Automatic tableware washing method and pack

Abstract

1. A method of washing dishes in a domestic dishwasher, comprising the steps of: loading dishes into the dishwasher; supplying a first high-alkalinity composition to the dishwasher to produce a first wash liquor having a pH of 11 or greater; supplying a second low-alkalinity composition to the dishwasher to produce a second wash liquor having a pH of less than 11; and subjecting the dishes to the first composition before subjecting them to the second composition.

Description

Technical Field

[0001] The present invention belongs to the field of automatic dishwashing. In particular, the present invention relates to a method for providing effective cleaning, in particular the removal of tea stains and / or stubborn food stains such as cooked stains, burnt-on stains, and charred stains. This method provides good removal of tea stains even in the absence of a bleaching agent and when used in hard water. Also provided is a pack for use in the method of the present invention.

Background Art

[0002] The removal of tea stains and stubborn food stains such as cooked stains, burnt-on stains, and charred stains from dishes seems to be a recurring problem in automatic dishwashing.

[0003] International Publication No. WO 2020 / 104611 (A1) provides a method for removing stains, particularly tea stains, in automatic dishwashing without using a bleaching agent. This method includes releasing a first detergent at a temperature below 40°C and releasing a main detergent during the main wash cycle when the temperature inside the dishwasher during the main wash cycle exceeds a predetermined temperature threshold.

[0004] The object of the present invention is to provide an alternative method for removing tea stains.

[0005] Formulators of automatic dishwashing detergents are constantly seeking ways to improve the performance of the detergents. Cooked soil, baked-on soil, and charred soil are one of the most difficult soils to remove. Removing cooked soil, baked-on soil, and charred soil from dishes may require soaking the soiled dishes prior to the mechanical action. Clearly, the automatic dishwashing process alone cannot adequately remove cooked soil, baked-on soil, and charred soil. In particular, cooked soil, baked-on soil, and charred soil containing proteins such as meat, eggs, and dairy products. When the detergent does not contain phosphates, it is more difficult to remove cooked soil, baked-on soil, and charred soil. European Patent Application Publication No. 3 339 410 (A1) teaches the use of alkyl amphocarboxylate surfactants to improve the removal of cooked soil, baked-on soil, and charred soil from dishes.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide another method or to further improve the removal of cooked soil, baked-on soil, and charred soil.

Means for Solving the Problems

[0008] According to a first aspect of the present invention, there is provided a method for washing dishes in a household dishwashing machine. The method comprises the following steps, namely, a) placing the dishes in the dishwashing machine; b) Supplying a first highly alkaline composition to a dishwashing machine to produce a first cleaning liquid having a pH of 11 or more, preferably 11.5 or more, more preferably about 12 or more, preferably, the highly alkaline composition contains an alkali metal hydroxide, the step of producing, c) Supplying a second low alkalinity composition to a dishwashing machine to produce a second cleaning liquid having a pH of less than 11, preferably more than 9; and d) subjecting the tableware to the first composition before subjecting it to the second composition.

[0009] According to a second aspect of the present invention, an automatic dishwashing pack is provided. The pack is suitable for use in the method of the present invention. The pack comprises at least two different compartments, the first compartment containing a first highly alkaline composition capable of providing a pH of more than 11, preferably about 12 or more, when added to the wash water, and the second compartment containing a second low alkalinity composition capable of providing a pH of less than 11, preferably about 9 or more, when added to the wash water.

[0010] According to a third aspect of the present invention, there is provided the use of the method of the present invention for providing tea stain removal and / or removal of cooked stains, burnt-on stains, and charred stains.

[0011] The elements of the first aspect of the present invention are mutatis mutandis applicable to the second and third aspects of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention encompasses a method for washing tableware in a dishwashing machine, a pack for use in this method, and the use of the method for providing tea stain removal and / or removal of cooked stains, burnt-on stains, and charred stains. This method is carried out in a domestic dishwashing machine.

[0013] The automatic dishwashing machine may be of the mechanical type for household or commercial / institutional use. Generally, the differences relate to size, throughput, and the duration of the dishwashing process. This can mean that the machines are designed in very different ways. Industrial / institutional machines often have much shorter but more energy-intensive (e.g., higher temperature) cycles compared to household machines, and / or use much more aggressive chemical properties.

[0014] Typically, these require a certain contact time with the dirt being processed to function effectively and do not use enzymes because the commercial cycle times are too short. In the case of commercially available dishwashing machines, the machine can be based on a conveyor system where the dishes move through one or more tanks of the dishwashing machine. In household machines, however, the dishes generally remain stationary in one tank inside the dishwashing machine, and all the washing steps are carried out within that single tank. In household dishwashing, it has been conventional to include bleaches and enzymes in the detergent.

[0015] As used herein, "dishes" means cooking utensils, tableware, and dinnerware, i.e., all items related to the cooking and serving of food and beverages that are normally washed inside a dishwashing machine.

[0016] 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 concentrations of ingredients or compositions relate to the active portion of such ingredient or composition, and impurities that may be present in commercially available sources of such ingredient or composition, e.g., residual solvents or by-products, are excluded. Unless specifically stated or the context requires otherwise, the embodiments described herein apply equally to all aspects of the invention. Percentages recited are by weight unless specifically stated otherwise or the context requires otherwise.

[0017] Unless otherwise specified, all measurements are carried out at 25°C.

[0018] The method of the present invention The method of the present invention comprises the following steps carried out in a domestic dishwasher, namely: a) putting dishes into the dishwasher; b) supplying a first highly alkaline composition to the dishwasher to subject the dishwasher to a first cleaning liquid having a pH of 11 or more, preferably more than 11.5, more preferably about 12 or more, particularly about 12; c) supplying a second low-alkalinity composition to the dishwasher to subject the dishwasher to a second cleaning liquid having a pH of less than 11, preferably about 9 or more.

[0019] The first composition is supplied to the dishwasher before the second composition, and preferably, the first composition is supplied at least 3 minutes, preferably at least 5 minutes, before the second composition. The first cleaning liquid can be discharged before introducing fresh water to form the second cleaning liquid. Alternatively, the second cleaning liquid can be formed by adding the second composition to the first cleaning liquid. In this case, an intermediate step of adding a neutralizing agent is preferred. Preferably, an acid can be added. A preferred acid for use herein is citric acid.

[0020] The pH of the first cleaning liquid can be decreased by the presence of dirt derived from the soiled dishes, and part of the dirt such as fat is acidic in nature and decreases the pH of the first cleaning liquid. It seems that better cleaning can be obtained when the pH is maintained constant. "Constant" herein means that during at least 50%, more preferably at least 60% of the time the dishes are exposed to the first cleaning liquid, the pH does not change by more than 0.5 pH units, preferably not more than 0.3 pH units.

[0021] Preferably, the pH of the first cleaning liquid is maintained constant by repeated addition of an alkalizing agent, more preferably by adding an alkali source such as sodium hydroxide.

[0022] In the context of the present application, a "dishwashing program" preferably includes a pre-washing, pre-rinsing and / or rinsing cycle in addition to the main washing cycle, and is a completed washing process that can be selected and operated by a program switch of a dishwasher. The duration of the washing program is advantageously at least 15 minutes, advantageously 20 - 360 minutes, preferably 20 - 90 minutes. Within the scope of the significance of the present application, a "short program" lasts less than 60 minutes and a "long program" lasts 60 minutes or more.

[0023] Household dishwashers can usually provide a plurality of programs, such as a basic washing program for washing moderately dried and soiled dishes, an intensive washing program for washing very soiled dishes or in the case of food residues that are particularly difficult to remove (very dry or burnt stains), an economy washing program for washing lightly soiled dishes or a partial quantity of dishes, a high-speed washing program for washing a partial quantity of dishes more quickly when desired, such as a previous cycle, etc. Each program includes a plurality of consecutive steps. Usually, one or two low-temperature pre-washing cycles, a washing cycle (also known as the main wash), a low-temperature rinsing cycle, a high-temperature rinsing cycle, and optionally a drying cycle. Different compositions can be added to the water of the dishwasher between different cycles of the program to assist in washing. Preferably, the first composition is supplied for pre-washing and the second composition is supplied for the main washing cycle.

[0024] During the process of the selected dishwashing program, a household dishwasher generally executes one or more cycles such as a pre-wash, a main wash, an intermediate rinse cycle, a final rinse cycle, and then a drying cycle to complete the program. During each cycle, the cleaning liquid is distributed, especially sprayed, into the processing chamber of the dishwasher cavity by a rotating spray arm, a fixed spray nozzle, such as a top spray head, a movable spray nozzle, such as a top spinning unit, and / or any other liquid distribution device, where the cleaning liquid is applied to the items to be cleaned, such as dishes and / or cutlery, supported by at least one loading unit, preferably a removable or pull-out drawer rack or a cutlery drawer. For this purpose, the dishwasher is preferably supplied with the cleaning liquid via at least one supply line by an operating circulation pump, and the cleaning liquid is collected at the bottom of the dishwasher cavity, preferably in a recess, especially a sump for dirty water. If the cleaning liquid has to be heated during each liquid-guided cleaning sub-cycle, the cleaning liquid is heated by a heating facility. This can be part of the circulation pump. At the end of each liquid-guided cleaning sub-cycle, part or all of the cleaning liquid present in the processing chamber of the dishwasher cavity in each case is pumped out by a drainage pump.

[0025] The first composition preferably contains an alkali metal hydroxide, more preferably sodium hydroxide. The first composition is added to the washing water to form a first cleaning liquid. The first cleaning liquid has a pH greater than 11, preferably greater than 11.5, more preferably about 12 or more. To maintain the pH constant, it is preferred to add additional alkali metal hydroxide to the first cleaning liquid. Preferably, the pH is maintained constant for at least 2 minutes, more preferably for at least 3 minutes.

[0026] The pH of the composition of the present invention can be measured in a 1% weight / volume aqueous solution in distilled water at 20°C.

[0027] In a preferred embodiment, the second composition contains an enzyme and does not contain a bleaching agent, a bleach catalyst, and a bleach activator. Surprisingly, it has been found that the method of the present invention provides good removal of tea stains even without using a bleaching agent.

[0028] In another preferred embodiment, the first composition contains a mixture comprising an alkanolamine, a glycol ether, and a complexing agent. Preferably, the mixture contains triethanolamine, dipropylene glycol butyl ether, and a salt of methylglycine diacetic acid. This embodiment provides good removal of cooked stains, baked-on stains, and charred stains. This is also the case even for a short program.

[0029] In another preferred embodiment, the second composition contains a mixture comprising an alkanolamine, a glycol ether, and a complexing agent. Preferably, the mixture contains triethanolamine, dipropylene glycol butyl ether, and a salt of methylglycine diacetic acid. This embodiment provides good removal of cooked stains, baked-on stains, and charred stains, especially in a long program.

[0030] In another preferred embodiment, the first composition contains an alkyl amphocarboxylate surfactant. The carboxylate group in the alkyl amphocarboxylate surfactant contains 2 to 4 carbon atoms, and the alkyl group in the alkyl amphocarboxylate surfactant contains 6 to 24 carbon atoms. Preferably, the alkyl amphocarboxylate surfactant contains sodium cocoamphoacetate. Preferably, the temperature of the first cleaning liquid is 30 °C or higher, more preferably above 40 °C. Surprisingly, it has been found that when the alkyl amphocarboxylate is part of the first composition rather than the second composition, cooked stains, baked-on stains, and charred stains are removed better. This advantage is obtained even for a short program.

[0031] The pack of the present invention The pack of the present invention contains the first and second compositions of the method of the present invention. The compositions are provided in at least two separate compartments. The pack can have three or more compartments, for example, a first compartment containing an alkali metal hydroxide and a different compartment containing a mixture, the mixture containing an alkanolamine, a glycol ether and a complexing agent and / or an alkyl amphocarboxylate surfactant. The second compartment can contain an enzyme, and the different compartments may contain a builder and / or a dispersant polymer. The pack can be inserted directly into the dishwasher or its contents can be used to fill an existing storage reservoir of the dishwasher.

[0032] A pack or reservoir containing the composition of the method of the present invention can be placed inside or outside the dishwasher. When placed inside the dishwasher, the pack or storage reservoir can be integrated into the automatic dishwasher (i.e., a storage reservoir permanently fixed (built-in) in the automatic dishwasher), or can be self-standing (i.e., an independent storage reservoir that can be inserted inside the automatic dishwasher).

[0033] An example of an integrated storage reservoir is a receptacle incorporated into the door of an automatic dishwasher and connected to the inside of the dishwasher by a supply line.

[0034] The pack can be used as a removable dosing device. The dosing device can be, for example, an automated unit comprising the pack and a dispensing unit capable of releasing controlled amounts of different compositions at different times, for example, during pre-washing and main washing. Different types of hardware can be part of the dosing device for controlling the dispensing of the cleaning composition or for communicating with an external device such as a data processing unit, a dishwasher, or a mobile device or server that can be operated by the user.

[0035] The pack has very good thermal stability, especially when it is placed inside the dishwasher.

[0036] Preferably, 1 to 15 grams, more preferably 2 to 8 grams of the first composition are supplied first, followed by 1 to 25 grams, more preferably 2 to 20 grams of the second composition being supplied thereafter. When the first and second compositions are supplied in the same cycle, it is preferred to add 1 to 5 grams of a neutralizing agent, preferably an organic acid, more preferably citric acid.

[0037] 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 pamphlet) or inside the dishwasher during at least 2, preferably at least 4, particularly preferably at least 8, especially at least 12 separate dishwasher programs before being metered into the interior of the dishwasher.

[0038] The dosing system can be linked to a sensor that can determine the amount of composition required based on the input of the sensor. Sensors that may be used include pH, turbidity, temperature, humidity, conductivity, etc. The dishwasher may require data processing capabilities to achieve this. The dishwasher preferably has connectivity to other devices. This may take the form of, for example, wi-fi, mobile data, Bluetooth®. This may allow the dishwasher to be remotely monitored and / or controlled. Preferably, this also allows the machine to connect to the Internet.

[0039] The volume of a preferred storage reservoir containing one or more chambers is 10 to 1000 mL, preferably 20 to 800 mL, particularly 50 to 500 mL.

[0040] Alternatively, the first composition can be supplied to the dishes in the form of a spray before the dishes are placed in the dishwasher. The sprayed composition forms a first cleaning liquid when it comes into contact with the washing water.

[0041] The first composition contains an alkali source, preferably an alkali metal hydroxide, more preferably sodium hydroxide.

[0042] The first composition may also contain a mixture comprising an alkanolamine, a glycol ether and a complexing agent. Typical examples of alkanolamines include triethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, tripropanolamine, etc. Preferably, the alkanolamine contains triethanolamine. Preferably, the alkanolamine and the glycol ether are present in the mixture in a weight ratio of 3:1 to 1:3. Preferably, the alkanolamine contains triethanolamine. The glycol ether is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol phenyl ether and mixtures thereof. A preferred glycol ether for use herein is dipropylene glycol butyl ether. Preferably, the alkanolamine and the glycol ether are present in the mixture in a weight ratio of 3:1 to 1:3.

[0043] A preferred complexing agent for use herein is methylglycine diacetic acid. The mixture preferably contains triethanolamine, dipropylene glycol butyl ether and methylglycine diacetic acid. Alternatively, the mixture can be used in the second composition.

[0044] Preferably, the first composition does not contain an enzyme. "Does not contain" means herein that the composition contains less than 0.1% by weight of the enzyme in the composition.

[0045] Alkyl amphocarboxylate surfactant The first composition may contain an alkyl amphocarboxylate surfactant. The alkyl amphocarboxylate surfactant includes any amphoteric carboxylate surfactant. Amphoteric surfactants characteristically contain both a basic functional group and an acidic functional group. In the surfactant, the basic center is either a secondary amine group or a tertiary amine group depending on whether the molecule is a monocarboxylate or a dicarboxylate. The acid characteristic is provided by one or more carboxylate groups. In an acidic solution, the surfactant is a cationic amine salt. In an alkaline solution, it is an anionic carboxylate salt.

[0046] The carboxylate groups in the surfactant of the present invention preferably contain 2 to 4 carbon atoms, and more preferably the carboxylate groups are selected from the group consisting of acetate, propionate, and mixtures thereof. The alkyl group of the surfactant of the present invention preferably contains 6 to 24 carbon atoms, more preferably 8 to 18 carbon atoms, and the alkyl group preferably results from a fatty acid selected from the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, and mixtures thereof. Preferably, the alkyl group results from coconut oil.

[0047] Preferably, the alkyl amphocarboxylate surfactant is selected from the group consisting of alkyl amphoacetate, alkyl amphodiacetate, alkyl amphopropionate, alkyl amphodipropionate, and mixtures thereof, and more preferably is selected from the group consisting of sodium cocoamphoacetate, sodium lauroamphoacetate, disodium cocoamphodiacetate, sodium capryloamphopropionate, disodium capryloamphodipropionate, and mixtures thereof. Sodium cocoamphoacetate is a preferred alkyl amphocarboxylate surfactant for use herein.

[0048] Commercially available alkyl amphocarboxylate surfactants that may be used in accordance with the present invention include AMPHOSOL® 1C sold by Stepan Company, MACKAM® HPC 32L, MACKAM® 2CY-75 and MIRANOL® Ultra sold by Solvey.

[0049] The alkyl amphocarboxylate surfactant is preferably present in an amount in the range of 0.5 to 10% by weight, more preferably 0.5 to 2% by weight of the first composition.

[0050] The second composition The second composition preferably includes an enzyme and optionally a complexing agent, a polymer, inorganic builders (preferably carbonates and silicates), a nonionic surfactant, etc. In some embodiments, the second composition does not include a bleaching agent, a bleach catalyst, and a bleach activator.

[0051] Complexing agent A complexing agent is a substance that can sequester hard ions, particularly calcium and / or magnesium.

[0052] The second composition may include 15% to 50% by weight, preferably 20% to 40% by weight, more preferably 20% to 35% by weight of a 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. A particularly preferred complexing agent for use herein is the salt of MGDA, particularly the trisodium salt of MGDA. A mixture of citrate and the trisodium salt of MGDA is also preferred for use herein. Preferably, the composition of the present invention includes 15% to 40% by weight of the trisodium salt of MGDA in the composition.

[0053] Inorganic builder The second composition preferably contains 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 composition of the present invention contains 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly 15 to 30% by weight of sodium carbonate based on the composition.

[0054] Polymer The polymer, when present, is used in any suitable amount of about 0.1% to about 30% by weight, preferably 0.5% to about 20% by weight, more preferably 1% to 15% by weight of the second composition. Sulfonated / carboxylated polymers are particularly suitable for the second composition.

[0055] 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 about 3,000 Da to about 50,000 Da, preferably about 5,000 Da to about 45,000 Da.

[0056] Preferred sulfonated monomers include 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, methallylsulfonic 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 one or more of the above acids or mixtures of their water-soluble salts.

[0057] Preferably, this polymer comprises various monomers in the following concentrations, namely, about 40 to about 90% by weight, preferably about 60 to about 90% by weight of one or more carboxylic acid monomers based on the polymer, about 5 to about 50% by weight, preferably about 10 to about 40% by weight of one or more sulfonic acid monomers based on the polymer, and optionally about 1 to about 30% by weight, preferably about 2 to about 20% by weight of one or more nonionic monomers based on the polymer. Particularly preferred polymers comprise at least one carboxylic acid monomer in an amount of about 70% to about 80% by weight of the polymer and at least one sulfonic acid monomer in an amount of about 20% to about 30% by weight of the polymer.

[0058] In the polymer, all or some of the carboxylic acid groups or sulfonic acid groups may be in the neutralized form, i.e., the acidic hydrogen atoms of the carboxylic acid groups and / or sulfonic acid groups in some or all of the acidic groups can be replaced by metal ions, preferably alkali metal ions, particularly sodium ions.

[0059] The carboxylic acid is preferably (meth)acrylic acid. The sulfonic acid monomer is preferably 2-acrylamido-2-propanesulfonic acid (AMPS).

[0060] Preferred commercially available polymers include Alcosperse 240, Aquatreat AR540, and Aquatreat MPS supplied by Alco Chemical, Acumer 3100, Acumer 2000, Acusol 587G and Acusol 588G supplied by Rohm & Haas, Goodrich K-798, K-775 and K-797 supplied by BF Goodrich, and ACP1042 supplied by ISP technologies Inc. Particularly preferred polymers are Acusol 587G and Acusol 588G supplied by Rohm & Haas.

[0061] Suitable polymers include low molecular weight anionic carboxylic acid polymers. They can 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 g / mol to about 50,000 g / mol, preferably about 5,000 g / mol to about 45,000 g / mol. The dispersant polymer can be a low molecular weight homopolymer of polyacrylate having an average molecular weight of 1,000 to 20,000, particularly 2,000 to 10,000, and particularly preferably 3,000 to 5,000.

[0062] The polymer can be a copolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and / or methacrylic acid and maleic acid, and a copolymer of acrylic acid and / or methacrylic acid and fumaric acid having a molecular weight of less than 70,000. Their molecular weights range from 2,000 to 80,000 g / mol, more preferably from 20,000 to 50,000 g / mol, particularly from 30,000 to 40,000 g / mol, and the ratio of (meth)acrylate to maleate or fumarate segment is 30:1 to 1:2.

[0063] The polymer can be a copolymer of acrylamide and acrylate having a molecular weight of 3,000 to 100,000, or 4,000 to 20,000, and an acrylamide content of less than 50% by weight, or less than 20% by weight of the dispersant polymer can also be used. Alternatively, such a polymer can have a molecular weight of 4,000 to 20,000 and an acrylamide content of 0% to 15% of the polymer.

[0064] Polymers suitable herein also include itaconic acid homopolymers and copolymers.

[0065] Alternatively, the polymer can be selected from the group consisting of alkoxylated polyalkyleneimine, alkoxylated polycarboxylate, polyethylene glycol, styrene copolymer, cellulose sulfate ester, carboxylated polysaccharide, amphiphilic graft copolymer, and mixtures thereof.

[0066] Further surfactant Surfactants suitable for use herein include nonionic surfactants in addition to alkyl amphocarboxylate surfactants, and preferably the composition does not contain any other surfactants. Conventionally, nonionic surfactants have been used in automatic dishwashing for surface modification purposes, particularly to avoid film formation and spotting and for sheeting to improve gloss. It has been found that nonionic surfactants can also contribute to preventing redeposition of dirt.

[0067] Preferably, the second composition contains a nonionic surfactant or a nonionic surfactant system, and more preferably, the nonionic surfactant or nonionic surfactant system has a phase inversion temperature between 40 and 70 °C, preferably between 45 and 65 °C, when measured at a concentration of 1% in distilled water. "Nonionic surfactant system" means, herein, a mixture of two or more nonionic surfactants. Nonionic surfactant systems are preferred for use herein. These are thought to have improved cleaning and finishing properties and good stability in the product compared to a single nonionic surfactant.

[0068] The phase inversion temperature is the temperature at which, at temperatures lower than it, the surfactant or its mixture is preferentially distributed in the aqueous phase as oil-swollen micelles, and at temperatures higher than it, it is preferentially distributed in the oily phase as water-swollen reverse micelles. The phase inversion temperature can be visually determined by identifying the temperature at which turbidity occurs.

[0069] The phase inversion temperature of the nonionic surfactant or system can be determined as follows. Prepare a solution containing 1 wt% of the corresponding surfactant or mixture in distilled water. After gently stirring the solution, analyze the phase inversion temperature to ensure that the process occurs at chemical equilibrium. The phase inversion temperature is measured in a thermostatically controlled bath by immersing the solution in a 75 mm sealed glass test tube. Weigh the test tube before and after the measurement of the phase inversion temperature to ensure no leakage. Gradually increase the temperature at a rate of less than 1 °C / min until the temperature reaches several degrees below the pre-predicted phase inversion temperature. The phase inversion temperature is visually determined at the first sign of turbidity.

[0070] Suitable nonionic surfactants include: i) ethoxylated nonionic surfactants prepared by the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with at least 12 moles, particularly preferably at least 16 moles, and even more preferably at least 20 moles of ethylene oxide per mole of the alcohol or alkylphenol; ii) alcohol alkoxylated surfactants having 6 to 20 carbon atoms and at least one ethoxy group and propoxy group. A mixture of surfactant i) and ii) is preferred for use herein.

[0071] Another suitable nonionic surfactant is an epoxy-capped poly(oxyalkylated) alcohol represented by the following formula: R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2] (I) wherein 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.

[0072] Preferably, the surfactant of formula I has at least about 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2]. According to the present invention, suitable surfactants of formula I are, for example, the POLY-TERGENT® SLF-18B nonionic surfactant of Olin Corporation, as described in International Publication No. WO 94 / 22800, published on October 13, 1994 by Olin Corporation.

[0073] Amine oxide surfactants are useful for use in the compositions of the present invention. C10-C18 alkyldimethylamine oxides and C10-18 acylamidalkyldimethylamine oxides are preferred.

[0074] Additional surfactants may be present at levels of 0.1-10% by weight, more preferably 0.2-5% by weight, particularly 0.3-3% by weight of the composition.

[0075] Enzyme The second composition preferably contains an enzyme. More preferably, they are amylase and protease.

[0076] When describing the enzyme variants herein, the following nomenclature is used for ease of reference: original amino acid: position: substituted amino acid. The one-letter code of the standard enzyme IUPAC amino acid is used.

[0077] Protease Proteases suitable for use in the second composition include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases such as subtilisin (EC 3.4.21.62). Suitable proteases include those of animal, plant or microbial origin. In one embodiment, such suitable proteases may be of microbial origin. Suitable proteases include chemically or genetically modified variants of the aforementioned suitable proteases. In one embodiment, the suitable protease may be an alkaline microbial protease or / and a serine protease such as a trypsin-type protease. Examples of suitable neutral or alkaline proteases include the following. (a) Subtilisin (EC 3.4.21.62), particularly those described in International Publication Nos. 2004 / 067737, 2015 / 091989, 2015 / 091990, 2015 / 024739, 2015 / 143360, US Patent Nos. 6,312,936, 5,679,630, 4,760,025, German Patent Publication Nos. 102006022216(A1), 102006022224(A1), International Publication Nos. 2015 / 089447, 2015 / 089441, 2016 / 066756, 2016 / 066757, 2016 / 069557, 2016 / 069563, 2016 / 069569, derived from Bacillus species such as Bacillus sp., B. 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 Fusarium protease described in International Publication No. 89 / 06270 and chymotrypsin protease derived from the genus Cellulomonas described in International Publication Nos. 05 / 052161 and 05 / 052146. (c) Metalloproteases, especially those derived from Bacillus amyloliquefaciens as described in WO 07 / 044993 (A2). Those derived from Bacillus, Brevibacillus, Thermoactinomyces, Geobacillus, Paenibacillus, Lysinibacillus or Streptomyces spp. as described in WO 2014194032, WO 2014194054 and WO 2014194117, those derived from Kribella alluminosa as described in WO 2015193488, and those derived from Streptomyces and Lysobacter as described in WO 2016075078. (d) Proteases having at least 90% identity to the subtilase derived from Bacillus sp. TY145, NCIMB 40339 as described in WO 92 / 17577 (Novozymes A / S), for example, proteases including variants of this Bacillus sp. TY145 subtilase as described in WO 2015024739 and WO 2016066757. (e) Proteases comprising variants found in WO 2016 / 205755 and WO 2018 / 118950, and comprising at least one amino acid substitution selected from the group consisting of 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, 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 US Patent No. 10,655,090 (B2). Preferred proteases have 100% identity with SEQ ID NO: 1 of US Patent No. 10,655,090 (B2). Another preferred protease has 1 to 4 modifications with respect to SEQ ID NO: 1 of US Patent No. 10,655,090 (B2).

[0078] Particularly preferred proteases for use in the second composition are as follows: (a) Using the BPN' numbering system and amino acid abbreviations shown in WO 00 / 37627 pamphlet incorporated herein by reference, a polypeptide showing at least 90%, preferably at least 95%, more preferably at least 98%, even more preferably at least 99%, particularly 100% identity with the wild-type enzyme derived from Bacillus lentus and containing mutations at one or more, preferably two or more, more preferably three or more of the following positions; V68A, N76D, N87S, S99D, S99AD, S99A, S101G, S101M, S103A, V104N / I, G118V, G118R, S128L, P129Q, S130A, Y167A, R170S, A194P, V205I, Q206L / D / E, Y209W and / or M222S, and / or, (b) A protease having at least 95%, more preferably at least 98%, even more preferably at least 99%, particularly 100% identity with the amino acid sequence of SEQ ID NO: 85 from WO 2016 / 205755 and containing at least one amino acid substitution (using the numbering of SEQ ID NO: 85) selected from the group consisting of: 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 comprising the following mutations (BPN numbering system) relative to either PB92 wild-type (SEQ ID NO: 2 of WO 08 / 010925) or subtilisin 309 wild-type (sequence by the PB92 backbone except for the natural mutation N87S). (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 selected 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.

[0079] Most preferred for use herein is a protease, which has at least 60% identity with the amino acid sequence of SEQ ID NO: 1 in WO 2019 / 125894 (A1) pamphlet and is a variant comprising at least one amino acid substitution (using the numbering of SEQ ID NO: 1) selected from the group consisting of: 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, it is a variant having at least 90% identity with the amino acid sequence of SEQ ID NO: 1, and the variant comprises at least one amino acid substitution (using the numbering of SEQ ID NO: 1) selected from the group consisting of P54T, S126A, D127E, F128G and M211L.

[0080] Another preferred protease for use herein comprises a protease, which is a variant having at least 90% identity with the amino acid sequence of SEQ ID NO: 1 in WO 2019 / 245839 (A1) pamphlet, and the variant comprises one or more amino acid substitutions at one or more positions corresponding to the positions of SEQ ID NO: 1 selected from: 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, 124E / 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, 157C / D / E An automatic dishwashing composition wherein the amino acid positions of the variant are numbered corresponding to the amino acid sequence of SEQ ID NO: 1.

[0081] 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 Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect 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. Patent No. 5,352,604 and which has the mutations S99D+S101R+S103A+V104I+G159S, hereinafter referred to as BLAP in this specification), BLAP R (BLAP having S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP having S3T+V4I+V205I) and BLAP F49 (BLAP having S3T+V4I+A194P+V199M+V205I+L217D); and KAP (subtilisin of Bacillus alkalophilus having the mutations A230V+S256G+S259N) manufactured by Kao Corporation.

[0082] Particularly preferred for use in this specification 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.

[0083] The preferred concentration of protease in the product of the present invention contains from about 0.05 to about 20 mg, more preferably from about 0.5 to about 15 mg, and particularly from about 2 to about 12 mg of active protease per gram of the composition.

[0084] Amylase The second composition can contain amylase. Suitable α - amylases include those of bacterial or fungal origin. Chemically or genetically modified variants are included. Preferred alkaline α - amylases are from Bacillus species such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis or other Bacillus species such as Bacillus sp. NCBI12289, NCBI12512, NCBI12513, DSM9375 (U.S. Patent No. 7,153,818), DSM12368, DSMZ number 12649, KSM AP1378 (WO 97 / 00324), KSM K36 or KSM K38 (European Patent No. 1,022,334). Preferred amylases include the following. (a) Variants described in WO 96 / 23873, WO 00 / 60060, WO 06 / 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 * Variants including deletions of (b) Variants showing at least 90% identity with the wild - type enzyme from Bacillus sp. 722, SEQ ID NO: 4 of WO 06 / 002643, especially variants having deletions at positions 183 and 184, and variants described in WO 00 / 60060, WO 2011 / 100410, and WO 2013 / 003659 which are incorporated herein by reference. (c) Variants showing at least 95% identity with the wild - type enzyme from Bacillus sp. 707 (SEQ ID NO: 7 of US Patent No. 6,093,562), especially those containing one or more mutations at the following positions: M202, M208, S255, R172 and / or M261. Preferably, the amylase contains one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and / or R172Q. Those containing the M202L or M202T mutation are particularly preferred. (d) Variants described in WO 09 / 149130, preferably SEQ ID NO: 1 or SEQ ID NO: 2 of WO 09 / 149130, showing at least 90% identity with the wild - type enzyme from Geobacillus Stearophermophilus or a truncated version thereof. (e) Variants showing at least 89% identity with SEQ ID NO: 1 of WO 2016 / 091688, especially those containing deletions 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" (SEQ ID NO: 3 of WO 2014 / 099523) derived from Paenibacillus curdlanolyticus YK9. (g) A variant showing at least 60% amino acid sequence identity with "CspAmy2 amylase" (SEQ ID NO: 1 of WO 2014 / 164777) derived from Cytophaga sp. (h) A variant showing at least 85% identity with AmyE (SEQ ID NO: 1 of WO 2009 / 149271) derived from Bacillus subtilis. (i) A variant showing at least 90% identity with the wild-type amylase derived from Bacillus sp. KSM-K38 having the accession number AB051102. (j) A variant showing at least 80% identity with the mature amino acid sequence of AAI10 derived from Bacillus sp. (SEQ ID NO: 7 in the pamphlet of WO 2016 / 180748), preferably containing a mutation in one or more of the following position modifications at one or more of the positions 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 showing 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 the mutation 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. A preferred amylase is the deletion G182* and G183 * both, optionally including one or more of the following series 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 showing at least 80% identity with the mature amino acid sequence of Alicyclobacillus amylase (SEQ ID NO: 8 in WO 2016 / 180748 pamphlet).

[0085] The amylase can be an enzyme subjected to genetic manipulation, and one or more of the amino acids that are prone to bleaching oxidation are replaced with amino acids that are less prone to oxidation. In particular, the methionine residue is preferably replaced with any other amino acid. In particular, it is preferable that the most oxidizable methionine is replaced. Preferably, the methionine at the position corresponding to 202 in SEQ ID NO: 2 is replaced. Preferably, the methionine at this position is replaced with threonine or leucine, preferably leucine.

[0086] 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® AT 9000 (Biozym Biotech Trading GmbH (Wehlistrasse 27b A-1200 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 (14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan)). In one embodiment, suitable amylases include ATLANTIC®, STAINZYME®, POWERASE®, INTENSA® and STAINZYME PLUS®, ACHIEVE ALPHA®, and mixtures thereof.

[0087] Preferably, the product of the present invention contains at least 0.01 mg, preferably about 0.05 to about 10 mg, more preferably about 0.1 to about 6 mg, particularly about 0.2 to about 5 mg of active amylase per gram of the composition.

[0088] Preferably, the protease and / or amylase of the second composition is in the form of granules, which granules contain more than 29% by weight of sodium sulfate, and / or the weight ratio of sodium sulfate to the active enzyme (protease and / or amylase) is 3:1 to 100:1, or preferably 4:1 to 30:1, or more preferably 5:1 to 20:1.

[0089] Crystal growth inhibitor A crystal growth inhibitor is a material that can bind to calcium carbonate crystals to prevent further growth of seeds such as aragonite and calcite.

[0090] A particularly preferred crystal growth inhibitor for use herein is HEDP (1-hydroxyethylidene 1,1-diphosphonic acid). The composition of the present invention preferably contains 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, particularly 0.5 to 2% by weight of a crystal growth inhibitor, preferably HEDP, of the second composition.

[0091] Metal care agent A metal care agent can prevent or reduce the clouding, corrosion or oxidation of metals including aluminum, stainless steel, and non-ferrous metals such as silver and copper. Preferably, the second composition contains 0.1 to 5% by weight, more preferably 0.2 to 4% by weight, especially 0.3 to 3% by weight of a metal care agent of the composition, and preferably, the metal care agent is benzotriazole (BTA).

[0092] Glass care agent A glass care agent protects the appearance of glass products during the dishwashing process. Preferably, the second composition contains 0.1 to 5% by weight, more preferably 0.2 to 4% by weight, especially 0.3 to 3% by weight of a glass care agent of the composition, and preferably, the glass care agent is a zinc salt.

[0093] Bleaching agent In some embodiments, the composition may preferably contain about 8 to about 30% by weight, more preferably about 9 to about 25% by weight, even more preferably about 9 to about 20% by weight of a bleaching agent of the composition.

[0094] Inorganic and organic bleaching agents are suitable for use herein. Examples of inorganic bleaching agents include perhydrates such as perborates, percarbonates, persulfates, and peroxysilicates. Inorganic perhydrates are usually alkali metal salts. The inorganic perhydrates can be included as crystalline solids without additional protection. Alternatively, the salts may be coated. Suitable coatings include sodium sulfate, sodium carbonate, sodium silicate, and mixtures thereof. The coating can be applied as a mixture applied to the surface or applied by sequential lamination.

[0095] Alkali metal percarbonates, particularly sodium percarbonate, are preferred bleaching agents for use herein. The percarbonate is most preferably incorporated into the product in a coated form that provides in-product stability.

[0096] Potassium monopersulfate is another inorganic perhydrate useful herein.

[0097] Typical organic bleaching agents are organic peroxyacids, particularly dodecanedioxy acid, tetradecanedioxy acid, and hexadecanedioxy acid. Mono- and diperazelic acids, mono- and diperbrassylic acids 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.

[0098] More typical organic bleaching agents include peroxy acids, specific examples of which are alkyl peroxy acids and aryl peroxy acids. Preferred representative examples are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acid, as well as peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)], o-carboxybenzamideperoxycaproic acid, N-nonenylamidopeladipic acid and N-nonenylamidosuccinate, and (c) aliphatic and araliphatic diperoxycarboxylic 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).

[0099] Bleaching activator Bleaching activators are typically organic peracid precursors that enhance the bleaching action during the washing process at temperatures of 60 °C or lower. Bleaching activators suitable for some embodiments include compounds that, under perhydrolysis conditions, preferably give aliphatic peroxoycarboxylic acids having 1 to 12 carbon atoms, particularly 2 to 10 carbon atoms, and / or optionally substituted perbenzoic acids. Suitable substances have an O-acyl group and / or an N-acyl group with a specified number of carbon atoms and / or an optionally substituted benzoyl group. Polyacylated alkylenediamines, particularly tetraacetylethylenediamine (TAED), acylated triazine derivatives, particularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, particularly tetraacetylglycoluril (TAGU), N-acylimides, particularly N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, particularly n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), decanoyloxybenzoic acid (DOBA), carboxylic anhydrides, particularly phthalic anhydride, acylated polyhydric alcohols, particularly triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and triethylacetyl citrate (TEAC) are also preferred. When present, the second composition contains 0.01 to 5, preferably 0.2 to 2% by weight of a bleaching activator, preferably TAED, based on the composition.

[0100] Bleaching catalyst In some embodiments, the second composition may contain a bleaching catalyst, preferably a metal-containing bleaching catalyst. More preferably, the metal-containing bleaching catalyst is a transition metal-containing bleaching catalyst, particularly a manganese- or cobalt-containing bleaching catalyst.

[0101] Preferred bleaching catalysts for use herein include mangantriazacyclononane and related complexes, Co, Cu, Mn and Fe bispyridylamine and related complexes; and pentaminecobalt(III) acetate and related complexes.

[0102] The second composition may contain a bleaching catalyst in an amount of 0.001 to 0.5%, more preferably 0.002 to 0.05% by weight of the composition. Preferably, the bleaching catalyst is a manganese bleaching catalyst, more preferably manganese 1,4,7-trimethyl-1,4,7-triazacyclononane.

Examples

[0103] (Example 1) As detailed below, two automatic dishwashing compositions were prepared.

[0104] I. Preparation of test compositions The following detergent compositions were used for the tests:

[0105]

Table 1

[0106] II. Test staining - tea cup Tea cups (Schönburg, thickness 6 - 8 mm) were soiled with black Assam tea prepared using the following procedure (adopted from the Recommendations for the Quality Evaluation of the Detergent Performance of Dishwashing Machines from Dishwashing Detergents of the IKW Working Group (Part B, updated 2015)). 1. Prepare 3 mmol of Ca and Mg (16.8°d) water and adjust the pH to 7.5 using HCl or NaOH. 2. Prepare an iron sulfate solution by adding 5 g of Fe2(SO4)3 + 1 ml of HCl (37%) to 1 liter of demineralized water. 3. Add 0.2 ml of ferric sulfate to 4 liters of 3 mmol of water and bring to a boil. 4. Prepare 2 tea bags each containing 30 g of Twinings Assam loose leaf tea. 5. When the water is boiling, add the tea bags and steep for 5 minutes. 6. After 5 minutes, fill the tea cups with 100 mL of tea that should be at approximately 93°C. 7. Remove 20 mL of tea every 5 minutes until the tea cups are empty. 8. Repeat this process once more to freshly brew the tea. 9. The soiled teacups are stored at room temperature and humidity for at least 3 days before use in the performance test.

[0107] III. Additional Ballast Soil 1 To apply additional soil stress to the test, add a soil mixture to the dishwasher as prepared by the procedure described below.

[0108] [Table 2]

[0109] Soil Preparation 1. Combine vegetable oil and whole eggs and mix well (about 30 minutes). 2. Add ketchup and mustard and continue to stir vigorously. 3. Melt the fat, cool to about 40 °C, then add to the mixture and mix well. 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 in a plastic pot and freeze.

[0110] IV. Test Washing Procedure

[0111] [Table 3]

[0112] (Example 1) Separate additions of 1 dose of detergent and NaOH solution were added to the automatic dishwasher as shown below. The NaOH solution was added according to the pH meter reading of the wash solution to reach and maintain pH 12 throughout the pre-wash (t = 3 - 12). The average NaOH addition over 4 runs is listed in the table below.

[0113] [Table 4]

[0114] The above items were placed in a dishwashing machine and washed 4 times using Formulations A and B, and sets of 8 teacups were obtained for each test leg (2 sets per wash). The teacups were then graded on a visual scale of 1 to 10, where 1 is no removal and 10 is complete removal of tea stains. The average teacup score was calculated and is shown below.

[0115]

Table 5

[0116] As can be seen, when the pH of the pre-wash is raised above pH 11 using NaOH, tea washing in the absence of bleach is improved.

[0117] (Examples 2 to 4) As detailed below, two automatic dishwashing compositions were prepared.

[0118] I. Preparation of Test Compositions The following detergent compositions were used to conduct the tests:

[0119]

Table 6

[0120] III. Test Stains a. BoBo Tiles The baked-on stains and char (BoBO) stains used were macaroni and cheese baked on stainless steel tiles, prepared using the following method: 1. 708 mL of water was boiled in a pan on top of the top of a cooking range, and 82.5 g of Kraft Macaroni & Cheese Dinner (registered trademark) dry pasta was added to the boiling water. 2. The pasta was boiled for 7 minutes. 3. In another container, 118 mL of whole milk and 10 g of margarine were mixed and microwaved at high power for 1.3 minutes to melt the margarine. 4. When the pasta was cooked, the water was drained, and the pasta was added to a food processor together with the milk and dry cheese and mixed for 2 minutes to make the mixture uniform. 5. Then, a stainless-steel style was prepared by applying a uniform layer of the mixture onto a standard metal template that was 1 mm thick and had eight holes drilled through it with a diameter of 7 mm. 6. The template was removed, leaving 80 macaroni and cheese spots with a diameter of 7 mm. 7. Then, the soiled tile was placed in an oven at 204 °C for 7 minutes.

[0121] III. Additional Ballast Soil 1 To add additional soil stress to the test, a soil mixture is added to the dishwasher as prepared by the procedure described below.

[0122]

Table 7

[0123] Soil Preparation 7. Combine the vegetable oil and whole eggs and mix well (about 30 minutes). 8. Add the ketchup and mustard and continue to stir vigorously. 9. Melt the fat, cool to about 40 °C, then add to the mixture and mix well. 10. Add the cream and milk and stir. 11. Add the powdered solid ingredients and mix everything into a smooth paste. 12. Put 50 g of the soil mixture into a plastic pot and freeze it.

[0124] IV. Test Washing Procedure

[0125]

Table 8

[0126] (Example 2) Each BoBo tile is placed in a bench-top rig that contains four compartments each mimicking the spray operation of a full-scale ADW machine. The tiles are washed in the bench-top rig for 10 minutes in 5 L of water at 8 gpg, 50 °C and adjusted to pH 12 using 9.5 mL of 50% NaOH solution. Then, test legs A - C are placed in a Beko automatic dishwashing machine. Then, the experiment is repeated.

[0127]

Table 9

[0128] The tiles are weighed before soil addition, after soil addition, and after washing to calculate the % of soil removed.

[0129]

Table 10

[0130] As can be seen, adding Miranol Ultra® L-32 E to the bench-top rig and subsequently washing at 35 °C in a Beko automatic dishwashing machine improves the washing of Bobo removal.

[0131] (Example 3) Each BoBo tile is placed in a bench-top rig that contains four compartments each mimicking the spray operation of a full-scale ADW machine. The tiles are washed in the bench-top rig for 10 minutes in 5 L of water at 8 gpg, 30 °C and adjusted to pH 12 using 9.5 mL of 50% NaOH solution. Then, test legs A - C are placed in a Miele automatic dishwashing machine, and test legs D and E are placed in a Beko automatic dishwashing machine. Then, the experiment is repeated.

[0132]

Table 11

[0133] Weigh the tile before soiling addition, after soiling addition, and after washing, and calculate the % of soiling removed.

[0134]

Table 12

[0135] As can be seen from the figure, the addition of triethanolamine, DOWANOL™ DPnB, and Trilon® Ultimate 1G improves Bobo removal.

[0136] The dimensions and values disclosed in this specification are not to 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 the functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.

Claims

1. A method for washing dishes in a household dishwashing machine, comprising: a) placing the dishes in the dishwashing machine; b) supplying a first highly alkaline composition to the dishwashing machine to produce a first cleaning liquid having a pH of 11.5 or higher; c) supplying a second low-alkalinity composition to the dishwashing machine to produce an alkaline second cleaning liquid having a pH of 9 or higher and less than 11; d) subjecting the dishes to the first composition before subjecting them to the second composition, wherein the method includes using a program having a pre-wash and a main wash, the first composition is supplied to the pre-wash, and the second composition is supplied to the main wash.

2. The method according to claim 1, wherein the dishes are subjected to the first composition at least 3 minutes before being subjected to the second composition.

3. The method according to claim 1 or 2, further comprising supplying an alkali source after the first cleaning liquid is produced to keep the initial pH of the first cleaning liquid constant.

4. The method according to any one of claims 1 to 3, wherein the maximum temperature of the first cleaning liquid is ambient temperature and the maximum temperature of the second cleaning liquid is higher than ambient temperature.

5. The method according to any one of claims 1 to 4, wherein the first composition contains an alkali metal hydroxide.

6. The method according to any one of claims 1 to 5, wherein the second composition contains an enzyme and the first and second compositions do not contain a bleaching agent.

7. The method according to any one of claims 1 to 6, wherein the first composition or the second composition contains a mixture containing an alkanolamine, a glycol ether, and a complexing agent, preferably, the mixture contains a salt of triethanolamine, dipropylene glycol butyl ether, and methylglycine diacetic acid.

8. The method according to claim 6, wherein the first composition contains the mixture and the method includes using a short program, or the second composition contains the mixture and the method includes using a long program.

9. The method according to any one of claims 1 to 6, wherein the first composition further comprises an alkyl amphocarboxylate surfactant, the carboxylate group in the alkyl amphocarboxylate surfactant contains 2 to 4 carbon atoms, and the alkyl group in the alkyl amphocarboxylate surfactant contains 6 to 24 carbon atoms.

10. The method according to claim 9, wherein the alkyl amphocarboxylate surfactant contains sodium cocoamphoacetate.

11. The method according to any one of claims 9 to 10, wherein the maximum temperature of the first cleaning liquid is 30 °C or higher.

12. An automatic dishwashing pack suitable for use in the method according to any one of claims 1 to 11, comprising at least two different compartments, a first compartment containing the first composition or a part thereof, and a second compartment containing the second composition or a part thereof.

13. The method according to any one of claims 1 to 11, wherein the pack according to claim 12 is disposed inside the dishwashing machine, and the first and second compositions are introduced into a plurality of automatic dishwashing programs.

14. Use of the method according to claim 6 for providing removal of tea stains, or use of the method according to any one of claims 7 to 11 for providing removal of cooked stains, burnt-on stains, and charred stains.

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