Method for removing starch-containing dry stain

Abstract

To provide a method for effectively removing starch-containing dry stain adhering to an article such as tableware.SOLUTION: The present invention pertains to a method for removing starch-containing dry stain that comprises bringing an aqueous composition containing (a) a sulfosuccinic alkyl ester having a C 8-14 alkyl group, (b) a surfactant (but excluding (a)), (c) an amylase, and water, into contact with starch-containing dry stain adhering to an article, and removing the stain by the application of external force.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for removing starch-containing dried stains. [Background technology]

[0002] Stains that adhere to hard items such as tableware include starch stains, protein stains, oily stains, and combinations of these. Common methods for washing dishes in a typical household include scrubbing the dishes with a cleaning solution on a flexible, porous material such as a sponge, and using a dishwasher.

[0003] On the other hand, it is also known that dishwashing detergents utilize surfactants such as sulfosuccinate-type surfactants and enzymes such as amylase. Patent Document 1 discloses a technology for a liquid dishwashing detergent composition containing dialkyl sulfosuccinic acid and an amylase enzyme. Furthermore, Patent Document 2 discloses a technology for a liquid detergent composition containing dialkyl sulfosuccinates that is effective against oil and / or starch stains, and this publication describes a technology utilizing enzymes. Furthermore, Patent Documents 3 and 4 disclose technologies for liquid cleaning agent compositions for tableware and / or hard articles around the kitchen that utilize alkyl sulfosuccinate and enzymes. Furthermore, Patent Document 5 discloses a method for removing starch stains, which involves (a) contacting an object to which starch stains are attached with a treatment solution containing 0.1% to 10% by mass of one or more compounds selected from polyhydric alcohols with a molecular weight of 150 or less, leaving the object for more than 30 minutes, and then removing the starch stains. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-100745 [Patent Document 2] Japanese Patent Publication No. 2008-507611 [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2019-182911 [Patent Document 4] Japanese Unexamined Patent Application Publication No. 2020-152757 [Patent Document 5] Japanese Unexamined Patent Application Publication No. 2021-80377 [Summary of the Invention] [Problems to be Solved by the Invention] ​​​​​​​​​​​​​​​​​​ The present invention relates to a method for removing starch-containing dried dirt (hereinafter referred to as starch-containing dried dirt) by applying an external force, wherein an aqueous composition containing (a) an alkyl sulfosuccinate having an alkyl group with 8 to 14 carbon atoms (hereinafter referred to as component (a)), (b) a surfactant (excluding component (a)) (hereinafter referred to as component (b)), (c) amylase (hereinafter referred to as component (c)), and water is brought into contact with the dried dirt containing starch adhering to an article (hereinafter referred to as starch-containing dried dirt). The present invention includes a method for removing starch-containing dried dirt, comprising bringing an aqueous composition of the present invention containing component (a), component (b), component (c), and water into contact with the dried dirt containing starch adhering to an article, and scrubbing it with a flexible material. [Effects of the Invention]

[0009] The present invention provides a method for removing dried, starch-containing stains that adhere to articles such as tableware, which is highly effective in removing them. More specifically, the present invention provides a removal method that can remove hard-to-remove dried starch-containing stains in a shorter amount of time. Because the removal method of the present invention provides high cleaning power against starch-containing dried stains in a short time, so-called speed cleaning becomes possible. [Modes for carrying out the invention]

[0010] In this invention, an aqueous composition containing component (a), component (b), component (c), and water is brought into contact with dried starch-containing dirt adhering to an article, and the dirt is removed by applying an external force to the contact area, such as scrubbing with a flexible material or applying a stream of water. In this invention, the combination of component (a) and component (b) promotes the penetration of component (c) into the dried starch-containing dirt, thereby weakening the dried starch-containing dirt, which can be easily removed in a short time by applying an external force. The inventors believe that promoting the penetration of component (c) into dried starch-containing dirt leads to an improvement in the enzymatic reaction of component (c), which in turn reduces the amount of cleaning power enhancing components such as surfactants and solvents used, and thus contributes to a sustainable society in terms of reducing CO2 emissions. First, the aqueous composition of this invention will be described.

[0011] (a) The component is an alkyl sulfosuccinate ester in which the alkyl group has 8 to 14 carbon atoms.

[0012] (a) The component may be a monoester or a diester. Preferably it is a diester, and more preferably a branched alkyl sulfosuccinate diester in which the alkyl group is a branched alkyl group.

[0013] (a) The alkyl group of component (a) has 8 or more carbon atoms, preferably 9 or more, and 14 or less, preferably 13 or less, more preferably 11 or less, and even more preferably 9 or 10 carbon atoms.

[0014] (a) The alkyl group of component is preferably a branched alkyl group, more preferably a branched alkyl group having 8 to 14 carbon atoms, even more preferably a branched alkyl group having 9 to 13 carbon atoms, and even more preferably a branched alkyl group having 9 or 10 carbon atoms. (a) The branched alkyl group of component (a) is preferably a branched alkyl group having a main chain with 6 or 7 carbon atoms and one or more side chains, with a total number of carbon atoms in the side chains of 3 or 4. (a) The branched alkyl group of the component is preferably a branched alkyl group selected from a 2-propylheptyl group and a 3,5,5-trimethylhexyl group, and more preferably a 2-propylheptyl group.

[0015] Examples of the component (a) include a branched alkyl sulfosuccinate represented by the following general formula (a1).

[0016] [Chemical formula]

[0017] [In the formula, R 1a , R 2a are each independently a branched alkyl group having 8 to 14 carbon atoms. A 1 , A 2 are each independently an alkylene group having 2 to 4 carbon atoms, x and y are the average number of moles of addition, and each is independently 0 or more and 6 or less. M 1 is a hydrogen atom or a cation. ]

[0018] Furthermore, examples of the component (a) include a branched alkyl sulfosuccinate represented by the following general formula (a1-1). This compound is a compound of the general formula (a1) where x = 0 and y = 0.

[0019] [Chemical formula]

[0020] [In the formula, R 1a , R 2a are each independently a branched alkyl group having 8 to 14 carbon atoms. M 1 is a hydrogen atom or a cation. ]

[0021] The following description can be applied to each of the general formula (a1) and the general formula (a1-1). R 1a , R 2a may have the same or different number of carbon atoms. R1a , R 2a The carbon atoms have 8 or more carbon atoms, preferably 9 or more, and 14 or less carbon atoms, preferably 13 or less, more preferably 11 or less, and even more preferably 9 or 10 carbon atoms. In this invention, hydrocarbon residues obtained by removing a hydroxyl group from a secondary alcohol are included in the chain-branched hydrocarbon group.

[0022] In the present invention, R 1a , R 2a In a chain-like branched hydrocarbon group, the hydrocarbon chain with the largest number of carbon atoms, counting from the carbon atom bonded to the oxygen atom, is designated as the main chain, and the hydrocarbon chains branching off from the main chain are designated as side chains. When there are two or more possible main chains, that is, when there are two or more hydrocarbon chains with the largest number of carbon atoms (hereinafter also referred to as the longest hydrocarbon chains), the main chains are determined in the following order. 1. The side chain branching from the longest hydrocarbon chain with the larger number of carbon atoms is designated as the main chain. 2. Next, if the number of carbon atoms in the side chains branching from the longest hydrocarbon chain is the same, the one with more side chains branching from the longest hydrocarbon chain will be considered the main chain. 3. Next, if the number of side chains branching from the longest hydrocarbon chain is the same, the main chain is the one with the side chains attached to the carbon atom closer to the oxygen atom, counting from the carbon atom bonded to the oxygen atom. 4. Next, if the carbon atoms in the side chains closest to the oxygen atom are in the same position, the one with more carbon atoms in the side chain closest to the oxygen atom will be considered the main chain. Furthermore, if two or more longest hydrocarbon chains have the same symmetrical structure, either one may be used as the main chain.

[0023] R 1a , R 2a In each branched alkyl group, the total number of carbon atoms constituting the side chain may be the same or different, but from the viewpoint of cleaning properties such as solid fats and foam suppression, it is preferably 3. In this invention, the total number of carbon atoms constituting the side chains refers to the sum of the carbon atoms in all side chains other than the main chain in a single branched alkyl group. If there are multiple side chains, it refers to the sum of the carbon atoms in all of those side chains.

[0024] R 1a , R 2a The number of side chains may be the same or different, and from the viewpoint of cleaning properties such as solid fats and foam suppression, it is 1 or more, preferably 3 or less, and more preferably 2 or less. In the present invention, the number of side chains refers to the number of side chains branching from the main chain, and the number of side chains does not change even if a side chain has further side chains branching from it. However, from the viewpoint of cleaning properties and foam suppression properties for solid fats, etc., a side chain may have further side chains branching from it.

[0025] R 1a , R 2a The number of branched carbon atoms may be the same or different, and from the viewpoint of cleaning properties such as solid fats and foam suppression, it is 1 or more, preferably 3 or less, and more preferably 2 or less. In this invention, the number of branched carbon atoms is the sum of the number of tertiary and quaternary carbon atoms in the chain-type branched hydrocarbon group.

[0026] R 1a , R 2a A preferred embodiment is R 1a , R 2a The total number of carbon atoms in each branched hydrocarbon chain is independently 9 to 11, and further 9 or 10; the number of carbon atoms in each main chain is independently 6 or 7; the number of carbon atoms constituting each side chain is independently 1 to 3; and the number of side chains is independently 1.

[0027] R 1a , R 2a The specific branched alkyl groups may be the same or different, and branched alkyl groups selected from 2-propylheptyl groups and 3,5,5-trimethylhexyl groups are preferred.

[0028] In general formula (a1), A 1 , A 2 Each of these is an alkylene group having 2 or more carbon atoms and 4 or fewer carbon atoms, preferably 3 or fewer. In general formula (a1), x and y are the average number of moles added, and from the viewpoint of cleaning properties and anti-foaming properties for solid fats, etc., they are independently 0 or more, and 6 or less, preferably 4 or less, more preferably 2 or less, and even more preferably 0. Furthermore, x+y is preferably 0 or greater, preferably 12 or less, more preferably 6 or less, even more preferably 3 or less, and even more preferably 0, from the viewpoint of cleaning properties such as solid fats and foam suppression.

[0029] In general formula (a1), M 1 This is a hydrogen ion, or an inorganic cation such as a sodium ion, ammonium ion, potassium ion, or magnesium ion, or an organic cation such as a monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, or morpholinium ion, preferably an inorganic cation selected from sodium ions, ammonium ions, potassium ions, and magnesium ions.

[0030] In general formula (a1), R 1a , R 2a The method for preparing the same compound is not particularly limited, but for example, it can be produced by referring to the method described in U.S. Patent Publication No. 2,028,091, and R 1a , R 2a As a method for preparing asymmetric compounds with different properties, for example, they can be manufactured by referring to Japanese Patent Publication No. 58-24555. (a) As a raw material for component (a), an alcohol with a predetermined number of carbon atoms to which an alkylene oxide has been added can also be used. Suitable alcohols used in the production of component (a) of the present invention include: (1) Primary alcohols such as 3,5,5-trimethylhexane-1-ol and 2-propylheptan-1-ol, (2) Secondary alcohols, such as 5-nonanol and 2,6-dimethyl-4-heptanol These are some examples.

[0031] The aqueous composition of the present invention may contain component (a) in amounts of, for example, 10 ppm or more, more than 100 ppm or more, more than 150 ppm or more, and 1000 ppm or less, and more than 700 ppm or less (ppm is by mass, the same applies hereinafter).

[0032] (b) Component is a surfactant [excluding component (a)]. (b) The components include one or more surfactants selected from (b1) anionic surfactants (excluding component (a)) (hereinafter referred to as component (b1)), (b2) amphoteric surfactants (hereinafter referred to as component (b3)), and (b3) nonionic surfactants (hereinafter referred to as component (b3)).

[0033] (b1) Examples of anionic surfactants of component (b1) include alkyl sulfate esters, polyoxyalkylene alkyl ether sulfate esters, alkane sulfonates, alkylbenzene sulfonates, higher fatty acids or their salts, polyoxyethylene alkyl ether carboxylic acids or their salts, N-acyl amino acids or their salts, alkyl phosphate esters, and polyoxyethylene alkyl ether phosphates. When the anionic surfactant has an alkyl group, the alkyl group may have 8 or more carbon atoms, moreover 12 or more, and 18 or less, and moreover 14 or less. When the anionic surfactant has a polyoxyalkylene group, the average number of added moles of oxyalkylene groups of the polyoxyalkylene group may be, for example, 0.1 or more, moreover 0.4 or more, and 4 or less, and moreover 2 or less. Examples of oxyalkylene groups include oxyethylene groups and oxypropylene groups. Examples of salts of anionic surfactants include alkali metal salts such as sodium salts and potassium salts. (b1) From the viewpoint of swelling the starch and promoting the enzymatic reaction, alkyl sulfate esters and polyoxyalkylene alkyl ether sulfate esters are preferred for component (b1).

[0034] Examples of amphoteric surfactants for component (b2) include N-alkanoyl (alkanoyl group is, for example, a lauroyl group or a myristyl group, and the same applies to the following alkanoyl groups) aminopropyl-N,N-dimethylamine oxide, N-long-chain alkyl (long-chain alkyl group is, for example, a lauryl group or a myristyl group, and the same applies to the following long-chain alkyl groups)-N,N-dimethylamine oxide, N-alkanoylaminopropyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-long-chain alkyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-long-chain alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, N-long-chain alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine. (b2) The component is preferably N-long-chain alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine.

[0035] (b3) Examples of nonionic surfactants of component (b3) include alkyl monoglyceryl ethers, polyoxyalkylene monoalkyl or alkenyl ethers, alkyl polyglycosides (glycoside-type nonionic surfactants), sorbitan-based nonionic surfactants, aliphatic alkanolamides, fatty acid monoglycerides, sucrose fatty acid esters, monoethanolamine, diethanolamine, methylmonoethanolamine, and amidates of alkanolamines with fatty acids such as lauric acid and myristic acid. When the nonionic surfactant has an alkyl or alkenyl group, the alkyl or alkenyl group may have 3 or more carbon atoms, moreover 5 or more, and 15 or less, and moreover 13 or less. Examples of oxyalkylene groups include oxyethylene groups and oxypropylene groups, with oxyethylene groups being preferred. (b3) Component is preferably an alkyl monoglyceryl ether, and more preferably a compound selected from glycerin mono-2-ethylhexyl ether, glycerin monoisodecyl ether, and glycerin mono-2-propylheptyl ether, from the viewpoint of promoting the enzymatic reaction, with glycerin mono-2-ethylhexyl ether being more preferred.

[0036] The aqueous composition of the present invention preferably contains component (b1), component (b2), and component (b3) as component (b). (b1) Component is a component that is preferably included in the aqueous composition of the present invention from the viewpoint of swelling the starch and promoting the enzymatic reaction. Component (b2) is preferable to include in the aqueous composition of the present invention because, when used in combination with component (b1) when starch and oil stains are present together, it enhances the cleaning power against oil stains and also enhances the cleaning power against stains that are present together with starch. (b3) Component is a component that is preferably included in the aqueous composition of the present invention from the viewpoint of promoting the enzymatic reaction.

[0037] The aqueous composition of the present invention preferably contains component (b1) as component (b). The mass ratio of the content of component (b1) to the total content of component (a) and component (b), (b1) / [(a)+(b)], is preferably 0.35 to 0.60 from the viewpoint of swelling the starch and promoting the enzymatic reaction. Furthermore, the mass ratio of the content of component (b1) to the total content of component (b), (b1) / (b), is preferably 0.1 to 1.0 from the viewpoint of swelling the starch and promoting the enzymatic reaction.

[0038] The aqueous composition of the present invention may contain component (b) in amounts of, for example, 1000 ppm or more, more than 2000 ppm or more, and 10000 ppm or less, and more than 8000 ppm or less.

[0039] The aqueous composition of the present invention has a mass ratio (a) / [(a)+(b)], which is the mass ratio of the content of component (a) to the total content of component (b), which is preferably 0.01 or more, more preferably 0.05 or more, and preferably 0.5 or less, and more preferably 0.15 or less, from the viewpoint of cleaning power.

[0040] The aqueous composition of the present invention has a mass ratio (a) / (b1) of the content of component (a) to the content of component (b1), which is preferably 0.05 or more, more preferably 0.1 or more, and preferably 0.5 or less, and more preferably 0.3 or less.

[0041] In the aqueous composition of the present invention, the mass ratio of the total content of component (a) and component (b1) to the content of component (b2), [(a)+(b1)] / (b2), is preferably 0.5 or higher, more preferably 0.8 or higher, and preferably 10 or lower, and more preferably 3 or lower, from the viewpoint of cleaning power against oily stains when starch stains and oily stains are present together.

[0042] In the aqueous composition of the present invention, the mass ratio of the content of component (b3) to the sum of the content of component (a) and the content of component (b), which is (b3) / [(a)+(b)], is preferably 0.02 or more, more preferably 0.03 or more, and preferably 0.5 or less, and more preferably 0.15 or less, from the viewpoint of enzyme-based cleaning effect.

[0043] (c) The component is amylase. Examples of amylases include bacteria such as Bacillus subtilis Marburg, Bacillus subtilis natto, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus cereus, Bacillus macerans, Pseudomonas stutzeri, and Klebusiella aerogenes, as well as actinomycetes such as Streptomyces griseus, and Aspergillus oryzae and Aspergillus niger. Many types of amylase can be used, including those obtained from various organisms such as fungi (e.g., niger), seeds of grasses and legumes, and digestive glands of animals such as humans and pigs. The amylase used in this invention can be obtained by inoculating host cells transformed with the aforementioned microorganisms or their mutant strains, or with recombinant vectors having DNA sequences encoding these enzymes or their mutants, into a culture medium containing an assimilated carbon source, nitrogen source, and other essential nutrients, culturing them according to conventional methods, and following general enzyme collection and purification methods. The enzyme solution obtained in this way can be used as is, but it can also be further purified, crystallized, powdered, or liquid-formulated by known methods. The amylase used in this invention is preferably α-amylase. Examples of commercially available amylases that can be used include the trademarked Rapidase (manufactured by Gistbrokers), the trademarked Termamyl, Duramyl, and Steinzyme (manufactured by Novozymes Japan Co., Ltd.), Amplify (manufactured by Novozymes), and the trademarked Plaster ST and Plaster OxAm (manufactured by Genencor International).

[0044] The aqueous composition of the present invention contains component (c) as an enzyme protein, preferably at a concentration of 0.1 ppm or more, more preferably at a concentration of 1 ppm or more, from the viewpoint of cleaning power, and preferably at a concentration of 1000 ppm or less, more preferably at a concentration of 500 ppm or less, from the viewpoint of economic efficiency. The enzyme protein of component (c) can be quantified using the Bio-Rad Protein Assay Kit II (catalog number 500-0002) according to the standard assay method, with bovine serum albumin provided with the kit used as the standard protein. Hereinafter, the content of component (c) refers to the amount as an enzyme protein unless otherwise specified.

[0045] The aqueous composition of the present invention has a mass ratio (a) / (c) of the content of component (a) to the content of component (c), which is preferably 10 or more, more preferably 200 or more, and preferably 5000 or less, and more preferably 500 or less.

[0046] The aqueous composition of the present invention has a mass ratio [(a)+(b1)] / (c), which is the mass ratio of the content of component (a), the content of component (b1), and the content of component (c) (as enzyme protein), preferably 500 or more, more preferably 1500 or more, and preferably 5000 or less, and more preferably 2500 or less.

[0047] The aqueous composition of the present invention may contain any components other than components (a) to (c). Optional components may include solvents, hydrotropes, dispersants, pH adjusters, thickeners, viscosity modifiers, fragrances, colorants, antioxidants, preservatives, antifoaming agents, bleaching agents, and bleaching activators.

[0048] The aqueous composition of the present invention contains water. The water is used in the remainder of the aqueous composition of the present invention.

[0049] Next, the removal method of the present invention will be described. In the removal method of the present invention, an aqueous composition containing component (a), component (b), component (c), and water is brought into contact with starch-containing dried dirt adhering to an article, and the dirt is removed by applying an external force. The external force can be applied by, for example, scrubbing with a flexible material, applying a water stream, or a combination thereof. In the present invention, it is preferable to apply the external force by scrubbing with a flexible material at least. In the present invention, the water stream may be pressurized water, for example, high-pressure shower water sprayed from a rotating nozzle in a dishwasher.

[0050] Examples of articles targeted by the removal method of the present invention include tableware and hard articles around the kitchen. Specifically, as tableware, for example (i) Dishes such as plates and bowls, (ii) Storage containers such as Tupperware and glass jars, (iii) Cooking utensils such as knives, cutting boards, pots, frying pans, and fish grills, (iv) Cooking appliances such as food processors and blenders, etc. These include components and utensils that come into contact with the food ingredients. For convenience, in this invention, these will be referred to as "tableware." Furthermore, hard materials used around the kitchen are items used in the vicinity of the kitchen, and specifically, for example, (1) Storage places for food, dishes, and cooking utensils such as refrigerators and cupboards, (2) Drains, countertops, range hoods, sinks, gas ranges, microwave ovens and other food preparation areas, (3) Floors, walls, etc. surrounding the storage area and the cooking area. In this invention, these are referred to as "hard articles for kitchen use" for convenience.

[0051] The materials used for tableware and other items include plastic (including silicone resin), metal, ceramics, wood, and combinations thereof.

[0052] Japanese Patent Publication No. 2021-80377 discloses a method for removing starch stains that can be easily removed from objects to which starch-containing stains have adhered. In this method, after bringing the object to which the starch stain has adhered into contact with the treatment liquid, the object is left for 30 minutes or more to suppress the drying of the starch and prevent the starch from hardening due to drying, thereby making it possible to easily remove the starch stain without, for example, rinsing. The present invention provides a method for removing starch-containing stains that can be removed quickly and easily in a short time, even from starch stains that have already dried, without the need for methods such as immersion in a treatment bath or application of a treatment solution before the starch dries. As described above, in the present invention, the combination of components (a) and (b) promotes the penetration of component (c) into the dirt, thereby weakening the dried starch dirt, and high cleaning power can be obtained in a short time by, for example, scrubbing with a flexible material. Component (b1) of component (b) has an excellent effect of swelling starch, so when used, the dirt decomposition reaction by component (c) is further promoted, resulting in even higher cleaning power.

[0053] The method for bringing the aqueous composition of the present invention into contact with starch-containing dried stains is not limited, but methods such as coating and immersion are possible. Coating can be done by methods such as bringing a flexible material impregnated with the aqueous composition of the present invention into contact with the stain, or by brushing the aqueous composition of the present invention onto the stain. When bringing a flexible material impregnated with the aqueous composition of the present invention into contact with the stain, scrubbing can also be done at the same time. For example, the aqueous composition of the present invention can be applied to a flexible material such as a water-soaked sponge, and the dish can be scrubbed by lathering it up by rubbing it several times by hand. Furthermore, in the removal method of the present invention, the aqueous composition of the present invention can be sprayed and brought into contact with the starch-containing dried stain. Spraying is preferably performed using a trigger sprayer.

[0054] The aqueous composition used in the removal method of the present invention can easily remove starch-containing dried stains by applying external force, such as scrubbing with a flexible material or applying a water stream, even with a short contact time with the stains. In the present invention, contact with the aqueous composition and scrubbing with a flexible material may be performed simultaneously. In the present invention, starch-containing dried stains can be scrubbed with a flexible material impregnated with the aqueous composition; that is, scrubbing can be performed while the aqueous composition is in contact with the starch-containing dried stains using a flexible material impregnated with the aqueous composition. Furthermore, in this invention, scrubbing with a flexible material and the application of water flow may be performed simultaneously. In this invention, after contacting the aqueous composition of the present invention with starch-containing dried stains, external force can be applied for, for example, less than 300 seconds, then within 60 seconds, then within 30 seconds, such as scrubbing with a flexible material, applying a stream of water, or a combination of these. In this invention, stubborn starch-containing dried stains can be removed with such short contact time. This is significantly shorter than the soaking time generally used. If the aqueous composition of the present invention is left for a certain period of time after contact, the lower limit of the standing time can be, for example, 1 second or more.

[0055] The flexible material used in this invention can be selected from cloth, sponge, or paper. A specific removal method involves, for example, applying the aqueous composition of the present invention to the flexible material to hold the composition, diluting it with water within the flexible material, and then scrubbing the dishes by lathering it up while rubbing it several times by hand. The amount of aqueous composition to be held in the flexible material is 300 g / m². 3 In addition, 1,000g / m 3 And, 50,000 g / m 3 Below, an additional 20,000 g / m 3 The following are preferable.

[0056] In the removal method of the present invention, it is preferable to rinse articles that have been subjected to external force, such as scrubbing with a flexible material, with water.

[0057] [Aspects of the present invention] The following are examples of embodiments of the present invention. The description of the method for removing starch-containing dried stains according to the present invention can be applied to these embodiments with necessary modifications. Furthermore, the description of each embodiment can be applied to other embodiments with necessary modifications.

[0058] <1> A method for removing starch-containing dried dirt (hereinafter referred to as starch-containing dried dirt) adhering to an article, comprising: (a) an alkyl sulfosuccinate ester having an alkyl group with 8 to 14 carbon atoms [hereinafter referred to as component (a)], (b) a surfactant [excluding component (a)] [hereinafter referred to as component (b)], (c) amylase [hereinafter referred to as component (c)], and water, by contacting the aqueous composition with the article and applying an external force to remove the dirt.

[0059] <2> (a) The alkyl group of component (a) has 8 or more carbon atoms, preferably 9 or more, and 14 or less, preferably 13 or less, more preferably 11 or less, and even more preferably 9 or 10 carbon atoms. <1> The method for removing starch-containing dried stains described in [the relevant document].

[0060] <3> (a) The alkyl group of component is a branched alkyl group, further a branched alkyl group having 8 to 14 carbon atoms, further a branched alkyl group having 9 to 13 carbon atoms, further a branched alkyl group having 9 or 10 carbon atoms, <1> or <2> The method for removing starch-containing dried stains described in [the relevant document].

[0061] <4> (a) The branched alkyl group of component is a branched alkyl group having a main chain with 6 or 7 carbon atoms and one or more side chains, with a total number of carbon atoms in the side chains of 3 or 4. <3> The method for removing starch-containing dried stains described in [the relevant document].

[0062] <5> (a) The branched alkyl group of component is a branched alkyl group selected from a 2-propylheptyl group and a 3,5,5-trimethylhexyl group, and is further a 2-propylheptyl group. <3> or <4> The method for removing starch-containing dried stains described in [the relevant document].

[0063] <6> (a) The component is a branched alkyl sulfosuccinate represented by the following formula (a1) or a salt thereof. <1> ~ <5> A method for removing starch-containing dried stains as described in any of the following.

[0064] [ka]

[0065] [In the formula, R 1a , R 2a Each of these is independently a branched alkyl group having 8 to 14 carbon atoms. 1 , A 2 Each of these is an alkylene group with 2 to 4 carbon atoms, and x and y are the average number of moles added, each independently between 0 and 6. 1 [This is a hydrogen atom or a cation.]

[0066] <7> In formula (a1), A 1 , A 2 Each of these is an alkylene group having 2 or more carbon atoms and 4 or fewer carbon atoms, preferably 3 or fewer carbon atoms. <6> The method for removing starch-containing dried stains described in [the relevant document].

[0067] <8> In formula (a1), x and y are the average number of added moles, and are independently 0 or greater and 6 or less, preferably 4 or less, more preferably 2 or less, and even more preferably 0. <6> or <7> The method for removing starch-containing dried stains described in [the relevant document].

[0068] <9> (a) The component is a branched alkyl sulfosuccinate represented by the following formula (a1-1) or a salt thereof. <1> ~ <6> A method for removing starch-containing dried stains as described in any of the following.

[0069] [ka]

[0070] [In the formula, R 1a , R 2a Each of these is independently a branched alkyl group having 8 to 14 carbon atoms. 1 [This is a hydrogen atom or a cation.]

[0071] <10> In equation (a1) or (a1-1), R 1a , R 2a The number of carbon atoms may be the same or different, and is 8 or more, preferably 9 or more, and 14 or less, preferably 13 or less, more preferably 11 or less, and even more preferably 9 or 10. <6> ~ <9> A method for removing starch-containing dried stains as described in any of the following.

[0072] <11> In formula (a1) or formula (a1-1), M 1 This is a hydrogen ion, or an inorganic cation such as a sodium ion, ammonium ion, potassium ion, or magnesium ion, or an organic cation such as a monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, or morpholinium ion, preferably an inorganic cation selected from sodium ions, ammonium ions, potassium ions, and magnesium ions. <6> ~ <10> A method for removing starch-containing dried stains as described in any of the following.

[0073] <12> The aqueous composition contains component (a) in amounts of 10 ppm or more, 100 ppm or more, 150 ppm or more, 1000 ppm or less, and 700 ppm or less. <1> ~ <11> A method for removing starch-containing dried stains as described in any of the following.

[0074] <13> (b) Component is one or more surfactants selected from (b1) anionic surfactants (excluding component (a)), (b2) amphoteric surfactants, and (b3) nonionic surfactants. <1> ~ <12> A method for removing starch-containing dried stains as described in any of the following.

[0075] <14> (b1) The anionic surfactant of component (b1) is one or more selected from alkyl sulfate salts, polyoxyalkylene alkyl ether sulfate salts, alkane sulfonates, alkylbenzene sulfonates, higher fatty acids or their salts, polyoxyethylene alkyl ether carboxylic acids or their salts, N-acyl amino acids or their salts, alkyl phosphate salts, and polyoxyethylene alkyl ether phosphates. <13> The method for removing starch-containing dried stains described in [the relevant document].

[0076] <15> (b1) The anionic surfactant of component (b1) has an alkyl group, and the alkyl group has 8 or more carbon atoms, moreover 12 or more, and moreover 18 or less, and moreover 14 or less. <13> or <14> The method for removing starch-containing dried stains described in [the relevant document].

[0077] <16> (b1) The anionic surfactant of component (b1) has a polyoxyalkylene group, and the average number of added moles of oxyalkylene groups is 0.1 or more, moreover 0.4 or more, and 4 or less, and moreover 2 or less. <13> ~ <15> A method for removing starch-containing dried stains as described in any of the following.

[0078] <17> (b1) The anionic surfactant of component (b1) has a polyoxyalkylene group, and the oxyalkylene group of the polyoxyalkylene group is an oxyethylene group and / or an oxypropylene group. <13> ~ <16> A method for removing starch-containing dried stains as described in any of the following.

[0079] <18> (b1) The anionic surfactant component is a salt, and the salt is one or more selected from alkali metal salts such as sodium salts and potassium salts. <13> ~ <17> A method for removing starch-containing dried stains as described in any of the following.

[0080] <19> (b2) The amphoteric surfactants of component (b2) are N-alkanoyl (alkanoyl group is, for example, a lauroyl group or a myristyl group, and the same applies to the following alkanoyl groups) aminopropyl-N,N-dimethylamine oxide, N-long-chain alkyl (long-chain alkyl is, for example, a lauryl group or a myristyl group, and the same applies to the following long-chain alkyl)-N,N-dimethylamine oxide, N-alkanoylaminopropyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-long-chain alkyl-N,N-dimethyl-N-carboxymethylammonium One or more selected from methylammonium betaine, N-long-chain alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, N-long-chain alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine. <13> ~ <18> A method for removing starch-containing dried stains as described in any of the following.

[0081] <20> (b2) The component is N-long-chain alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine. <13> ~ <19> A method for removing starch-containing dried stains as described in any of the following.

[0082] <21> (b3) The nonionic surfactant of component (b3) is one or more selected from alkyl monoglyceryl ethers, polyoxyalkylene monoalkyl or alkenyl ethers, alkyl polyglycosides (glycoside-type nonionic surfactants), sorbitan-based nonionic surfactants, aliphatic alkanolamides, fatty acid monoglycerides, sucrose fatty acid esters, and amidates of alkanolamines such as monoethanolamine, diethanolamine, and methylmonoethanolamine with fatty acids such as lauric acid and myristic acid. <13> ~ <20> A method for removing starch-containing dried stains as described in any of the following.

[0083] <22> (b3) The component is an alkyl monoglyceryl ether, and furthermore, one or more selected from glycerin mono-2-ethylhexyl ether, glycerin monoisodecyl ether, and glycerin mono-2-propylheptyl ether, and furthermore, glycerin mono-2-ethylhexyl ether. <13> ~ <21> A method for removing starch-containing dried stains as described in any of the following.

[0084] <23> The aqueous composition contains component (b) in amounts of 1000 ppm or more, more than 2000 ppm or more, and less than 10000 ppm and less than 8000 ppm. <1> ~ <22> A method for removing starch-containing dried stains as described in any of the following.

[0085] <24> The aqueous composition contains component (b1), and the mass ratio of the content of component (b1) to the total content of component (a) and component (b) in the aqueous composition, (b1) / [(a)+(b)], is 0.35 or more and 0.60 or less. <1> ~ <23> A method for removing starch-containing dried stains as described in any of the following.

[0086] <25> The aqueous composition contains component (b1), and the mass ratio of the content of component (b1) to the total content of component (b) in the aqueous composition, (b1) / (b), is 0.1 or more and 1.0 or less. <1> ~ <24> A method for removing starch-containing dried stains as described in any of the following.

[0087] <26> The aqueous composition has a mass ratio of the content of component (a) to the total content of component (b), which is (a) / [(a)+(b)], preferably 0.01 or more, more preferably 0.05 or more, and preferably 0.5 or less, and more preferably 0.15 or less. <1> ~ <25> A method for removing starch-containing dried stains as described in any of the following.

[0088] <27> The aqueous composition contains component (b1), and the mass ratio of the content of component (a) to the content of component (b1) in the aqueous composition, (a) / (b1), is preferably 0.05 or more, more preferably 0.1 or more, and preferably 0.5 or less, more preferably 0.3 or less. <13> ~ <26> A method for removing starch-containing dried stains as described in any of the following.

[0089] <28> The aqueous composition contains component (b1) and component (b2), and the mass ratio of the total content of component (a) and component (b1) to the content of component (b2) in the aqueous composition, [(a) + (b1)] / (b2), is preferably 0.5 or more, more preferably 0.8 or more, and preferably 10 or less, more preferably 3 or less. <13> ~ <27> A method for removing starch-containing dried stains as described in any of the following.

[0090] <29> The aqueous composition contains component (b3), and the mass ratio of the content of component (b3) to the sum of the content of component (a) and component (b) in the aqueous composition, (b3) / [(a)+(b)], is preferably 0.02 or more, more preferably 0.03 or more, and preferably 0.5 or less, and more preferably 0.15 or less. <13> ~ <28> A method for removing starch-containing dried stains as described in any of the following.

[0091] <30> (c) Components include bacteria such as Bacillus subtilis Marburg, Bacillus subtilis natto, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus cereus, Bacillus macerans, Pseudomonas stutzeri, Klebusiella aerogenes, actinomycetes such as Streptomyces griseus, Aspergillus oryzae, and Aspergillus niger. One or more amylases obtained from fungi such as niger, seeds of grasses and legumes, and digestive glands of animals such as humans and pigs, preferably α-amylase, more preferably one or more amylases selected from the following: trade names Rapidase (Gistobrokers), Termamyl, Duramyl and Steinzyme (Novozymes Japan Co., Ltd.), Amplify (Novozymes), and Plaster ST and Plaster OxAm (Genencore International). <1> ~ <29> A method for removing starch-containing dried stains as described in any of the following.

[0092] <31> The aqueous composition contains component (c) as an enzyme protein in a concentration of 0.1 ppm or more, further 1 ppm or more, and 1000 ppm or less, and further 500 ppm or less. <1> ~ <30> A method for removing starch-containing dried stains as described in any of the following.

[0093] <32> The aqueous composition has a mass ratio (a) / (c) of the content of component (a) to the content of component (c), which is preferably 10 or more, more preferably 200 or more, and preferably 5000 or less, more preferably 500 or less. <1> ~ <31> A method for removing starch-containing dried stains as described in any of the following.

[0094] <33> The aqueous composition contains component (b1), and the mass ratio of the content of component (a), the content of component (b1), and the content of component (c) (as enzyme protein), [(a) + (b1)] / (c), is preferably 500 or more, more preferably 1500 or more, and preferably 5000 or less, more preferably 2500 or less. <1> ~ <32> A method for removing starch-containing dried stains as described in any of the following.

[0095] <34> External force is applied by at least one of scrubbing with a flexible material and / or by applying a water flow, and further by scrubbing with a flexible material. <1> ~ <33> A method for removing starch-containing dried stains as described in any of the following.

[0096] <35> Dry, starch-containing dirt is scrubbed away using a flexible material impregnated with an aqueous composition. <34> The method for removing starch-containing dried stains described in [the relevant document].

[0097] <36> The flexible material is selected from cloth, sponge, and paper. <34> or <35> The method for removing starch-containing dried stains described in [the relevant document].

[0098] <37> Using a trigger sprayer, spray the aqueous composition and bring it into contact with the starch-containing dry stain. <1> ~ <37> A method for removing starch-containing dried stains as described in any of the following.

[0099] <38> After bringing the aqueous composition into contact with the starch-containing dried stain, apply external force within 300 seconds, preferably by scrubbing with a flexible material. <1> ~ <32> A method for removing starch-containing dried stains as described in any of the following.

[0100] <39> Applying an external force by using water flow, <1> ~ <33> A method for removing starch-containing dried stains as described in any of the following.

[0101] <40> The water flow is pressurized water, and furthermore, because it is sprayed from a rotating nozzle inside the dishwasher, it is high-pressure shower water. <39> The method for removing starch-containing dried stains described in [the relevant document]. [Examples]

[0102] <Examples 1, 2 and Comparative Example 1> A glass slide was coated with meat sauce (600 μm thick) and dried at 25°C for 24 hours. 2.0 g of the aqueous composition shown in Tables 1 and 2 was impregnated into a sponge piece (W57.5 mm × D37.5 mm × H35 mm) and thoroughly lathered. The glass slide coated with the dirt and the sponge were fixed in a JSPS-type friction fastness tester (manufactured by Tester Sangyo Co., Ltd., model AB-301) so that the dirt and the aqueous composition on the sponge were in contact, and rubbed for 10 seconds (stroke length: 50 mm, speed: 50 mm / s). After rinsing with water for 10 seconds using a wash bottle, the cleaning rate was calculated from the mass of the glass slide before and after cleaning (N=2). The results are shown in Tables 1 and 2. The remainder of the aqueous composition in Tables 1 and 2 is water, which was prepared by first preparing a concentrated stock solution of the specified concentration and diluting it with 3.5°DH water. The pH of the aqueous composition was adjusted to 7 with sodium hydroxide or hydrochloric acid.

[0103] [Table 1]

[0104] [Table 2]

[0105] The components in the table are as follows: (c) The concentration of the component is based on the amount as enzyme protein. (a-1): Sodium di(2-propylheptyl) sulfosuccinate (R in general formula (a1-1)) 1a , R 2a (A compound in which each of the groups is a 2-propylheptyl group and M is sodium) (a-2): Di(2-ethylhexyl) sodium sulfosuccinate (R in general formula (a1-1)) 1a , R 2a (A compound in which each of the groups is a 2-ethylhexyl group and M is sodium) (b1-1): One mole of natural alcohol with an alkyl chain having 12 carbon atoms is mixed with 0.6 moles of propylene oxide, then sulfurized with sulfur trioxide and neutralized with sodium hydroxide (neutralized until the pH of a 10% diluted solution with water reaches 11). (b1-2): Alkylbenzenesulfonic acid (Kao Corporation, Neoperex GS) (b1-3): Hexadecyl sulfate sodium (Fujifilm Wako Pure Chemical Corporation) (b2-1): Lauryl hydroxysulfobetaine (Kao Corporation, Anchitol 20HD) (b3-1): Glycerin mono-2-ethylhexyl ether Amylase: Amplify Prime 100L (Novozymes)

[0106] From the comparison of the examples and comparative examples in Table 1, it can be seen that using components (a) and (b) in combination improves the cleaning power against meat sauce stains, which are dry stains containing starch. In the examples, it is presumed that the combined use of components (a) and (b) allowed component (a) to penetrate deep into the meat sauce stains, making it easier for the amylase in component (c) to act, while the cleaning effects of components (a) and (b) combined also contributed to the improved cleaning power.

[0107] <Example 3 and Comparative Example 3> A glass slide was coated with curry sauce (600 μm thick) and dried at 50°C for 2 hours. 2.0 g of the aqueous composition shown in Table 3 was impregnated into a sponge piece (W57.5 mm × D37.5 mm × H35 mm) and thoroughly lathered. The glass slide coated with the dirt and the sponge were fixed in a JSPS-type friction fastness tester (manufactured by Tester Sangyo Co., Ltd., model AB-301) so that the dirt and the aqueous composition on the sponge were in contact, and rubbed for 10 seconds (stroke length: 50 mm, speed: 50 mm / s). After rinsing with water for 10 seconds using a wash bottle, the cleaning rate was calculated from the mass of the glass slide before and after cleaning (N=2). The results are shown in Table 3. The remainder of the aqueous composition in Table 3 is water, which was prepared by first preparing a concentrated stock solution of the specified concentration and diluting it with 3.5°DH water. The pH of the aqueous composition was adjusted to 7 with sodium hydroxide or hydrochloric acid. Furthermore, the components listed in Table 3 are the same as those used in Example 1, etc.

[0108] [Table 3]

Claims

1. A method for removing starch-containing dry stains, comprising contacting an aqueous composition containing (a) an alkyl sulfosuccinate ester (hereinafter referred to as component (a)), wherein the alkyl group is a branched alkyl group having from 9 to 13 carbon atoms, (b) a surfactant (excluding component (a)) (hereinafter referred to as component (b)), (c) amylase (hereinafter referred to as component (c)), and water with a dry stain containing starch adhered to an article (hereinafter referred to as starch-containing dry stain), and removing the stain by applying an external force.

2. 2. The method for removing starch-containing dry stains according to claim 1, wherein the external force is applied by scrubbing with a flexible material.

3. 3. The method for removing starch-containing dry stains according to claim 2, wherein the starch-containing dry stains are scrubbed with a flexible material impregnated with the aqueous composition.

4. 3. The method for removing starch-containing dry stains according to claim 2, wherein the flexible material is a material selected from the group consisting of cloth, sponge, and paper.

5. 2. A method for removing starch-containing dry stains according to claim 1, wherein the branched alkyl group of component (a) is a branched alkyl group having a main chain of 6 or 7 carbon atoms and one or more side chains, the total number of carbon atoms in the side chains being 3 or 4.

6. 2. The method for removing starch-containing dry stains according to claim 1, wherein the branched alkyl group of component (a) is a branched alkyl group selected from the group consisting of a 2-propylheptyl group and a 3,5,5-trimethylhexyl group.

7. 2. A method for removing starch-containing dry stains according to claim 1, wherein the component (b) is one or more surfactants selected from (b1) anionic surfactants (excluding the component (a)) (hereinafter referred to as the component (b1)), (b2) amphoteric surfactants, and (b3) nonionic surfactants.

8. 8. A method for removing starch-containing dry stains according to claim 7, wherein the aqueous composition contains component (b1), and the mass ratio of the content of component (a) to the content of component (b1) to the content of component (c) in the aqueous composition, [(a) + (b1)] / (c), is 500 or more and 5,000 or less.

9. 9. The method for removing starch-containing dry stains according to claim 1, wherein an external force is applied within 300 seconds after the aqueous composition is brought into contact with the starch-containing dry stain.