Starch stain adhesion inhibitor

Abstract

To provide a starch stain adhesion inhibitor that prevents the adhesion of starch stains due to dryness or the like, making it easy to remove the starch stains from an object, such as tableware, even if it is let stand with the starch stains thereon.SOLUTION: Provided is a starch stain adhesion inhibitor that contains (a) at least one compound selected from a C2-8 carboxylic acid and a salt thereof as an active ingredient, and further contains (b) a surfactant (excluding specific compositions 1, 2, 3, 4, 5, and 6).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an agent for preventing starch stain adhesion and a method for removing starch stains. [Background technology]

[0002] In recent years, the lifestyle is changing from a family-centered to an individual-centered lifestyle, and the number of opportunities to eat together as a family at home is on the decline. For this reason, rather than washing dishes after each meal, the trend is spreading to, for example, store a day's worth of dirty dishes in the sink and wash them when time is available. However, in this case, dirt can adhere strongly to dishes and other items due to drying, and strong mechanical force is required to wash them, which requires a great deal of effort. Therefore, there is a strong demand for technology that can easily remove surfaces to which dirt has adhered strongly.

[0003] Patent Document 1 discloses a technique for a hard surface cleaner containing an organic acid such as lactic acid. Patent Document 2 discloses a technique for a dipping cleaner composition containing a dicarboxylic acid. Patent Document 3 discloses a technique for a dishwashing cleaner composition containing a dibasic acid such as tartaric acid or malic acid. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2018-522116 [Patent Document 2] JP 2004-196901 A [Patent Document 3] JP 2006-188648 A Summary of the Invention [Problem to be solved by the invention]

[0005] Conventional cleaning agents and pretreatment agents remove dirt by cleaning within a relatively short time after the dirt adheres to the object, or by immersing the object in a treatment bath. However, if the object is left for a longer period of time without being immersed in the treatment bath, the dirt dries and adheres firmly to the object, making it very difficult to remove. The present inventors have found that one of the reasons why dirt adheres firmly and becomes difficult to remove is the influence of starch contained in the dirt. However, conventional cleaning agents and pretreatment agents have not been sufficiently studied to prevent starch from adhering.

[0006] To provide a starch stain fixing inhibitor which prevents the fixing of starch stains due to drying or the like and makes it easy to remove starch stains from objects such as tableware even if the objects are left unattended, and a method for removing starch stains. [Means for solving the problem]

[0007] The present invention relates to an agent for preventing adhesion of starch stains, which contains as an active ingredient (a) one or more compounds selected from carboxylic acids having from 2 to 8 carbon atoms and their salts (hereinafter referred to as component (a)).

[0008] The present invention also relates to a method for removing starch stains, which comprises contacting an object having starch stains thereon with a treatment liquid containing the starch stain fixation inhibitor of the present invention and water, and then leaving the object for a predetermined period of time before removing the starch stains. Effect of the Invention

[0009] According to the present invention, there is provided a starch stain adhesion inhibitor that prevents the adhesion of starch stains due to drying or the like, and makes it easy to remove starch stains from objects such as tableware even if they are left unattended, and a method for removing starch stains. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] [Starch stain adhesion inhibitor] <Component (a)> The starch stain fixation inhibitor of the present invention contains, as an active ingredient, component (a), one or more compounds selected from carboxylic acids having from 2 to 8 carbon atoms and salts thereof.

[0011] The inventors have investigated the cause of starch-containing stains adhering to the surface of tableware over time, and have found that it is due to the aggregation of carbohydrates caused by drying. They have also found that in order to prevent this aggregation, it is difficult to simply slow down the drying process, but it is necessary to suppress the formation of hydrogen bonds between carbohydrates formed by drying, and to make the carbohydrates more easily hydrated by simply introducing water, even after drying. Component (a) of the present invention is believed to have the effect of suppressing the formation of hydrogen bonds between carbohydrates that are formed after drying, and furthermore, aiding the hydration of solidified carbohydrates. Although the mechanism of action has not been fully elucidated, it is believed that component (a), a carboxylic acid compound with a relatively small molecular weight, penetrates between the carbohydrates and breaks the hydrogen bonds between the carbohydrates through the action of its carbonyl group, while its anionic electrostatic action causes the carbohydrates to swell and promotes hydration.

[0012] Examples of the component (a) include one or more compounds selected from monocarboxylic acids having 2 to 8 carbon atoms, dicarboxylic acids having 2 to 8 carbon atoms, tricarboxylic acids having 4 to 8 carbon atoms, and salts thereof.

[0013] From the viewpoint of preventing adhesion, the monocarboxylic acid is preferably a monocarboxylic acid having 2 to 5 carbon atoms, and more preferably acetic acid, propionic acid, butanoic acid, lactic acid, glycolic acid, or hydroxybutyric acid. From the viewpoint of preventing adhesion, the dicarboxylic acid is preferably a dicarboxylic acid having 2 to 6 carbon atoms, and more preferably oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartronic acid, glyceric acid, or tartaric acid. Examples of tricarboxylic acids that can be used to prevent adhesion include citric acid and isocitric acid.

[0014] From the viewpoint of preventing adhesion, the component (a) may be a compound selected from monocarboxylic acid having 2 to 5 carbon atoms, hydroxymonocarboxylic acid, dicarboxylic acid, hydroxydicarboxylic acid, and citric acid. More specifically, the component (a) may be one or more compounds selected from malic acid, lactic acid, fumaric acid, succinic acid, glycolic acid, propionic acid, citric acid, and salts thereof. The component (a) is preferably one or more compounds selected from malic acid, lactic acid, fumaric acid, succinic acid, glycolic acid, propionic acid, and salts thereof. From the viewpoint of preventing adhesion, the component (a) is more preferably a compound selected from malic acid and its salts.

[0015] <Optional ingredients, etc.> [(b) Component] The starch stain adhesion inhibitor of the present invention preferably contains a penetrating agent as component (b) from the viewpoint of promoting the penetration of component (a) into starch-containing stains and promoting the penetration of water into dried starch, thereby preventing the adhesion of starch. The component (b) includes a surfactant. The component (b) may be one or more surfactants selected from amphoteric surfactants, amine oxide surfactants, nonionic surfactants, and anionic surfactants.

[0016] The amphoteric surfactant may be one or more amphoteric surfactants selected from sulfobetaine and carbobetaine.

[0017] Examples of sulfobetaines include N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, in which the carbon number of the alkyl group is preferably 10 or more, preferably 18 or less, and more preferably 14 or less; N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, in which the carbon number of the alkyl group is preferably 10 or more, preferably 18 or less, and more preferably 14 or less; N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, in which the carbon number of the alkanoyl group is preferably 10 or more, preferably 18 or less, and more preferably 14 or less; and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, in which the carbon number of the alkanoyl group is preferably 10 or more, preferably 18 or less, and more preferably 14 or less.

[0018] Examples of carbobetaines include N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaines in which the number of carbon atoms in the alkyl group is preferably 10 or more, preferably 18 or less, and more preferably 14 or less, and compounds represented by the following general formula (b1).

[0019] [ka]

[0020] [In the formula, R 1b represents an alkyl or alkenyl group having 7 to 21 carbon atoms; R 2b represents a propylene group, and R 3b and R 4b each independently represents an alkyl group having 1 to 3 carbon atoms.

[0021] In general formula (b1), R 1b is preferably an alkyl or alkenyl group having an integer of 9 or more, more preferably 11 or more, and preferably 15 or less, more preferably 13 or less, and is preferably a nonyl group, a decyl group, an undecyl group, a dodecyl group, or a tridecyl group. In general formula (b1), R 3band R 4b are each independently preferably a methyl group.

[0022] As the amine oxide surfactant, a compound represented by the following general formula (b2) is preferable.

[0023] [ka]

[0024] [In the formula, R 5b represents a hydrocarbon group having 8 to 22 carbon atoms, preferably an alkyl or alkenyl group, more preferably an alkyl group; R 6b and R 7b are the same or different and each represents an alkyl group having 1 to 3 carbon atoms. D represents an -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having 1 to 5 carbon atoms. m and p represent m=0 and p=0 or m=1 and p=1.

[0025] In the above general formula (b2), R 5b R is preferably an alkyl group having 10 to 18 carbon atoms, more preferably an alkyl group having 12 to 16 carbon atoms, even more preferably an alkyl group having 12 to 14 carbon atoms, and still more preferably an alkyl group having 12 carbon atoms. 6b , R 7b is preferably a methyl group having one carbon atom.

[0026] Examples of nonionic surfactants include glyceryl ether type surfactants, glycoside type surfactants, and alcohol alkoxylate type surfactants.

[0027] As the glyceryl ether surfactant, a compound represented by the following general formula (b3) is preferable. R 8b -[OCH2CH(OH)CH2] u -OH (b3) [In the formula, R 8bis an alkyl group having 8 to 10 carbon atoms, and u is a number of 1 to 3. In general formula (b3), R 8b is preferably a branched alkyl group, more preferably a branched alkyl group selected from a 2-ethylhexyl group, an isononyl group, and an isodecyl group, and further preferably a 2-ethylhexyl group. u is preferably the number 1 or 2, and more preferably 1. The glyceryl ether surfactant is more preferably 2-ethylhexyl monoglyceryl ether.

[0028] Examples of the glycoside surfactant include a glycoside surfactant having a hydrocarbon group having 8 to 16 carbon atoms. Examples of the glycoside surfactant having a hydrocarbon group having 8 to 16 carbon atoms include a compound represented by the following general formula (b4). R 9b (OR 10b ) x G y (b4) [In the formula, R 9b represents a hydrocarbon group having 8 to 16 carbon atoms, and R 10b represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a sugar having 5 or 6 carbon atoms, x represents a number having an average value of 0 to 5, and y represents a number having an average value of 1 to 3.

[0029] The alcohol alkoxylate surfactant may be a polyoxyalkylene alkyl or alkenyl ether, specifically a compound represented by the following general formula (b5): R 11b -O-(AO) q -H (b5) [In the formula, R 11b is an alkyl or alkenyl group having 8 to 18 carbon atoms, AO is an alkyleneoxy group having 2 or 3 carbon atoms, and q is the average number of moles added, which is a number of 1 to 30.

[0030] The anionic surfactant is preferably an anionic surfactant having a hydrocarbon group, preferably an alkyl group, having 8 or more carbon atoms, preferably 10 or more and 20 or less, preferably 18 or less, more preferably 16 or less, and is preferably one or more anionic surfactants selected from alkylarylsulfonic acid type surfactants, sulfate ester type surfactants, alkanesulfonic acid type surfactants, olefinsulfonic acid type surfactants, and sulfofatty acid ester type surfactants.

[0031] Examples of the alkylarylsulfonic acid surfactant include alkylbenzenesulfonates, specifically alkylbenzenesulfonates having an alkyl group having 6 to 15 carbon atoms.

[0032] Examples of sulfate ester type surfactants include anionic surfactants having a hydrocarbon group having 8 to 20 carbon atoms and a sulfate ester group. From the viewpoint of detergency, the hydrocarbon group has a carbon number of 8 or more, preferably 10 or more, more preferably 12 or more, and 20 or less, preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less. The hydrocarbon group is preferably an alkyl group. Examples of the sulfate type surfactant include alkyl sulfates and polyoxyalkylene alkyl ether sulfates. As the alkyl sulfate ester salt, an alkyl sulfate ester salt having an alkyl group having 8 or more carbon atoms, preferably 10 or more carbon atoms, and 20 or less, preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less carbon atoms, and further having a linear or branched alkyl group, is suitable. The polyoxyalkylene alkyl ether sulfate is preferably a polyoxyalkylene alkyl ether sulfate having an alkyl group having 8 or more carbon atoms, preferably 10 or more, and 20 or less, preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less, further a straight-chain or branched-chain alkyl group, and an average addition mole number of oxyalkylene groups having 2 to 3 carbon atoms is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and preferably 6 or less, more preferably 3 or less, and even more preferably 2.0 or less. The oxyalkylene group is preferably an ethylene group.

[0033] Examples of the alkanesulfonic acid surfactant include alkanesulfonates having an alkane moiety with 8 or more carbon atoms, preferably 10 or more, more preferably 14 or more, and 20 or less, preferably 18 or less.

[0034] Examples of olefin sulfonic acid type surfactants include α-olefin sulfonates and internal olefin sulfonates. The α-olefin sulfonates include those having an olefin moiety with 8 or more carbon atoms, preferably 10 or more, more preferably 14 or more, and 22 or less, preferably 20 or less, more preferably 18 or less. The internal olefin sulfonates include those having an olefin moiety with 8 or more carbon atoms, preferably 12 or more, more preferably 16 or more, and 24 or less, preferably 20 or less, more preferably 18 or less.

[0035] Examples of sulfofatty acid ester surfactants include α-sulfofatty acid salts in which the fatty acid moiety has 10 to 18 carbon atoms, and α-sulfofatty acid lower alkyl ester salts in which the fatty acid moiety has 10 to 18 carbon atoms and the ester moiety has 1 to 5 carbon atoms.

[0036] Suitable salts of anionic surfactants include inorganic salts selected from sodium salts, ammonium salts, potassium salts, magnesium salts, etc., and organic ammonium salts selected from monoethanolammonium salts, diethanolammonium salts, triethanolammonium salts, morpholinium salts, etc.

[0037] From the viewpoint of penetrability, the anionic surfactant is preferably one or more anionic surfactants selected from alkylbenzene sulfonates, alkyl sulfates, and polyoxyalkylene alkyl ether sulfates (the average number of moles added of oxyalkylene groups, preferably oxyethylene groups, is 0.4 or more and 2.0 or less), each of which has an alkyl group with a carbon number of 10 or more and 14 or less.

[0038] Examples of the component (b) include (bx) a surfactant having a starch swelling ratio of 150% or more and 300% or less (hereinafter referred to as component (bx)). The proportion of component (bx) in component (b) may be 60% by mass or more and 100% by mass or less. <Starch swelling rate> 1 ml of a water mixture containing 10% by mass of potato starch is added to a glass NMR tube having an inner diameter of 4.20±0.02 mm and a length of 178 mm, the tube is capped and left to stand at 25°C for 1 hour, the height of the starch precipitate is measured, and the height of the starch precipitate is taken as the reference precipitate height L0 (mm). Next, the cap is removed and 1 ml of a 100 mM aqueous solution of the surfactant to be measured is added to the contents of the NMR tube, the tube is capped and stirred at 2000 rpm for 5 minutes, left to stand at 25°C for 24 hours, the height of the starch precipitate is measured, and the height of the precipitate after standing is taken as the reference precipitate height L0 (mm). 24 The starch swelling ratio is calculated by the following formula: As the agitator, an IKA MS 3 Basic Vortexer manufactured by Overstock Lab Equipment can be used. Starch swelling rate (%) = (L 24 / L0)×100

[0039] The component (b) is preferably one or more surfactants selected from anionic surfactants, amphoteric surfactants, amine oxide surfactants, and alkyl glyceryl ether surfactants. Since anionic surfactants tend to affect the effect of the component (a), from the viewpoint of improving the permeability, the ratio of the anionic surfactant in the component (b) is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0040] The starch stain adhesion inhibitor of the present invention preferably contains, as component (b), one or more surfactants selected from amphoteric surfactants, amine oxide type surfactants, and alkyl glyceryl ether type surfactants, and more preferably contains an amphoteric surfactant, an amine oxide type surfactant, and an alkyl glyceryl ether type surfactant.

[0041] When the starch stain adhesion inhibitor of the present invention contains the component (b), the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is, from the viewpoint of enhancing the starch adhesion prevention effect of the component (a), preferably 0.25 or more, more preferably 0.5 or more, even more preferably 1 or more, and preferably 5 or less, more preferably 4 or less, even more preferably 3 or less.

[0042] [(c) component] From the viewpoint of stability, the starch stain adhesion inhibitor of the present invention preferably contains an organic solvent as component (c). When a nonionic surfactant is used as component (b), the mixture may tend to become cloudy, so it is preferable to use component (c) to improve this.

[0043] As the component (c), an alkyl glycol ether having an alkyl group with 1 or more and 6 or less carbon atoms is preferable, and a compound represented by the following general formula (c1) is more preferable. R 1c -(OR 2c ) r -OH (c1) [In general formula (c1), R1c is an alkyl group having 1 or more carbon atoms, preferably 2 or more, more preferably 3 or more, and 6 or less, preferably 5 or less, R 2c is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group, and r is an integer of 1 to 3.] More specifically, the component (c) may be one or more selected from butyl diglycol, hexyl glycol, hexyl diglycol, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, butyl glycol, dipropylene glycol monopropyl ether, and propylene glycol monopropyl ether.

[0044] When the starch stain adhesion inhibitor of the present invention contains the (c) component, the mass ratio (a) / (c) of the content of the (a) component to the content of the (c) component is, from the viewpoint of further enhancing stability, preferably 0.1 or more, more preferably 0.15 or more, and preferably 0.5 or less, more preferably 0.3 or less.

[0045] When the starch stain adhesion inhibitor of the present invention contains the components (b) and (c), the mass ratio (b) / (c) of the content of the component (b) to the content of the component (c) is preferably 0.4 or more, more preferably 0.5 or more, and preferably 1.3 or less, more preferably 2.0 or less, from the viewpoint of further enhancing stability. This mass ratio is more preferable when the starch stain adhesion inhibitor of the present invention contains a nonionic surfactant as the component (b).

[0046] [Other ingredients] In addition to component (a) and optional components (b) and (c), the starch stain fixation inhibitor of the present invention may contain other components such as hydrotropes, dispersants, pH adjusters, thickeners, viscosity adjusters, fragrances, colorants, antioxidants, preservatives, foam suppressors, bleaching agents, and bleach activators, provided such components do not impair the object of the present invention.

[0047] The starch stain sticking inhibitor of the present invention may be a starch stain sticking inhibitor composition containing component (a). The starch stain adhesion inhibitor of the present invention may be a liquid or solid (powder). When the starch stain adhesion inhibitor of the present invention is a liquid, it may contain water. The starch stain adhesion inhibitor of the present invention is preferably a liquid composition containing component (a) and water. When the starch stain adhesion inhibitor of the present invention is a liquid composition containing water, it preferably has the same pH (25°C) as the treatment liquid of the present invention described below. In addition, when the starch stain adhesion inhibitor of the present invention is a liquid composition containing water, the contents of the components (a), (b), and (c) in the composition may be the same as those of the treatment liquid of the present invention.

[0048] The starch stain-fixing inhibitor of the present invention is suitable as a starch stain-fixing inhibitor for hard articles, and further suitable as a starch stain-fixing inhibitor for tableware.

[0049] [Method for removing starch stains] The present invention relates to a method for removing starch stains, which comprises contacting an object having starch stains thereon with a treatment liquid containing the starch stain fixation inhibitor of the present invention and water (hereinafter referred to as the treatment liquid of the present invention), leaving the object for a predetermined period of time, and then removing the starch stains.

[0050] The treatment liquid of the present invention contains the starch stain fixation inhibitor of the present invention and water. The treatment liquid of the present invention may be a cleaning pretreatment composition. That is, the treatment liquid of the present invention contains component (a) and water, and optionally contains component (b), component (c), etc. The components (a), (b) and (c) in the treatment liquid of the present invention are the same as those described in the starch stain fixation inhibitor of the present invention, and the preferred embodiments are also the same. The starch stain removing method of the present invention can be appropriately applied to the aspects described in the starch stain fixing inhibitor of the present invention.

[0051] From the viewpoint of preventing sticking, the treatment liquid of the present invention contains component (a) in an amount of preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 0.75 mass % or more, and preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 3 mass % or less.

[0052] From the viewpoint of preventing adhesion, the treatment liquid of the present invention contains the component (b) in an amount of preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.75% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less. Yes.

[0053] When the treatment liquid of the present invention contains component (b), from the viewpoint of further enhancing anti-sticking properties, the mass ratio of the content of component (a) to the content of component (b), (a) / (b), is preferably 0.25 or more, more preferably 0.5 or more, even more preferably 1 or more, and is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less.

[0054] From the viewpoint of further enhancing stability, the treatment liquid of the present invention contains component (c) in an amount of preferably 2 mass % or more, more preferably 3 mass % or more, even more preferably 4 mass % or more, and preferably 10 mass % or less, more preferably 8 mass % or less, even more preferably 6 mass % or less.

[0055] When the treatment liquid of the present invention contains the component (c), the mass ratio (a) / (c) of the content of the component (a) to the content of the component (c) is, from the viewpoint of further enhancing stability, preferably 0.1 or more, more preferably 0.15 or more, and preferably 0.5 or less, more preferably 0.3 or less.

[0056] When the treatment liquid of the present invention contains components (b) and (c), the mass ratio (b) / (c) of the content of component (b) to the content of component (c) is preferably 0.4 or more, more preferably 0.5 or more, and preferably 1.3 or less, more preferably 2.0 or less, from the viewpoint of further enhancing stability. This mass ratio is more preferable when the treatment liquid of the present invention contains a nonionic surfactant as component (b).

[0057] The treatment liquid of the present invention contains water in an amount of preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less, even more preferably 97% by mass or less.

[0058] From the viewpoint of mildness to hands, the pH of the treatment solution of the present invention is preferably 2 or more, more preferably 4 or more, even more preferably 5 or more, and preferably 10 or less, more preferably 9 or less, even more preferably 8 or less. The pH may be measured at 25° C. In the present invention, the pH of the treatment solution is measured by a glass electrode method.

[0059] In the method for removing starch stains of the present invention, the object having starch stains attached thereto may be immersed in the treatment liquid and brought into contact with the object. However, from the viewpoint of efficiently increasing the cleaning power, a method in which the treatment liquid is sprayed or applied and brought into contact with the object is preferred. The method of contacting the treatment liquid of the present invention with an object having starch stains is preferably spraying or coating, and more preferably spraying in droplets or coating in foam. Specifically, it is preferable to use a spray means, that is, to use a cleaning pretreatment agent article in which the treatment liquid of the present invention is filled in a container equipped with a sprayer. The present invention provides a cleaning pretreatment agent article in a spray container in which the treatment liquid of the present invention is filled in a container equipped with a sprayer. In the present invention, the treatment liquid can be sprayed and brought into contact with the object. In the present invention, the treatment liquid can be brought into contact with the object in the form of a foam. In the present invention, the treatment liquid can be sprayed in the form of foam and brought into contact with the object.

[0060] Examples of the container equipped with the sprayer include manual spray devices that do not use a propellant, such as trigger-type spray containers and pump-type spray containers, and aerosols that use a propellant. The container equipped with the sprayer is preferably a trigger-type spray that can spray or apply the contents in the form of droplets or foam, and more preferably a trigger-type spray equipped with a mechanism for spraying the contents in the form of droplets or a mechanism for forming foam (foam-forming mechanism).

[0061] When a trigger-type spray equipped with a mechanism for spraying the treatment liquid in the form of droplets is used in the spray-container-packed cleaning pretreatment agent article, the nozzle diameter of the spray container containing the treatment liquid is preferably 0.1 mm or more, more preferably 0.3 mm or more, and preferably 2 mm or less, more preferably 1 mm or less, so that spraying is easy, the sprayed droplets are not rough, the sprayed droplets are not sprayed in a straight line, and the spray area is not extremely narrow. When a trigger-type spray equipped with a mechanism for spraying droplets is used, the cleaning pretreatment agent article in a spray container sprays preferably 0.1 mL or more, more preferably 0.3 mL or more, and preferably 5 mL or less, more preferably 2 mL or less of the composition in one operation.

[0062] Furthermore, when a trigger-type spray equipped with a foam-forming mechanism is used in the cleaning pretreatment agent article contained in the spray container, it is preferable to use one having a spin element and a liquid passage plate having several rod-shaped protrusions disposed in a circular space having a diameter of 4 to 8 mm. The spin element here is a mechanism that imparts spin to a liquid flow through the spin element and finally ejects the liquid from a nozzle, and the detailed structure of the spin element can be seen in JP-A-8-332422, JP-A-8-108102, Fig. 4(b), JP-A-2002-68265, and the like.

[0063] When a trigger-type spray equipped with a foam-forming mechanism is used, the cleaning pretreatment agent article in a spray container sprays preferably 0.5 mL or more, more preferably 1 mL or more, and preferably 30 mL or less, more preferably 15 mL or less, and even more preferably 5 mL or less of the treatment liquid in one operation.

[0064] The liquid passage plate, another member of the foam-forming mechanism, has preferably 3 to 8 rod-shaped protrusions provided in a circular space with a diameter of 5 to 7 mm, and preferably has rectangular rod-shaped protrusions with a width of 0.8 to 1.2 mm and a length of 2 to 4 mm when the plate is viewed in plan. The area occupied by the rod-shaped protrusions relative to the space excluding the rod-shaped protrusions is preferably 30% or more, more preferably 40% or more, and preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less. By providing such a liquid passage plate, the adhesion and retention of bubbles on the vertical surface is improved.

[0065] The container of the cleaning pretreatment agent article in a spray container may be a commonly used container. For example, it may be obtained from polyethylene, polypropylene, or polyethylene terephthalate as a raw material, and may be manufactured by blow molding or the like. The thickness of the container may differ between the bottom and sides, and is preferably 0.01 to 2 mm, and the container capacity is preferably 100 to 1000 mL. The amount of the treatment liquid of the present invention filled in the container is preferably 200 to 500 mL for ease of handling. The liquid is filled while leaving a reasonable space.

[0066] After the treatment liquid of the present invention is brought into contact with an object such as tableware having starch stains, the object may be left for a predetermined time before the starch stains are removed. The predetermined time is preferably 10 minutes or more, more preferably more than 30 minutes, even more preferably more than 60 minutes, even more preferably more than 90 minutes, even more preferably more than 120 minutes, and 480 minutes or less, more preferably 360 minutes or less, and even more preferably 240 minutes or less. In this case, the time when the treatment liquid first comes into contact with the tableware may be regarded as the start of the leaving period. The temperature during leaving may be room temperature, for example, 10°C or more and 30°C or less.

[0067] The removal of starch stains is preferably carried out by contacting the tableware with a liquid medium (hereinafter referred to as a cleaning liquid) that contains water and is different from the treatment liquid. In addition, the removal of starch stains is preferably carried out by scrubbing the tableware with a flexible absorbent such as a sponge or a cloth product such as a dishcloth, if necessary, to remove the starch stains.

[0068] The cleaning liquid may be water, but an aqueous solution containing a surfactant is preferred. As the surfactant, the anionic surfactants listed as the (b) component [hereinafter referred to as the (b1) component] are preferred. Specifically, one or more anionic surfactants selected from polyoxyalkylene alkyl ether sulfate salts having an alkyl group with 8 to 18 carbon atoms, alkyl sulfate salts having an alkyl group with 8 to 18 carbon atoms, and salts of mono- or diesters of fatty alcohols having 5 to 18 carbon atoms and sulfosuccinic acid are preferred. In the present invention, it is preferred to remove stains from tableware stained with starch using a cleaning liquid containing the (b1) component at a concentration of preferably 5% by mass or more, more preferably 7% by mass or more, even more preferably 9% by mass or more, and preferably 20% by mass or less, more preferably 18% by mass or less, even more preferably 14% by mass or less, and water.

[0069] In terms of the effect of removing starch-containing stains, the cleaning solution of the present invention preferably contains, in addition to component (b1), one or more surfactants selected from the above-mentioned component (b), i.e., amphoteric surfactants, amine oxide surfactants, and nonionic surfactants (hereinafter referred to as component (b2)). The cleaning solution preferably contains component (b2) in an amount of 3% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less. In terms of the effect of removing stains containing starch, the mass ratio of the content of the component (b1) to the content of the component (b2) in the cleaning liquid, (b1) / (b2), is preferably 0.9 or more and 2.0 or less.

[0070] By contacting an object having starch stains, such as tableware, with a treatment liquid containing the starch stain adhesion inhibitor of the present invention and water, leaving it for a predetermined period of time, and then treating it with a cleaning liquid, such as a cleaning liquid containing water and a surfactant, it becomes possible to easily remove starch stains without much effort, and after treatment with the cleaning liquid, a high cleaning effect can be obtained simply by rinsing off the surfactant with water.

[0071] In the present invention, the object is preferably tableware. An embodiment of the present invention can include a method for removing starch stains, which comprises contacting tableware having starch stains with a treatment liquid containing the starch stain fixation inhibitor of the present invention and water, leaving the tableware for a predetermined time, and then removing the starch stains. EXAMPLES

[0072] A treatment liquid for preventing the adhesion of starch stains shown in Table 1 was prepared using the components shown in Table 1, and the following items were evaluated. The results are shown in Table 1. The treatment liquid for preventing the adhesion of starch stains shown in Table 1 was prepared by a conventional method. That is, component (a), component (b) and other components were added to an appropriate amount of ion-exchanged water (60°C) and dissolved at 60°C, and then sodium hydroxide and / or hydrochloric acid was added to adjust the pH (25°C) to the value shown in Table 1, and then the mixture was cooled to room temperature (25°C). Note that the mass% of the blended components in Table 1 are all values ​​based on the active components.

[0073] <Cleaning power rating 1> A mixture of curry (Bon Curry, manufactured by Otsuka Foods Co., Ltd.), cooked rice, and egg in a mass ratio of 1:1:1 was prepared as a model complex stain. This model complex stain was mixed with the prepared treatment liquid for preventing adhesion of starch stains in a mass ratio of 2:1 to prepare a mixed liquid. The mass of a glass test piece measuring 25 mm (width) x 75 mm (length) x 1 mm (thickness) was measured using a four-digit balance (x). One side of the glass test piece was evenly coated with the prepared mixed liquid so that the amount was 0.3 g, and this was used as a stained piece. The mass of the stained piece was measured using a four-digit balance (y). This stained piece was After leaving the coating at 25°C for 180 minutes, the coating was rinsed with ion-exchanged water for 10 seconds. After rinsing, the soiled piece was dried and its mass was measured using a four-digit balance (z). The cleaning rate was calculated using the following formula: Cleaning rate (%) = {(y)-(z)} / {(y)-(x)} x 100 In the cleaning power evaluation 1, it can be judged that the higher the cleaning rate, the easier it is to remove starch by rinsing and the more the starch is prevented from sticking.

[0074] <Cleaning power rating 2> A model contaminated dish was prepared by spreading 1 g of a model complex stain made by mixing curry (Bon Curry, manufactured by Otsuka Foods Co., Ltd.), cooked rice, and egg in a 1:1:1 mass ratio on a white ceramic dish (diameter 23.5 cm, catalog number: 618-3-609, round-edged 9-inch rim meat dish, listed in the tableware catalog). Each example composition in Table 1 was filled into a trigger-type spray container (Magiclean Handy Spray, manufactured by Kao Corporation) and sprayed evenly onto five model contaminated tableware placed horizontally, three times per piece, so that the spray adhered evenly to the model complex stains, and then left at 25°C for 180 minutes. Then, a commercially available sponge (product name: Kikuron A, Kikuron Co., Ltd.) soaked in 1 g of the following cleaning solution A and 30 g of tap water adjusted to 25°C was rubbed five times with the hands to create a lather. Using this sponge, an experienced panelist scrubbed the model soiled tableware one by one at a constant hand speed after leaving it, and evaluated the ease of removing the stains. Moreover, the same evaluation was carried out using each of the comparative compositions in Table 1. As a result, when each example composition in Table 1 was used, stains could be completely removed from all five model stained dishes by scrubbing each piece five or fewer times, whereas when each comparative example composition in Table 1 was used, it was necessary to scrub each of the five model stained dishes more than ten times to completely remove the stains. Cleaning solution A. Polyoxyethylene (average number of moles added: 2.0 moles) alkyl (carbon number: 12) sulfate ester salt (10% by mass) N-lauryl-N,N-dimethyl-N-(2-hydroxysulfopropylpropyl)ammonium sulfobetaine (4.5% by weight), Lauryl dimethylamine oxide (4.5% by weight), Diethylene glycol monobutyl ether (6.0% by mass) Water (balance: total is 100% by mass) pH 7.8 at 20°C

[0075] [Table 1]

[0076] In the table, component (b) is as follows: AES: Polyoxyethylene (average number of added moles: 2.0) alkyl (carbon number: 12) ether sulfate sodium ester, EMAL 227HP, manufactured by Kao Corporation, starch swelling rate: 100% ·GE-EH: 2-Ethylhexyl monoglyceryl ether, starch swelling rate 240% Amine oxide: In the general formula (b2), R 5b is an alkyl group having 12 carbon atoms, R 6b and R 7b Methyl group, m=0, p=0 compound, Amphitol 20N, Kao Corporation, starch swelling rate 226% Sulfobetaine: N-lauryl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, Amphitol 20HD, Kao Corporation, starch swelling rate 210%

Claims

1. (a) An agent for preventing adhesion of starch stains, which contains, as an active ingredient, one or more compounds selected from carboxylic acids having from 2 to 8 carbon atoms and their salts [hereinafter referred to as component (a)], and further contains a surfactant [hereinafter referred to as component (b)] (however, excluding Composition 1, Composition 2, Composition 3, Composition 4, Composition 5 and Composition 6 below). Composition 1: A liquid detergent composition for hard surfaces, comprising a nonionic surfactant (A1) obtained by blending the following (A) and (B) in a mass ratio of (A):(B) = 3:1 to 20:1, an alkanolamine (B1), an enzyme (C1), a solubilizer (D1) consisting of at least one of a xylene sulfonate and a cumene sulfonate, a calcium additive, citric acid, and water, wherein the liquid detergent composition for hard surfaces contains 1 to 10 mass% of the nonionic surfactant (A1), 10 to 30 mass% of the alkanolamine (B1), and 0.1 to 5 mass% of the enzyme (C1) relative to the entire liquid detergent composition for hard surfaces, and the pH of the liquid detergent composition for hard surfaces at 25°C is set in the range of 8.0 to 10.

0. (a) Polyoxyethylene polyoxypropylene alkyl ether. (b) At least one of an ethylene oxide / propylene oxide adduct of trimethylolpropane and an ethylene oxide / propylene oxide adduct of glycerin. Composition 2: A neutral liquid detergent composition for automatic dishwashers, comprising the following components (A2) to (D2) in the following proportions relative to the total composition, and also comprising the following components (E2) to (G2), the pH of the composition at 25°C (JIS-Z-8802:1984 "pH measurement method") being set to 6.0 to 8.

0. (A2) Nonionic surfactant, 1 to 15% by mass (B2) at least one organic acid selected from organic acids and water-soluble salts thereof, 2.5 to 15% by mass (C2) Enzyme, 0.5-5% by mass (D2) Water-soluble solvent, 10 to 40% by mass (E2) Solubilizer (F2) Calcium additive (G2) Water Composition 3: A dishwasher detergent composition comprising a surfactant (A3), at least one element (B3) selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc, an aminocarboxylic acid-type sequestering agent (C3) that forms a complex with the component (B3), and a biguanide-based polymer (D3). Composition 4: A liquid detergent composition comprising 1 mass% or more of (A4) alkyl ethoxylate sulfate, (B4) alkyl ethoxylate (average EO addition mole number 5 to 25) and / or aromatic sulfonate, (C4) a total of 20 to 60 mass% of a surfactant, and sodium citrate, (D4) a pH of 5 to 7 at 25°C, a viscosity of 200 mPa s or less, a viscosity of a 2-fold diluted solution when diluted 2-fold with ion exchanged water that is equal to or less than the viscosity of the liquid before dilution, and a viscosity of a 5-fold diluted solution when diluted 5-fold that is 40% or less of the viscosity of the liquid before dilution. Composition 5: A liquid cleaning composition for hard surfaces comprising (A5) sodium di-2-ethylhexyl sulfosuccinate, (B5) dimethyldodecylamine oxide, (C5) 2-ethylhexyl glyceryl ether, (D5) butyl diglycol, (E5) paratoluenesulfonic acid monohydrate, and (F5) citric acid. Composition 6: A liquid cleaning composition for hard surfaces comprising (A6) sodium di-2-ethylhexyl sulfosuccinate, (B6) 2-ethylhexyl glyceryl ether, (C6) lauryl hydroxysulfobetaine, (D6) butyl diglycol, (E6) paratoluenesulfonic acid monohydrate, and (F6) citric acid.

2. The starch stain adhesion inhibitor according to claim 1, wherein the component (a) is one or more compounds selected from monocarboxylic acids having 2 to 8 carbon atoms, dicarboxylic acids having 2 to 8 carbon atoms, tricarboxylic acids having 4 to 8 carbon atoms, and salts thereof.

3. 3. The starch stain fixation inhibitor according to claim 1 or 2, wherein the component (a) is one or more compounds selected from the group consisting of malic acid, lactic acid, fumaric acid, succinic acid, glycolic acid, propionic acid, citric acid, and salts thereof.

4. The starch stain adhesion inhibitor according to any one of claims 1 to 3, comprising as component (b) a surfactant (bx) having a starch swelling rate of 150% or more and 300% or less [hereinafter referred to as component (bx)].

5. The starch stain adhesion inhibitor according to claim 4, wherein the ratio of the (bx) component in the (b) component is 60 mass % or more and 100 mass % or less.

6. The starch stain fixation inhibitor according to any one of claims 1 to 5, wherein the component (b) is one or more surfactants selected from the group consisting of amphoteric surfactants, amine oxide surfactants, nonionic surfactants, and anionic surfactants.

7. A method for removing starch stains, comprising contacting an object having starch stains with a treatment liquid containing the starch stain fixation inhibitor according to any one of claims 1 to 6 and water, and then leaving the object for a predetermined period of time to remove the starch stains, Prevents starch stains from sticking, making them easier to remove even if the stained object is left unattended. How to remove starch stains.

8. 8. The method for removing starch stains according to claim 7, wherein the predetermined time is 10 minutes or more.

9. 9. The method for removing starch stains according to claim 7 or 8, wherein the treatment liquid contains 0.1% by mass or more and 10% by mass or less of the starch stain adhesion inhibitor (a).

10. The method for removing starch stains according to any one of claims 7 to 9, wherein the treatment liquid is sprayed and brought into contact with the object.

11. The method for removing starch stains according to any one of claims 7 to 10, wherein the treatment liquid is brought into contact with the object in the form of a foam.

12. The method for removing starch stains according to any one of claims 7 to 11, wherein the object is tableware.

13. The method for removing starch stains according to any one of claims 7 to 12, wherein the removal of starch stains is carried out by contact with a liquid medium that contains water and is different from the treatment liquid.

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