Starch stain 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 a starch stain inhibitor and a method for removing starch stains. [Background technology]

[0002] In recent years, there has been a shift from family-centered lifestyles to individual-centered lifestyles, and opportunities for families to eat together at home are decreasing. As a result, instead of washing dishes after every meal, habits such as accumulating dirty dishes in the sink for the day and washing them when time permits are becoming more widespread. However, in this case, dirt can become firmly attached to dishes due to drying, requiring strong mechanical force to clean them, which is extremely laborious. Therefore, there is a strong demand for technology that can easily remove stubbornly attached dirt from surfaces.

[0003] Patent Document 1 discloses technology for hard surface cleaning agents containing organic acids such as lactic acid. Patent Document 2 discloses technology for immersion cleaning agent compositions containing dicarboxylic acids. Patent Document 3 discloses technology for dishwashing detergent compositions containing dibasic acids such as tartaric acid and malic acid. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2018-522116 [Patent Document 2] Japanese Patent Publication No. 2004-196901 [Patent Document 3] Japanese Patent Publication No. 2006-188648 [Overview of the project] [Problems that the invention aims to solve]

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

[0006] The present invention provides an anti-starch stain adhesion agent that prevents the adhesion of starch stains due to drying or the like, and makes it easy to remove objects such as dishes to which starch stains have adhered even when left unattended, and a method for removing starch stains.

Means for Solving the Problems

[0007] The present invention relates to an anti-starch stain adhesion agent containing, as an active ingredient, one or more compounds selected from carboxylic acids having 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, in which a treatment liquid containing the anti-starch stain adhesion agent of the present invention and water is brought into contact with an object to which starch stains have adhered, and then the object is left for a predetermined time and then the starch stains are removed.

Effects of the Invention

[0009] According to the present invention, there are provided an anti-starch stain adhesion agent that prevents the adhesion of starch stains due to drying or the like, and makes it easy to remove objects such as dishes to which starch stains have adhered even when left unattended, and a method for removing starch stains.

Modes for Carrying Out the Invention

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

[0011] As a result of investigating the cause of the adhesion of stains containing starch to the surface of dishes and the like over time, the inventors of the present invention have clarified that it is caused by the aggregation of carbohydrates due to drying. And in order to prevent this aggregation, it is difficult to simply delay drying, and it is necessary to suppress the formation of hydrogen bonds between carbohydrates formed by drying, and by introducing water even after further drying, it is possible to easily make it easy to hydrate. The component (a) of the present invention is considered to have the effect of suppressing the formation of hydrogen bonds between carbohydrates formed after drying and assisting the hydration of the solidified carbohydrates. Although the mechanism of action has not been fully elucidated, it is considered that the component (a), which is a carboxylic acid compound with a relatively small molecular weight, penetrates between carbohydrates, breaks the hydrogen bonds between carbohydrates by the action of its carbonyl group, and swells the carbohydrates by its anionic electrostatic action to promote 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] As the monocarboxylic acid, from the viewpoint of preventing fixation, preferably monocarboxylic acids having 2 to 5 carbon atoms are mentioned, more preferably acetic acid, propionic acid, butanoic acid, lactic acid, glycolic acid, hydroxybutyric acid. As the dicarboxylic acid, from the viewpoint of preventing fixation, preferably dicarboxylic acids having 2 to 6 carbon atoms are mentioned, more preferably oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartronic acid, glyceric acid, tartaric acid. As the tricarboxylic acid, from the viewpoint of preventing fixation, citric acid and isocitric acid are mentioned.

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

[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 assisting the penetration of component (a) into starch-containing stains and preventing starch adhesion by assisting the penetration of water into dried starch. (b) Examples of components include surfactants. (b) The component may be one or more surfactants selected from amphoteric surfactants, amine oxide type surfactants, nonionic surfactants, and anionic surfactants.

[0016] Examples of amphoteric surfactants include one or more amphoteric surfactants selected from sulfobetaine and carbobetine.

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

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

[0019] [ka]

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

[0021] In general formula (b1), R 1b The alkyl or alkenyl group is preferably 9 or more, more preferably 11 or more, and preferably 15 or less, more preferably 13 or less, with nonyl, decyl, undecyl, dodecyl, and tridecyl groups being preferred. In general formula (b1), R 3band R 4b is each independently preferably a methyl group.

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

[0023] [Chemical formula]

[0024] [In the formula, R 5b represents a hydrocarbon group having 8 to 22 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, R 6b and R 7b represent the same or different alkyl groups having 1 to 3 carbon atoms. D represents a -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 is preferably an alkyl group having 10 to 18 carbon atoms, more preferably an alkyl group having 12 to 16 carbon atoms, still more preferably an alkyl group having 12 to 14 carbon atoms, and even more preferably an alkyl group having 12 carbon atoms. R 6b , R 7b is preferably a methyl group having 1 carbon atom.

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

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

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

[0029] Examples of alcohol alkoxylate-type surfactants include polyoxyalkylene alkyl or alkenyl ethers. Specifically, examples include compounds represented by the following general formula (b5). R 11b -O-(AO) q -H (b5) [In the formula, R 11b [wherein is an alkyl or alkenyl group having 8 to 18 carbon atoms, AO is an alkylene oxy group having 2 or 3 carbon atoms, and q is the average number of moles added, which is between 1 and 30.]

[0030] As an anionic surfactant, an anionic surfactant having a hydrocarbon group with 8 or more carbon atoms, preferably 10 or more, and 20 or less, preferably 18 or less, more preferably 16 or less, preferably an alkyl group, is preferred, and one or more anionic surfactants selected from alkylarylsulfonic acid type surfactants, sulfate ester type surfactants, alkanesulfonic acid type surfactants, olefin sulfonic acid type surfactants, and sulfo fatty acid ester type surfactants are preferred.

[0031] Examples of alkylaryl sulfonic acid type surfactants include alkylbenzene sulfonates. Specifically, alkylbenzene sulfonates having an alkyl group with 6 to 15 carbon atoms are examples.

[0032] Examples of sulfate ester-type surfactants include anionic surfactants having a hydrocarbon group with 8 to 20 carbon atoms and a sulfate ester group. From the viewpoint of cleaning power, the hydrocarbon group has 8 or more carbon atoms, 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 sulfate ester-type surfactants include alkyl sulfate esters and polyoxyalkylene alkyl ether sulfate esters. Suitable alkyl sulfate ester salts include alkyl groups 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, and furthermore, linear or branched alkyl groups. As the polyoxyalkylene alkyl ether sulfate salt, a polyoxyalkylene alkyl ether sulfate salt is preferred that has 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, and further linear or branched alkyl groups, and the average number of added moles 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 alkanesulfonic acid-type surfactants include alkanesulfonates in which the alkane portion has 8 or more carbon atoms, preferably 10 or more, more preferably 14 or more, and 20 or fewer carbon atoms, preferably 18 or fewer.

[0034] Examples of olefin sulfonate-type surfactants include α-olefin sulfonates and internal olefin sulfonates. α-olefin sulfonates have 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, and more preferably 18 or less. Internal olefin sulfonates have 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, and more preferably 18 or less.

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

[0036] As the salt of the anionic surfactant, 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. are preferred.

[0037] The anionic surfactant is preferably one or more anionic surfactants selected from alkylbenzene sulfonates, alkyl sulfate esters, and polyoxyalkylene alkyl ether sulfate esters (where the average number of added moles of oxyalkylene groups, preferably oxyethylene groups, is 0.4 or more and 2.0 or less) from the viewpoint of permeability.

[0038] (b) Examples of component (bx) include surfactants having a starch swelling rate 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> In a glass NMR tube with an inner diameter of 4.20 ± 0.02 mm and a length of 178 mm, 1 ml of a water mixture containing 10% by mass of potato starch is added. After capping, the tube is left to stand at 25°C for 1 hour, and the height of the starch precipitate is measured and designated 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. After capping, the tube is stirred at 2000 rpm for 5 minutes, and then left to stand at 25°C for 24 hours. The height of the starch precipitate is measured and designated as the precipitate height L0 (mm) after standing. 24 The starch swelling rate is calculated using the following formula. An IKA MS 3 Basic Vortexer, manufactured by Overstocklabequipment, can be used as the agitator. Starch swelling rate (%) = (L 24 / L0)×100

[0039] (b) Component is preferably one or more surfactants selected from anionic surfactants, amphoteric surfactants, amine oxide type surfactants, and alkyl glyceryl ether type surfactants. Since anionic surfactants tend to easily affect the effect of component (a), from the viewpoint of improving permeability, the proportion of anionic surfactant in 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 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 amphoteric surfactants, amine oxide type surfactants, and alkyl glyceryl ether type surfactants.

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

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

[0043] (c) The component is preferably an alkyl glycol ether having 1 to 6 carbon atoms in the alkyl group, and more preferably a compound of the following general formula (c1). R 1c -(OR 2c ) r -OH (c1) [In general formula (c1), R1c R 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. 2c is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group, and r is an integer from 1 to 3. (c) More specifically, the components include 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 component (c), the mass ratio (a) / (c), which is the content of component (a) to the content of component (c), is preferably 0.1 or more, more preferably 0.15 or more, and preferably 0.5 or less, and more preferably 0.3 or less, from the viewpoint of further enhancing stability.

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

[0046] [Other ingredients, etc.] In addition to component (a), optional component (b), and component (c), the starch stain inhibitor of the present invention may contain other components such as hydrotropes, dispersants, pH adjusters, thickeners, viscosity modifiers, fragrances, colorants, antioxidants, preservatives, antifoaming agents, bleaching agents, and bleaching activators, to the extent that they do not impair the purpose of the present invention.

[0047] The starch stain inhibitor of the present invention may be a starch stain inhibitor composition containing component (a). The starch stain inhibitor of the present invention may be a liquid or a solid (powder). If the starch stain inhibitor of the present invention is a liquid, it may contain water. Preferably, the starch stain inhibitor of the present invention is a liquid composition containing component (a) and water. If the starch stain inhibitor of the present invention is a liquid composition containing water, it is preferable to have the same pH (25°C) as the treatment solution of the present invention described later. Furthermore, if the starch stain inhibitor of the present invention is a liquid composition containing water, the content of components (a), (b), and (c) in the composition may be the same as that of the treatment solution of the present invention.

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

[0049] [Method for removing starch stains] The present invention relates to a method for removing starch stains, comprising bringing a treatment solution containing the starch stain inhibitor of the present invention and water (hereinafter referred to as the "treatment solution of the present invention") into contact with an object to which starch stains have adhered, leaving the object for a predetermined time, and then removing the starch stains.

[0050] The treatment solution of the present invention contains the starch stain adhesion inhibitor of the present invention and water. The treatment solution of the present invention may be a pre-treatment agent composition for cleaning. That is, the treatment solution of the present invention contains component (a) and water, and optionally contains component (b), component (c), etc. Components (a), (b), and (c) in the treatment solution of the present invention are the same as those described in the starch stain adhesion inhibitor of the present invention, and the preferred embodiments are also the same. The method for removing starch stains according to the present invention can be appropriately applied to the embodiments described in the description of the starch stain adhesion inhibitor of the present invention.

[0051] From the viewpoint of preventing adhesion, the processing liquid of the present invention preferably contains component (a) in an amount of 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, and even more preferably 3% by mass or less.

[0052] From the viewpoint of preventing adhesion, the processing liquid of the present invention contains component (b) preferably at 0.1% by mass or more, more preferably at 0.5% by mass or more, even more preferably at 0.75% by mass or more, and preferably at 10% by mass or less, more preferably at 5% by mass or less, and even more preferably at 3% by mass or less. To possess.

[0053] When the processing solution of the present invention contains component (b), from the viewpoint of further improving the anti-adhesion properties, the mass ratio (a) / (b), which is the content of component (a) to the content of component (b), is 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, and even more preferably 3 or less.

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

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

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

[0057] The processing solution of the present invention preferably contains water at a rate of 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, and even more preferably 97% by mass or less.

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

[0059] In the method for removing starch stains according to the present invention, the object to which the starch stain is attached may be immersed in the treatment solution and brought into contact with it. However, from the viewpoint of efficiently increasing the cleaning power, it is preferable to spray or apply the treatment solution and bring it into contact with the object. The method of bringing the treatment solution of the present invention into contact with an object to which starch stains are attached is preferably by spraying or coating, and more preferably by spraying in droplet form or coating in foam form. Specifically, it is preferable to use a spray means, that is, to use a cleaning pretreatment agent article in which the treatment solution of the present invention is filled into a container equipped with a sprayer. The present invention provides a cleaning pretreatment agent article in a spray container, in which the treatment solution of the present invention is filled into a container equipped with a sprayer. In the present invention, the processing liquid can be sprayed and brought into contact with the target object. In the present invention, the processing liquid can be brought into contact with the target object in a foamy state. In the present invention, the processing liquid can be sprayed in a foamy form and brought into contact with the target object.

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

[0061] In the aforementioned pre-treatment agent article for cleaning contained in a spray container, when a trigger-type spray equipped with a mechanism for spraying the treatment liquid in droplet form is used, the nozzle diameter of the spray nozzle of the spray container containing the treatment liquid is preferably in the range of 0.1 mm or more, more preferably 0.3 mm or more, and preferably 2 mm or less, and more preferably 1 mm or less, in order to ensure ease of spraying, that the sprayed droplets are not rough, that the spray is not linear, and that the sprayable area does not become extremely narrow. When using a trigger-type spray equipped with a mechanism for spraying in droplet form, the pre-treatment agent article for cleaning contained in the spray container is sprayed in a single operation at a rate of preferably 0.1 mL or more, more preferably 0.3 mL or more, and preferably 5 mL or less, and more preferably 2 mL or less.

[0062] Furthermore, in the case of the pre-treatment agent article for cleaning contained in a spray container, when a trigger-type spray equipped with a foam-forming mechanism is used, it is preferable that the spray has a spin element and a liquid passage plate in a circular space with a diameter of 4 to 8 mm on which several rod-shaped protrusions are installed. Here, the spin element is a mechanism that imparts spin to the flow of a liquid through the spin element and finally ejects it from the nozzle. For detailed information on its structure, please refer to Figure 4(b) of Japanese Patent Publication No. Hei 8-332422 and Japanese Patent Publication No. Hei 8-108102, and Figure 1 of Japanese Patent Publication No. 2002-68265.

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

[0064] Another component of the foam formation mechanism, the liquid passage plate, has a circular space with a diameter of 5 to 7 mm, in which rod-shaped protrusions are preferably placed, preferably 3 to 8 rod-shaped protrusions. When the plate is viewed in plan view, rectangular rod-shaped protrusions with a width of 0.8 to 1.2 mm and a length of 2 to 4 mm are preferable. Furthermore, the area occupied by the rod-shaped protrusions in the space excluding the rod-shaped protrusions is preferably 30% or more, more preferably 40% or more, preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less. By installing such a liquid passage plate, the adhesion and retention of foam on the vertical surface is improved.

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

[0066] After bringing the treatment solution of the present invention into contact with an object such as tableware that has starch stains attached, the object should 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, even more preferably 360 minutes or less, and even more preferably 240 minutes or less. In this case, the time when the treatment solution first comes into contact with the tableware may be considered the start of the standing period. The temperature during standing can be room temperature, for example, 10°C to 30°C.

[0067] It is preferable to remove starch stains by contact with a liquid medium containing water and different from the treatment solution [hereinafter referred to as the cleaning solution]. Furthermore, it is preferable to remove starch stains by rubbing the dishes with a flexible absorbent such as a sponge or a cloth such as a dishcloth, as needed.

[0068] The cleaning solution may be water, but an aqueous solution containing a surfactant is preferred. As the surfactant, an anionic surfactant listed as component (b) [hereinafter referred to as component (b1)] is preferred. Specifically, one or more anionic surfactants selected from polyoxyalkylene alkyl ether sulfate salts with an alkyl group having 8 to 18 carbon atoms, alkyl sulfate salts with an alkyl group having 8 to 18 carbon atoms, and mono or diester salts of fatty alcohols with 5 to 18 carbon atoms and sulfosuccinic acid are preferred. In the present invention, it is preferable to remove stains from dishes with starch stains using a cleaning solution containing component (b1) in an amount 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] The cleaning solution of the present invention preferably contains, in addition to component (b1), one or more surfactants selected from the above-mentioned components (b), namely amphoteric surfactants, amine oxide-type surfactants, and nonionic surfactants [hereinafter referred to as component (b2)], in addition to component (b1), from the viewpoint of its effect in removing starch-containing stains. 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, and even more preferably 10% by mass or less. Furthermore, in terms of the effectiveness of removing starch-containing stains, the mass ratio of the content of component (b1) to the content of component (b2) in the cleaning solution, (b1) / (b2), is preferably 0.9 or more and 2.0 or less.

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

[0071] In this invention, it is preferable that the object is tableware. One embodiment of this invention is a method for removing starch stains, in which a treatment solution containing the starch stain inhibitor of the present invention and water is brought into contact with tableware to which starch stains have adhered, the tableware is left for a predetermined time, and then the starch stains are removed. [Examples]

[0072] Using the components shown in Table 1, a treatment solution for preventing starch stain adhesion, as shown in Table 1, was prepared and evaluated for the following items. The results are shown in Table 1. The treatment solutions for preventing starch stain adhesion in Table 1 were prepared by a conventional method. That is, components (a), (b), and other components were added to an appropriate amount of deionized water (60°C), dissolved at 60°C, and then sodium hydroxide and / or hydrochloric acid were added to adjust the pH (25°C) to the values ​​shown in Table 1, after which it was cooled to room temperature (25°C). Note that the mass percentages of the components in Table 1 are all based on the effective content.

[0073] <Cleaning power evaluation 1> A mixture of curry (Bon Curry, manufactured by Otsuka Foods Co., Ltd.), cooked rice, and egg was prepared in a mass ratio of 1:1:1 to create a model composite stain. This model composite stain was mixed with a prepared starch stain adhesion prevention treatment solution in a mass ratio of 2:1 to prepare a mixture. The mass of a glass test piece measuring 25 mm (width) x 75 mm (height) x 1 mm (thickness) was measured using a four-digit balance (x). The prepared mixture was uniformly applied to one side of the glass test piece to a mass of 0.3 g to create a stain piece. The mass of this stain piece was measured using a four-digit balance (y). After application, the material was left at 25°C for 180 minutes, then rinsed with deionized water for 10 seconds. After rinsing, the soiled piece was dried and its mass was measured using a four-digit balance (z). The cleaning efficiency was calculated using the following formula. Cleaning rate (%) = {(y)-(z)} / {(y)-(x)} × 100 In the cleaning power evaluation 1, a higher cleaning rate indicates that starch is easier to remove by rinsing and that starch adhesion is prevented.

[0074] <Cleaning power evaluation 2> A model contaminated dish was created by spreading 1g of a model composite stain, which was made by mixing curry (Bon Curry, manufactured by Otsuka Foods Co., Ltd.), cooked rice, and egg in a 1:1:1 mass ratio, onto a white ceramic plate (23.5cm in diameter, catalog number: 618-3-609, 9-inch rimmed meat plate, listed in the tableware catalog). Each example composition in Table 1 was filled into a trigger-type spray container (Magic Clean Handy Spray, manufactured by Kao Corporation), and sprayed evenly onto five model soiled dishes placed horizontally, three times per dish to ensure even adhesion to the model complex stains. The dishes were then left at 25°C for 180 minutes. Next, a commercially available sponge (product name: Kikuron A, Kikuron Co., Ltd.) soaked in 1g of cleaning solution A and 30g of tap water warmed to 25°C was kneaded five times by hand to create lather. Using this sponge, a skilled panelist scrubbed each of the soiled model dishes one by one at a constant speed, evaluating how easily the dirt was removed. Furthermore, similar evaluations were performed using each comparative example composition shown in Table 1. As a result, when using each example composition in Table 1, the stains could be completely removed from all five contaminated model dishes by scrubbing each dish five times or less. However, when using each comparative example composition in Table 1, it was necessary to scrub each of the five contaminated model dishes ten times or more to completely remove the stains. Cleaning solution A. • Polyoxyethylene (average number of added moles: 2.0 moles) alkyl (12 carbon atoms) sulfate salt (10% by mass) • N-lauryl-N,N-dimethyl-N-(2-hydroxysulfopropylpropyl)ammonium sulfobetaine (4.5% by mass) • Lauryldimethylamine oxide (4.5% by mass), • Diethylene glycol monobutyl ether (6.0% by mass) • Water (remaining: total is 100% by mass) pH 7.8 at 20℃

[0075] [Table 1]

[0076] In the table, component (b) is as follows: AES: Sodium polyoxyethylene (average number of added moles 2.0) alkyl (12 carbon atoms) ether sulfate, Emal 227HP, manufactured by Kao Corporation, starch swelling rate 100% GE-EH: 2-Ethylhexyl monoglyceryl ether, starch swelling rate 240% • Amine oxide: In general formula (b2), R 5b is an alkyl group with 12 carbon atoms, R 6b and R 7b A compound with a methyl group, m=0, p=0, anchitol 20N, manufactured by Kao Corporation, with a starch swelling rate of 226%. • Sulfobetaine: N-lauryl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, Anchitol 20HD, manufactured by Kao Corporation, starch swelling rate 210%

Claims

1. A method for removing starch stains, comprising: before leaving an object to stand, bringing a treatment solution into contact with an object to which starch stains have been attached, leaving the object to stand for a predetermined time, and then removing the starch stains, The object in question is tableware, The aforementioned processing liquid (a) One or more compounds selected from malic acid, lactic acid, fumaric acid, succinic acid, glycolic acid, propionic acid, citric acid, and salts thereof (hereinafter referred to as component (a)), (b) A surfactant having a starch swelling rate of 150% or more and 300% or less, comprising one or more surfactants selected from amphoteric surfactants, amine oxide type surfactants, and alkyl glyceryl ether type surfactants (hereinafter referred to as component (b)) and water, The mass ratio (a) / (b) of the content of component (a) to the content of component (b) in the processing liquid is 0.25 or more and 5 or less. How to remove starch stains.

2. The method for removing starch stains according to claim 1, wherein the predetermined time is 10 minutes or more.

3. The method for removing starch stains according to claim 1 or 2, wherein the processing liquid contains 0.1% by mass or more and 10% by mass or less of component (a).

4. A method for removing starch stains according to any one of claims 1 to 3, comprising spraying the processing liquid and bringing it into contact with the target object.

5. A method for removing starch stains according to any one of claims 1 to 4, wherein the processing liquid is brought into contact with the target object in a foamy state.

6. A method for removing starch stains according to any one of claims 1 to 5, wherein the starch stains are removed by contact with a liquid medium containing water and different from the treatment solution.

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