value was converted to a percentage scale, which is referred to as transparency (%). A difference of 2 transparency is significant. Transparency(%)=100-((Average Grayscale Value / 255) * 100)

[0126] A speckle is defined as a circular cluster larger than 4 pixels that has a higher gray scale (4 units) relative to the background, and a grit is defined as a circular cluster smaller than 4 pixels that has a higher gray scale (4 units) relative to the background.

[0127] [Table 11]

[0128] The method of the present invention provides improved clarity and reduced speckle and grit counts on both glass and plastic.

[0129] Dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

Claims

1. 1. A method of washing dishes in a domestic dishwashing machine using a program including a wash cycle and a rinse cycle, comprising: a) placing the dishware in the dishwasher; b) providing a cleaning composition comprising an enzyme to the wash cycle to form a wash liquor and subjecting the dishware to the wash liquor; c) providing an enzyme-free rinse composition comprising methylglycine diacetic acid and / or a salt thereof to said rinse cycle to form a rinse liquor having a pH greater than 9 and subjecting said dishware to said rinse liquor.

2. The method of claim 1 , wherein the rinse composition is bleach-free.

3. The method of claim 1 or 2, wherein the cleaning composition comprises a protease and an amylase.

4. The method of any one of claims 1 to 3, wherein the washing solution has a pH greater than 9.

5. The method of any one of claims 1 to 4, wherein the rinse composition comprises an alkali metal hydroxide.

6. The method of any one of claims 1 to 5, wherein the rinse composition comprises a complexing agent.

7. The method of any one of claims 1 to 6, wherein the rinse composition comprises a non-ionic surfactant.

8. The method according to any one of claims 1 to 7, wherein the maximum temperature of the rinsing liquid is less than 50°C.

9. The method according to any one of claims 1 to 8, wherein the method comprises an intermediate rinsing step between steps b) and c).

10. The method according to any one of claims 1 to 9, wherein the method comprises an additional rinsing step after step c).

11. The method of any one of claims 1 to 10, wherein the composition is delivered from a multi-dose system.

12. 12. An alkaline rinse composition for use in the method of any one of claims 1 to 11, said composition having a pH greater than 9 when measured in a 1 wt % solution in distilled water at 25°C, comprising methylglycine diacetic acid and / or salts thereof, and a non-ionic surfactant, and being free of bleach, enzymes, and anionic detersive surfactants having an alkyl chain length greater than 10 carbon atoms.

13. 12. An automatic dishwashing pack suitable for use in the method according to any one of claims 1 to 11, said pack comprising at least two distinct compartments, a first compartment comprising the cleaning composition and a second compartment comprising the rinsing composition.

14. Use of the method of any one of claims 1 to 11 to provide proteinaceous soil removal during the rinse cycle of an automatic dishwasher.

15. 13. Use of the composition of claim 12 in the rinse cycle of an automatic dishwashing machine, wherein the temperature of the rinse liquid is below 50°C to provide grit prevention and shine to the dishware.

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