Foamable detergent composition

Abstract

To provide: a foamable detergent composition which has good storage stability in a low-temperature condition considering winter season and has excellent foam rinsing properties with excellent foamability in use of the composition in a diluted state; and a washing method of a hard surface with the same.SOLUTION: A foamable detergent composition contains: 0.005 mass% or more and 5 mass% or less of the following component (a); 0.01 mass% or more and 15 mass% or less of the following component (b); 0.01 mass% or more and 15 mass% or less of the following component (c); 0.01 mass% or more and 15 mass% or less of the following component (d); 0.05 mass% or more and 10 mass% or less of the following component (e); and water. The mass ratio (b) / (c) of a component (b) content to a component (c) content is 1 / 10 or more and 10 / 1 or less: the component (a) is a carboxylic acid having a branched chain hydrocarbon group having a total carbon number of 11 or more and 23 or less and / or a salt thereof; the component (b) is a 8-10C fatty acid and / or a salt thereof; the component (c) is an anion surfactant (but excluding the component (a) and the component (b)); the component (d) is an alkaline agent; and the component (e) is a sequestering agent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a foaming cleaning composition and a method for cleaning hard surfaces. [Background technology]

[0002] In food processing plants, when production schedules are interrupted, the equipment and facilities used in food processing and / or cooking are periodically cleaned to ensure sanitary conditions. Examples of equipment to be cleaned include net conveyors, freezers, slicers, rice polishers, etc., and examples of facilities include floors, walls, work tables, etc. Since these cleaning objects are large in scale and have intricate and complicated parts, foaming cleaning, in which a cleaning agent is foamed into a foam and applied to the cleaning object, is usually used as a method for cleaning them efficiently. Such foaming cleaners are required to have a high cleaning effect as a measure against food poisoning and other pathogens, and for this reason they generally contain high concentrations of inorganic alkaline agents and water-soluble inorganic salts such as hypochlorous acid. In addition, foaming cleaning agents use large amounts of rinsing water, so from an environmental consideration standpoint, technology that has good defoaming properties and can reduce rinsing water is required.

[0003] Patent Document 1 discloses a method for cleaning an object to be cleaned using a foaming detergent composition that contains (A) a specified alkyl and / or alkenyl dimethylamine oxide, (B) an alkaline agent, (C) a specified branched fatty acid and / or a salt thereof, (D) water, and an optional sequestering agent, and in which the mass ratio of (A) / (C) is a specified value. Patent Document 2 discloses a foaming cleaning agent composition for food and beverage manufacturing equipment, which contains (A) an alkaline agent, (B) an anionic surfactant, (C) a specific alkyldimethylamine oxide, (D) an aromatic sulfonate, (E) a water-soluble calcium compound, (F) a metal ion sequestering agent, and water in specific proportions. Patent Document 3 discloses a foaming detergent composition containing (A) an alkaline agent, (B) an anionic surfactant, (C) a specified alkyldimethylamine oxide, and (D) a specified fatty acid having 6 to 14 carbon atoms or a salt thereof in specified ratios, and describes in the examples foaming detergents containing fatty acids having 7 or 8 carbon atoms. Patent Document 4 describes a foaming detergent composition which contains a straight-chain fatty acid such as lauric acid or oleic acid, an alkyldimethylamine oxide, and an anionic surfactant, and which has excellent foaming properties, storage stability, and dilution stability, and which has excellent foam-removal properties during rinsing to inhibit corrosion of aluminum materials. Patent Document 5 describes a foaming cleaning agent composition which contains dimethylamine oxide, an alkaline agent, mainly iso-branched fatty acids, phosphonic acid, and water, has good foaming properties, foam retention, and foam removal properties, and is used in food and beverage manufacturing plants and kitchens. Patent Documents 6 and 7 describe cleaning agents for hard surfaces that contain an amine oxide and a carboxylic acid or its salt having a branched chain hydrocarbon group having 11 to 12 carbon atoms and have excellent foam stability and rinsing properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-199619 A [Patent Document 2] JP 2010-150307 A [Patent Document 3] JP 2013-249383 A [Patent Document 4] JP 2021-181553 A [Patent Document 5] JP 2018-168328 A [Patent Document 6] JP 2019-73732 A [Patent Document 7] JP 2018-203853 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a foaming cleaning agent composition that has good storage stability under low-temperature conditions assumed to be used in winter, and that has excellent foaming properties when used diluted and also has excellent foam rinsing properties, and a method for cleaning hard surfaces using the same. [Means for solving the problem]

[0006] The present invention relates to a foaming cleaning agent composition comprising: 0.005% by mass or more and 5% by mass or less of the following component (a); 0.01% by mass or more and 15% by mass or less of the following component (b); 0.01% by mass or more and 15% by mass or less of the following component (c); 0.01% by mass or more and 15% by mass or less of the following component (d); 0.05% by mass or more and 10% by mass or less of the following component (e); and water, wherein the mass ratio (b) / (c) of the content of the component (b) to the content of the component (c) is 1 / 10 or more and 10 / 1 or less. Component (a): A carboxylic acid and / or a salt thereof having a branched chain hydrocarbon group with a total carbon number of 11 to 23. (b) Component: fatty acid having 8 to 10 carbon atoms and / or its salt Component (c): Anionic surfactant (excluding components (a) and (b)) (d) Ingredient: Alkaline agent (e) Ingredient: Sequestering agent

[0007] The present invention also relates to a method for cleaning a hard surface, which comprises mixing the foaming cleaning agent composition of the present invention with water to obtain a diluted solution, which is foamed and brought into contact with the hard surface. Effect of the Invention

[0008] The present invention provides a foaming cleaning agent composition that has good storage stability under low-temperature conditions assumed to be used in winter, has excellent foaming properties when used diluted, and also has excellent foam rinsing properties, and a method for cleaning hard surfaces using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The reasons why the foaming cleaning agent composition of the present invention and the cleaning method for hard surfaces using the same have good storage stability under low-temperature conditions assumed to be in winter and have excellent foaming properties when used in a diluted form while also having excellent foam rinsing properties are not necessarily clear, but are presumed to be as follows. When a foamed cleaning composition is used to create a foam and then brought into contact with a hard surface for cleaning, and the foam is then rinsed off, the foam has been improved in rinsing properties by blending a fatty acid, which is generally used as a defoamer, into the foaming cleaning composition. When the fatty acid is used, calcium ions contained in water and the fatty acid are associated to form scum, which destroys the foam film on the hard surface and defoams the foam. However, a large amount of fatty acid is required to form scum and defoam, and it is difficult to defoam with a small amount of fatty acid. On the other hand, the foaming cleaning agent composition of the present invention contains, as component (a), a carboxylic acid and / or a salt thereof having a specific branched chain hydrocarbon group, and when the foamed foaming cleaning agent composition of the present invention is brought into contact with a hard surface, component (a) can form a liquid condensed film, i.e., an oily domain, on the hard surface, thereby making the foam film on the hard surface non-uniform and defoaming. Therefore, it is believed that the foaming cleaning agent composition of the present invention can achieve excellent foam rinsing properties even with a small amount of component (a). Regarding storage stability under low temperature conditions in winter, for example, when a linear secondary alkylbenzene sulfonate, an alkane sulfonate type anionic surfactant, or a sulfate type anionic surfactant is used as the anionic surfactant of the foaming component (c), the salts of these surfactants, especially potassium salts, have a high Kraft point and a low solubility, which affects storage stability at low temperatures. On the other hand, fatty acid salts, especially potassium salts, have excellent solubility, and the short-chain fatty acid salts of the component (b) in particular have excellent solubility in aqueous solutions, so that the foaming detergent composition of the present invention is considered to contribute to the storage stability of the anionic surfactant at low temperatures by using the components (b) and (c) in combination. In addition, if an excessive amount of the component (c) is present in the foaming detergent composition of the present invention, the low-temperature storage stability is impaired, so the mass ratio (b) / (c) needs to be 1 / 10 or more. However, the present invention is not limited to this mechanism of action.

[0010] [Foaming cleaning agent composition] <Component (a)> The foaming detergent composition of the present invention contains, as component (a), a carboxylic acid and / or a salt thereof having a branched chain hydrocarbon group with a total carbon number of 11 to 23. The carboxylic acid and / or a salt thereof having a branched chain hydrocarbon group as component (a) refers to a branched fatty acid and / or a salt thereof consisting of one branched chain hydrocarbon group and one carboxylic acid group, and may also be called a branched aliphatic carboxylic acid and / or a salt thereof. Furthermore, the component (a) of the present invention is preferably a carboxylic acid and / or a salt thereof in which the main chain of the branched chain hydrocarbon group has 7 to 21 carbon atoms and all side chains are branched at the third or higher position of the main chain. The component (a) in the foaming detergent composition of the present invention may be a mixture of carboxylic acids and / or salts thereof having the same structure or having branched chain hydrocarbon groups with different branching positions. Furthermore, in the present invention, a mixture of two or more carboxylic acids and / or salts thereof having branched chain hydrocarbon groups with different branching positions is more preferable. Carboxylic acids and / or salts thereof having different structures may be mixed in the composition of the present invention, and the carboxylic acid and / or salt thereof itself may be a mixture. From the viewpoint of production, it is more preferable to produce a mixture of carboxylic acids and / or salts thereof having different structures and incorporate this in the composition.

[0011] From the viewpoint of rinsing properties, the carboxylic acid of component (a) is preferably a monocarboxylic acid.The salt of component (a) is preferably an alkali metal salt, more preferably a sodium salt or potassium salt.

[0012] In the present invention, the branched chain hydrocarbon group refers to a hydrocarbon group having a main chain and a side chain, and having one or more branched carbon atoms as described below. Among the branched chain hydrocarbon groups, the hydrocarbon chain with the largest carbon number counted from the carbon atom bonded to the carboxylic acid is the main chain, and the hydrocarbon chains branched and bonded to the main chain are side chains.

[0013] When two or more main chains are considered, 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 chain), the main chain is determined in the following order. 1. The side chain branching off from the longest hydrocarbon chain has the larger number of carbon atoms and is considered the main chain. 2. Next, if the number of carbon atoms in the side chains branching off from the longest hydrocarbon chain are the same, the chain with the greater number of side chains branching off from the longest hydrocarbon chain is determined to be the main chain. 3. Next, if the number of side chains branching off from the longest hydrocarbon chain is the same, the one having a side chain on the carbon atom closer to the oxygen atom of the carboxylic acid, counting from the carbon atom bonded to the oxygen atom of the carboxylic acid, is considered to be the main chain. 4. Next, if the position of the carbon atom having a side chain closest to the oxygen atom of the carboxylic acid is the same, the side chain with the greater number of carbon atoms closest to the oxygen atom of the carboxylic acid is considered to be the main chain. When two or more longest hydrocarbon chains have the same symmetrical structure, either one may be used as the main chain.

[0014] From the viewpoint of rinsing ability, the total number of carbon atoms in the branched chain hydrocarbon groups is 11 or more, preferably 15 or more, more preferably 16 or more, and 23 or less, preferably 22 or less, more preferably 21 or less, more preferably 20 or less, more preferably 19 or less, and more preferably 18 or less.

[0015] In the branched chain hydrocarbon group, the number of carbon atoms in the main chain is preferably 10 or more, more preferably 14 or more, even more preferably 15 or more, and preferably 22 or less, more preferably 21 or less, more preferably 20 or less, more preferably 19 or less, more preferably 18 or less, and more preferably 17 or less, from the viewpoint of rinsing performance. The number of carbon atoms in the main chain does not include the number of carbon atoms in the side chain. In addition, the number of carbon atoms in the longest main chain of the branched chain hydrocarbon group is the number obtained by subtracting the carbon number of the methyl group, which is 1, in most cases where there is one methyl group branch. For example, when the total number of carbon atoms in the branched chain hydrocarbon group is 23, the maximum number of carbon atoms in the main chain is 22.

[0016] In the branched chain hydrocarbon group, the branching positions of all side chains are preferably the 3rd or higher position of the main chain from the viewpoint of rinsing ability, where the carbon atom of the main chain bonded to the carboxylic acid is counted as the 1st position. In the branched chain hydrocarbon group, the number of carbon atoms in the side chain is preferably 1 or more, and preferably 10 or less, more preferably 5 or less, even more preferably 2 or less, and still more preferably 1, from the viewpoint of rinsing performance. The number of carbon atoms in the side chain refers to the number of carbon atoms in one side chain bonded to the main chain. A side chain having one carbon atom is preferably a methyl group. In the branched chain hydrocarbon group, from the viewpoint of rinsing ability, the number of side chains is preferably 1 or more and preferably 3 or less, more preferably 2 or less, and even more preferably 1. Note that 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 a further side chain branching from the side chain.

[0017] As described above, the component (a) is preferably a mixture of carboxylic acids and / or salts thereof having chain-type branched hydrocarbon groups with different branching positions. As a preferable requirement, the component (a) is preferably a mixture of carboxylic acids and / or salts thereof having chain-type branched hydrocarbon groups with different branching positions (hereinafter sometimes referred to as branched fatty acids) with the chain-type branched hydrocarbon groups having preferably one to three side chains with a carbon number of 1 to 3, more preferably one side chain with a carbon number of 1, and the branching positions of the side chains are distributed at the third position or higher of the main chain. Specifically, the component (a) is preferably a mixture of branched aliphatic primary carboxylic acids (hereinafter sometimes referred to as methyl-branched fatty acids) and / or salts thereof, each of which has one to three, more preferably one, methyl group branched from the third position on the main chain of the aliphatic primary monocarboxylic acid and which has different branching positions. The mixture is preferably a mixture of two or more, more preferably three or more, and preferably twelve or fewer, more preferably eleven or fewer. The component (a) can be a commercially available product, and branched fatty acids with different structures may be mixed and used. When producing the component, the production method is not particularly limited, but a mixture of fatty acids having methyl-branched chain-type branched hydrocarbons with different branching positions can be prepared, for example, as a by-product in the process of polymerizing unsaturated fatty acids with one or more double bonds using an acid catalyst. The production method described in Japanese Patent No. 3303947 can be used to obtain a mixture of saturated methyl-branched fatty acids with different branching positions. It can be confirmed that the obtained branched fatty acids are a mixture of fatty acids with different branching positions by separating them using GC-MS. Component (a) is more likely to form the oily domain that is a feature of the present invention when it is a mixture in which the branching positions of the side chains are distributed at the third or higher position of the main chain than when it is a single component in which the branching positions of the side chains are the same. This leads to superior rinsing properties of the foam of the foaming detergent composition, and is also preferable to iso-branched fatty acids from the viewpoint of production costs. In addition, the chain hydrocarbon group of component (a) is preferably a saturated hydrocarbon group, but when unsaturated fatty acids are used as the raw material for production, unreacted unsaturated fatty acids, saturated straight chain, dimer acids, etc. may be contained, but by reducing the by-products through purification, they may be mixed in to an extent that does not have an effect. Aliphatic carboxylic acids with different carbon numbers may also be mixed in. The component (a) exists as a carboxylic acid or a carboxylate anion in the foaming detergent composition depending on the pH. When preparing the foaming detergent composition of the present invention, the component (a) may be added as a carboxylic acid and neutralized with an alkali metal hydroxide, or may be added as a carboxylic acid.

[0018] <(b) Component> From the viewpoints of low-temperature storage stability and foaming property, the foaming detergent composition of the present invention preferably further contains, as component (b), a fatty acid having from 8 to 10 carbon atoms and / or a salt thereof. The number of carbon atoms in the fatty acid of component (b) is preferably 8 from the viewpoints of low-temperature storage stability and foaming property. The salt of component (b) is preferably an alkali metal salt, more preferably a sodium salt or potassium salt.

[0019] <(c) component> The foaming cleanser composition of the present invention contains an anionic surfactant as component (c), provided that component (c) excludes those that fall under components (a) and (b).

[0020] Examples of the anionic surfactant of component (c) include one or more selected from alkylbenzenesulfonic acids or their salts, alkanesulfonic acids or their salts, polyoxyalkylene alkyl or alkenyl ether sulfates or their salts, alkyl or alkenyl sulfates or their salts, olefinsulfonic acids or their salts, fatty acids having an oxyalkylene group or their salts, alkyl or alkenyl ether carboxylic acids or their salts, α-sulfofatty acids or their salts, N-acylamino acids or their salts, mono- or di-phosphates, and sulfosuccinates or their salts. The carbon number of the alkyl group or alkenyl group of the anionic surfactant is, for example, 8 to 22 carbon atoms, preferably 10 to 16 carbon atoms, and more preferably 12 to 14 carbon atoms. In the polyoxyalkylene group of the anionic surfactant, the oxyalkylene group is preferably one or more groups selected from an oxyethylene group and an oxypropylene group, and is preferably an oxyethylene group. In the polyoxyalkylene group, the average number of moles added of the oxyalkylene group is, for example, 0 to 10, and preferably 1 to 3. Examples of counter ions of the anionic groups of these anionic surfactants include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; and alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

[0021] From the viewpoint of foaming property and cleaning property, the component (c) is preferably one or more selected from alkylbenzenesulfonic acid or a salt thereof, alkanesulfonic acid or a salt thereof, alkyl or alkenyl sulfate ester or a salt thereof, polyoxyalkylene alkyl or alkenyl sulfate ester or a salt thereof, and fatty acid having an oxyalkylene group or a salt thereof, and more preferably one or more selected from alkanesulfonic acid having a hydrocarbon group having from 10 to 24 carbon atoms or a salt thereof, and alkylbenzenesulfonic acid having a hydrocarbon group having from 10 to 24 carbon atoms or a salt thereof (hereinafter referred to as component (c1)).

[0022] The hydrocarbon groups of component (c1) are partially or entirely alkyl or alkenyl groups having from 10 to 24 carbon atoms, with alkyl groups having from 10 to 24 carbon atoms being preferred. Furthermore, the alkyl group more preferably contains one secondary carbon atom linked to the sulfonic acid group. However, when the hydrocarbon group of component (c1) is an alkylbenzene of alkylbenzenesulfonic acid or its salt, the number of carbon atoms in the alkyl group is preferably 10 or more and 18 or less. The hydrocarbon group of component (c1) preferably has 12 or more carbon atoms, more preferably 14 or more carbon atoms, and preferably has 22 or less carbon atoms, more preferably 20 or less carbon atoms. The component (c1) may be at least one selected from secondary alkane sulfonic acid or a salt thereof, and linear alkylbenzene sulfonic acid or a salt thereof. Therefore, the component (c1) preferably contains a secondary alkyl group, and examples of the compound include at least one selected from secondary alkanesulfonic acids or salts thereof in which a sulfonic acid group is bonded to the secondary carbon atom of the alkyl group, and linear alkylbenzenesulfonic acids or salts thereof in which the secondary carbon atom of a linear alkyl group is bonded to a benzene ring and the sulfonic acid group is bonded to the para position relative to the linear alkyl group bonded to the benzene ring (hereinafter referred to as linear alkylbenzenesulfonic acids or salts thereof).

[0023] From the viewpoint of cleaning properties, the foaming detergent composition of the present invention further contains an alkaline agent as component (d).

[0024] The alkaline agent of the component (d) may be at least one selected from alkali metal hydroxides, alkali metal carbonates, alkali metal silicates, and amine compounds. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Alkali metal carbonates include sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Examples of alkali metal silicates include sodium silicate and potassium silicate. Examples of sodium silicate include sodium orthosilicate, sodium metasilicate, sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, sodium metasilicate pentahydrate, sodium metasilicate nonahydrate, etc. Examples of potassium silicate include potassium orthosilicate, potassium metasilicate, potassium A silicate, potassium B silicate, potassium C silicate, etc. The amine compound can include alkanolamines.

[0025] From the viewpoint of cleaning properties and rinsing properties, the component (d) is preferably one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate, and more preferably one or more selected from sodium hydroxide and potassium hydroxide.

[0026] In the present invention, it is possible to use an alkali metal silicate (hereinafter referred to as component (d-1)) as component (d), but this is not preferred because it causes a phenomenon of whitening after cleaning. Therefore, the content of component (d-1) in component (d) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, and it is preferable that the foaming detergent composition of the present invention does not contain component (d-1).

[0027] From the viewpoint of foaming properties, the foaming detergent composition of the present invention contains a sequestering agent as component (e). More specifically, the component (e) may be one or more selected from phosphoric acid or its salt, phosphonic acid or its salt, aminocarboxylic acid or its salt, dicarboxylic acid or its salt, tricarboxylic acid or its salt, oxycarboxylic acid or its salt, and carboxylic acid polymer or its salt. These salts also include hydrates (hydrated salts).

[0028] Specific examples of phosphoric acid or a salt thereof include one or more selected from pyrophosphoric acid or a salt thereof, tripolyphosphoric acid or a salt thereof, metaphosphoric acid or a salt thereof, and phytic acid or a salt thereof. Specific examples of the phosphonic acid or a salt thereof include one or more selected from hydroxyethanediphosphonic acid or a salt thereof, aminotrimethylenephosphonic acid or a salt thereof, ethylenediaminetetramethylenephosphonic acid or a salt thereof, and phosphonobutanetricarboxylic acid or a salt thereof. Specific examples of the aminocarboxylic acid or a salt thereof include one or more selected from edetic acid (EDTA) or a salt thereof, nitrilotriacetic acid (NTA) or a salt thereof, hydroxyethyliminodiacetic acid (HIDA) or a salt thereof, tetrasodium 3-hydroxy-2,2'-iminodisuccinate (HIDS) or a salt thereof, diethylenetriaminepentaacetic acid (DPTA) or a salt thereof, hydroxyethylethylenediaminetriacetic acid (HEDTA) or a salt thereof, dihydroxyethylglycine (DHEG) or a salt thereof, L-glutamic acid diacetate (GLDA) or a salt thereof, methylglycine diacetate (MGDA) or a salt thereof, and the like. Specific examples of dicarboxylic acids or salts thereof include one or more selected from oxalic acid or salts, malonic acid or salts, succinic acid or salts, glutaric acid or salts, phthalic acid or salts, isophthalic acid or salts, and the like. Specific examples of tricarboxylic acids or salts thereof include one or more selected from propanetricarboxylic acid or salts thereof, and cyclohexanetricarboxylic acid or salts thereof. Specific examples of the oxycarboxylic acid or a salt thereof include one or more selected from citric acid or a salt thereof, malic acid or a salt thereof, tartaric acid or a salt thereof, gluconic acid or a salt thereof, oxalic acid or a salt thereof, maleic acid or a salt thereof, malonic acid or a salt thereof, succinic acid or a salt thereof, aspartic acid or a salt thereof, and glutamic acid or a salt thereof. The carboxylic acid polymer or its salt may be at least one selected from an acrylic maleic acid copolymer or its salt, a polyacrylic acid polymer or its salt, and the like.

[0029] The component (e) acts as a sequestering agent and improves foaming properties by lowering the pK Ca It is preferable that the calcium stability constant (Ca stability constant) is greater than 3.0. (e) pK of the component Ca was measured by the following method. <pK Ca Measurement method> As a buffer solution, prepare an aqueous solution containing 0.1 M KOH, 0.1 M NH4Cl, and 0.1 M NH4OH. All sample solutions are prepared using this buffer solution. The temperature of all sample solutions is kept at 20°C during measurement. 2+ For example, the concentration was measured using an Orion ion meter 920A and Ca 2+ An ion electrode can be used. First, obtain the relationship between calcium chloride concentration and the electrode potential, and create a calibration curve. -2 mol / L solution, 5.36×10 -4 Prepare a 100 ml solution of the sample compound. Add 1 ml of calcium chloride solution to 100 ml of the prepared solution of the sample compound and stir for 5 minutes. 2+ Ca concentration 2+ The measurement is performed using an ion electrode. The sample compound is Ca 2+ Assuming that a 1:1 chelate complex is formed, the pK Ca Calculate the calcium stability constant (Ca stability constant).

[0030]

number

[0031] From the viewpoint of effectively achieving both excellent low-temperature storage stability and good foaming, the component (e) is preferably one or more selected from phosphoric acid or a salt thereof, and phosphonic acid or a salt thereof, and more preferably phosphonic acid or a salt thereof. More specifically, component (e) is more preferably one or more selected from sodium aminotrimethylene phosphonate, potassium aminotrimethylene phosphonate, sodium 1-hydroxyethylidene-1,1-diphosphonate, potassium 1-hydroxyethylidene-1,1-diphosphonate, sodium 2-phosphonobutane-1,2,4-tricarboxylate, potassium 2-phosphonobutane-1,2,4-tricarboxylate, sodium ethylenediaminetetramethylene phosphonate, potassium ethylenediaminetetramethylene phosphonate, sodium diethylenetriaminepentamethylene phosphonate, and potassium diethylenetriaminepentamethylene phosphonate, and among these, one or more selected from phosphonobutanetricarboxylic acid or a salt thereof, and hydroxyethanediphosphonic acid or a salt thereof is even more preferable, and is also excellent from the viewpoint of foam stability when diluted and used in a foaming cleaning agent composition containing component (f) described below.

[0032] <Composition, etc.> From the viewpoint of rinsing property, the foaming detergent composition of the present invention contains component (a) in an amount of 0.005% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 5% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less. From the viewpoint of low-temperature storage stability of the foaming detergent composition, the content of component (a) is preferably the upper limit or less. In the present invention, the mass of the component (a) is expressed as a value converted into a potassium salt.

[0033] From the viewpoint of storage stability under low temperature conditions in winter, the foaming detergent composition of the present invention contains component (b) in an amount of 0.01 mass % or more, preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 1 mass % or more, still more preferably 2 mass % or more, and still more preferably 4 mass % or less. In the present invention, the mass of the component (b) is expressed as a value converted into a potassium salt.

[0034] From the viewpoints of rinsing ability, foaming property and cleaning property, the foaming detergent composition of the present invention contains component (c) in an amount of 0.01 mass % or more, preferably 0.15 mass % or more, more preferably 0.5 mass % or more, even more preferably 1 mass % or more, still more preferably 2 mass % or more, and 15 mass % or less, preferably 10 mass % or less, more preferably 8 mass % or less, even more preferably 6 mass % or less, and still more preferably 4 mass % or less. In the present invention, the mass of component (c) is expressed as a value converted into the potassium salt.

[0035] From the viewpoint of cleaning properties, the foaming detergent composition of the present invention contains component (d) in an amount of 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.08% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. When an alkali metal hydroxide is contained as component (d), it indicates a combination of an alkali metal ion and a hydroxyl ion present in the foaming detergent composition, i.e., a free alkali, and does not count a combination with another counter ion. For example, when an organic acid is separately blended, even if it is blended as an alkali metal hydroxide, it becomes a counter ion of the organic acid and is not counted as an alkali metal hydroxide. In addition, when hypochlorite is contained as component (f) described later, an aqueous solution of 3% hydrogen peroxide is gradually added to reduce the hypochlorite until oxygen gas is no longer generated, and then the total alkali metal hydroxide concentration is measured by titration, and the free alkali value obtained by subtracting the concentrations of counter ions of other components from the total alkali metal hydroxide concentration is taken as the alkali metal hydroxide concentration. The concentrations of other alkali agents are measured by using known methods.

[0036] From the viewpoint of foaming property when used in a diluted form, the foaming cleaning agent composition of the present invention contains component (e) in an amount of 0.05 mass % or more, preferably 0.5 mass % or more, more preferably 1.5 mass % or more, and 10 mass % or less, preferably 5 mass % or less, more preferably 4 mass % or less, and even more preferably 3 mass % or less. In the present invention, the mass of component (e) is expressed as a value converted into the potassium salt.

[0037] In the foaming detergent composition of the present invention, from the viewpoint of storage stability under low temperature conditions in winter, the mass ratio (b) / (c) of the content of component (b) to the content of component (c) is 1 / 10 or more, preferably 2 / 10 or more, more preferably 5 / 10 or more, even more preferably 1 / 1 or more, and 10 / 1 or less, preferably 8 / 1 or less, more preferably 5 / 1 or less, even more preferably 3 / 1 or less, and even more preferably 2 / 1 or less. Furthermore, when the foaming detergent composition of the present invention contains an alkylbenzenesulfonate salt as component (c) and contains potassium ions in the composition, the short-chain fatty acid of component (b) acts more effectively because the potassium salt of alkylbenzenesulfonic acid has a high Kraft point, and the storage stability of the foaming detergent composition of the present invention under low temperature conditions can be improved.

[0038] From the viewpoint of cleaning properties and disinfecting properties, the foaming cleaner composition of the present invention preferably contains an oxidizing halogen acid or a salt thereof as the component (f). The oxidizing halogen acid or its salt of component (f) may be one or more selected from hypochlorous acid, hypobromous acid, chlorous acid, and their salts, and from the viewpoint of bactericidal effect, hypochlorous acid or its salts are preferred. Also, the oxidizing halogen acid salt of component (f) may be an alkali metal salt of hypochlorous acid, hypobromous acid, or chlorous acid, and from the viewpoint of foam stability, an alkali metal salt of hypochlorous acid is preferred, and sodium hypochlorite is more preferred.

[0039] When the foamable cleaning agent composition of the present invention contains component (f), from the viewpoints of cleaning property and disinfecting property, the foamable cleaning agent composition contains component (f) in an amount of preferably 0.1 mass % or more, more preferably 1 mass % or more, even more preferably 3 mass % or more, and preferably 10 mass % or less, more preferably 7 mass % or less, even more preferably 5 mass % or less. In the present invention, the mass of the component (f) is expressed as a value converted into a sodium salt.

[0040] From the viewpoint of enhancing low-temperature storage stability, the foaming cleaning agent composition of the present invention may contain, as component (g), one or more hydrotropes selected from paratoluenesulfonic acid, metaxylenesulfonic acid, and salts thereof. When the foamable cleaning agent composition of the present invention contains component (g), from the viewpoint of improving low-temperature storage stability, the foamable cleaning agent composition contains component (g) in an amount of preferably 0.1 mass % or more, more preferably 1.5 mass % or more, even more preferably 2 mass % or more, and preferably 10 mass % or less, more preferably 7 mass % or less, even more preferably 5 mass % or less, and still more preferably 4 mass % or less. In the present invention, the mass of the component (g) is expressed as a value converted into a potassium salt.

[0041] In addition to the components (a) to (g), the foaming cleaner composition of the present invention may optionally contain other components, such as solvents such as ethanol, propylene glycol, polypropylene glycol, (poly)oxyethylene phenyl ether, known dispersants such as maleic acid- or acrylic acid-based polymers, pH adjusters such as lactic acid or citric acid, thickeners, viscosity adjusters, fragrances, colorants, antioxidants, preservatives, bleaching agents, bleaching activators, and the like, within the scope of the object of the present invention (excluding those corresponding to the components (a) to (g)).

[0042] The foaming cleaning agent composition of the present invention is preferably a liquid and may contain water. That is, the remainder of the foaming cleaning agent composition of the present invention other than the components (a) to (e) and any optional components is preferably water. The foaming cleaning agent composition of the present invention may contain water in an amount of preferably 60% by mass or more, more preferably 65% ​​by mass or more, even more preferably 70% by mass or more, still more preferably 75% by mass or more, still more preferably 80% by mass or more, and preferably less than 94% by mass, more preferably 93% by mass or less. As the water, it is preferable to use ion-exchanged water, sterilized ion-exchanged water, or the like.

[0043] The pH of the foaming detergent composition of the present invention at 25°C is preferably 12.5 or higher, more preferably 12.8 or higher, still more preferably 13.0 or higher, even more preferably 13.2 or higher, and, for example, 14 or lower from the viewpoint of detergency. The pH at 25°C can be measured by the glass electrode method. The pH of the foaming detergent composition of the present invention at 25°C is specifically measured by the following pH measurement method.

[0044] <pH Measurement Method> Connect a combined electrode for pH measurement (glass sliding sleeve type manufactured by HORIBA) to a pH meter (pH / Ion meter F-23 manufactured by HORIBA) and turn on the power. As the internal solution of the pH electrode, a saturated potassium chloride aqueous solution (3.33 mol / L) is used. Next, fill 100 mL beakers with a pH 6.86 standard solution (neutral phosphate standard solution), a pH 9.18 standard solution (borate standard solution), and a pH 12.0 standard solution (saturated calcium hydroxide standard solution), respectively, and immerse them in a constant temperature bath at 25°C for 30 minutes. Immerse the pH measurement electrode in the temperature-adjusted standard solution for 3 minutes, and perform calibration operations in the order of pH 6.86 → pH 9.18 → pH 12.0. Adjust the sample to be measured (the foaming detergent composition of the present invention) to 25°C, immerse the electrode of the above pH meter in the sample, and measure the pH after 1 minute. In addition, the pH at 25°C of a diluted solution obtained by diluting the foaming detergent composition of the present invention with water can also be measured by the same method. In that case, in the above description, the foaming detergent composition of the present invention shall be read as a diluted solution obtained by diluting the foaming detergent composition of the present invention with water.

[0045] The foaming detergent composition of the present invention may be used by diluting with water. For example, the foaming detergent composition of the present invention may be a foaming detergent composition used by diluting with water having a hardness of preferably 0.1° DH or more, more preferably 0.2° DH or more, even more preferably 0.3° DH or more, still more preferably 0.5° DH or more, still more preferably 1° DH or more, still more preferably 2° DH or more, and preferably 20° DH or less, more preferably 10° DH or less, still more preferably 8° DH or less, still more preferably 6° DH or less, during use. This water is preferably water containing calcium ions.

[0046] In this specification, water hardness (°DH) refers to German hardness, which indicates the concentration of calcium and magnesium in water expressed as 1 mg / L (ppm) = approximately 0.056°DH (1°DH = 17.8 ppm) in terms of CaCO3 concentration. The German hardness of water used for washing can be adjusted, for example, based on a value calculated from the type and amount of hardness components added. In addition, when water with unknown hardness such as tap water is used as the water used for washing, the German hardness of the water can be determined by the chelate titration method using disodium ethylenediaminetetraacetic acid, described below. A specific method for measuring the German hardness of water in this specification is shown below.

[0047] <Method of measuring water hardness in Germany> 〔reagent〕 0.01 mol / L EDTA·2Na solution: 0.01 mol / L aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01M EDTA-Na2, manufactured by Sigma-Aldrich) ·Universal BT indicator (product name: Universal BT, manufactured by Dojindo Laboratories Co., Ltd.) Ammonia buffer solution for hardness measurement (67.5 g of ammonium chloride dissolved in 570 mL of 28 w / v% ammonia water, and the total volume made up to 1000 mL with ion-exchanged water) [German hardness measurement] (1) Using a volumetric pipette, collect 20 mL of sample water into a conical beaker. (2) Add 2 mL of ammonia buffer solution for hardness measurement. (3) Add 0.5 mL of Universal BT indicator. After addition, confirm that the solution is reddish purple. (4) While shaking the conical beaker well, add 0.01 mol / L EDTA·2Na solution from the burette, and the end point of the titration is when the sample water turns blue. (5) The total hardness is calculated using the following formula. Hardness (°DH)=T×0.01×F×56.0774×100 / A T:0.01mol / L Titration amount of EDTA・2Na solution (mL) A: Sample volume (20 mL, volume of sample water) F: Factor of 0.01mol / L EDTA·2Na solution

[0048] The foaming cleaning agent composition of the present invention is preferably for hard surfaces of hard articles, and further for food processing equipment and / or cooking equipment. That is, the present invention is preferably a foaming cleaning agent composition for food processing equipment and / or cooking equipment. The foaming cleaning agent composition of the present invention is suitable for cleaning hard surfaces containing aluminum, such as hard surfaces of alloys containing aluminum and aluminum metal. In the present invention, the term "food processing equipment and / or cooking equipment" refers to equipment and facilities used in processing and / or cooking food in a food processing factory. Examples of such equipment include net conveyors, freezers, slicers, rice polishers, etc. In addition, examples of such facilities include floors, walls, work tables, etc.

[0049] [How to clean hard surfaces] The present invention provides a method for cleaning a hard surface, which comprises mixing the foaming cleaning agent composition of the present invention with water to obtain a diluted solution, which is foamed and brought into contact with the hard surface. The method for cleaning hard surfaces of the present invention can be appropriately applied to the embodiments described for the foaming cleaning agent composition of the present invention.

[0050] Furthermore, the method for cleaning a hard surface of the present invention may be a method for cleaning a hard surface, which comprises mixing the foaming cleaning agent composition of the present invention with water having a hardness of preferably 0.1° DH or more, more preferably 0.2° DH or more, even more preferably 0.3° DH or more, still more preferably 0.5° DH or more, still more preferably 1° DH or more, still more preferably 2° DH, and preferably 20° DH or less, more preferably 10° DH or less, still more preferably 8° DH or less, and still more preferably 6° DH or less, and foaming the diluted solution and contacting it with the hard surface.

[0051] More specifically, the foaming cleaning agent composition of the present invention can be suitably used in a method for cleaning food processing equipment and / or cooking equipment, which includes the following steps 1 to 3. However, the method for cleaning hard surfaces of the present invention is not limited to this specific example.

[0052] Step 1: A step of diluting the foaming cleaning agent composition of the present invention with water at a dilution ratio of 2 to 200 times (preferably 5 to 200 times) in advance and / or while diluting, spraying the foaming cleaning agent composition in the form of foam and attaching it to food processing equipment and / or cooking equipment. Step 2: Keeping the foam for a certain period of time Step 3: Rinse food processing and / or cooking equipment with water

[0053] In step 1, the foaming detergent composition of the present invention is pre-diluted with water at a dilution ratio of 2 to 200 times (preferably 5 to 200 times) and then sprayed in the form of foam. Alternatively, the foaming detergent composition is placed in a dedicated container and directly connected to a water supply by a hose or the like, and mixed while diluting and sprayed in the form of foam. The above-mentioned pre-dilution and simultaneous dilution can also be combined to spray a diluted solution of the foaming detergent composition in the form of foam. The dilution ratio in step 1 is 2 to 200 times, preferably 5 to 200 times, and more preferably 20 to 100 times.

[0054] The diluted solution of the foaming cleaning agent composition to be sprayed in the form of foam onto the hard surface in step 1 contains, from the viewpoint of rinsing ability, preferably 0.001% by mass or more of component (a) in the diluted solution, more preferably 0.003% by mass or more, even more preferably 0.005% by mass or more, and preferably 0.5% by mass or less, more preferably 0.05% by mass or less, even more preferably 0.01% by mass or less.

[0055] Furthermore, the diluted solution of the foaming cleaning agent composition to be sprayed in the form of foam onto a hard surface contains, from the viewpoints of rinsing ability, foaming ability and cleaning ability, preferably 0.005% by mass or more of component (b) in the diluted solution, more preferably 0.008% by mass or more, even more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and preferably 3% by mass or less, more preferably 1.2% by mass or less, even more preferably 0.6% by mass or less, still more preferably 0.3% by mass or less, and still more preferably 0.1% by mass or less.

[0056] Furthermore, the diluted solution of the foaming cleaning agent composition to be sprayed in the form of foam onto a hard surface contains, from the viewpoints of rinsing ability, foaming ability and cleaning ability, preferably 0.005% by mass or more, more preferably 0.008% by mass or more, even more preferably 0.01% by mass or more, still more preferably 0.03% by mass or more, and preferably 3% by mass or less, more preferably 1.2% by mass or less, even more preferably 0.6% by mass or less, still more preferably 0.3% by mass or less, still more preferably 0.1% by mass or less, and still more preferably 0.08% by mass or less of component (c).

[0057] From the viewpoint of cleaning performance, the diluted solution of the foaming cleaning composition to be sprayed in the form of foam onto a hard surface contains component (d) in the diluted solution in an amount of preferably 0.005% by mass or more, more preferably 0.008% by mass or more, even more preferably 0.01% by mass or more, still more preferably 0.03% by mass or more, and preferably 3% by mass or less, more preferably 1.2% by mass or less, even more preferably 0.6% by mass or less, still more preferably 0.3% by mass or less, still more preferably 0.1% by mass or less, and still more preferably 0.05% by mass or less.

[0058] From the viewpoint of foamability, the diluted solution of the foaming cleaning composition to be sprayed in the form of foam onto a hard surface contains component (e) in the diluted solution in an amount of preferably 0.005% by mass or more, more preferably 0.008% by mass or more, even more preferably 0.01% by mass or more, still more preferably 0.03% by mass or more, and preferably 2% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less, and still more preferably 0.05% by mass or less.

[0059] Furthermore, when the diluted solution of the foaming cleaning composition to be sprayed in the form of foam onto a hard surface contains component (f), from the viewpoint of disinfecting property, the diluted solution contains component (f) in an amount of preferably 0.01 mass % or more, more preferably 0.03 mass % or more, even more preferably 0.05 mass % or more, and preferably 0.6 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and still more preferably 0.1 mass % or less.

[0060] When the diluted solution of the foaming cleaning composition to be sprayed in the form of foam onto a hard surface contains component (g), the diluted solution contains component (g) in an amount of preferably 0.02% by mass or more, more preferably 0.025% by mass or more, even more preferably 0.03% by mass or more, and preferably 0.1% by mass or less, more preferably 0.07% by mass or less, and even more preferably 0.05% by mass or less, from the viewpoint of improving low-temperature storage stability.

[0061] In addition, the mass ratio (b) / (c) of the content of the component (b) to the content of the component (c) in the diluted solution is in the same range as in the foaming detergent composition described above.

[0062] Here, the water used for diluting the foaming detergent composition is generally assumed to be water containing hardness components, such as tap water. From the viewpoint of continuously spraying good foam and from the viewpoint of aluminum corrosion prevention, the hardness of the water used for diluting the foaming detergent composition is preferably 0.1°DH or more, more preferably 0.2°DH or more, even more preferably 0.3°DH or more, still more preferably 0.5°DH or more, still more preferably 1°DH or more, still more preferably 2°DH or more, and preferably 20°DH or less, more preferably 10°DH or less, still more preferably 8°DH or less, still more preferably 6°DH or less. From the viewpoint of cleaning performance, the pH of a diluted solution of the foaming cleaning composition at 25°C is preferably 12.0 or more, more preferably 12.2 or more, even more preferably 12.4 or more, and preferably 13.5 or less, more preferably 13.0 or less, even more preferably 12.8 or less.

[0063] A preferred embodiment of spraying the diluted solution of the foaming cleaning composition of the present invention in the form of foam is to fill a dedicated foam cleaner with an appropriate amount of the diluted solution obtained by diluting the foaming cleaning composition of the present invention with water to a predetermined ratio, and mix it with air / compressed air from the outside to spray it in the form of foam. The content of the composition in the diluted solution (cleaning liquid) obtained by diluting the foaming cleaning composition of the present invention is preferably 0.02% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 8% by mass or less, and even more preferably 0.02% by mass or more and 6% by mass or less. When the treatment area is large, such as a production line in a food processing factory, a foam cleaner (for example, "SCU-HF" manufactured by Spraying Co., Ltd., "KF-100" and "KF-200" manufactured by Kao Corporation, and "Foam iT" manufactured by C.B.S. Co., Ltd.) is preferably used. When the treatment area is small, such as a cooking utensil such as a cutting board, a hand sprayer capable of intermittently generating foam, such as a trigger sprayer or a foamer sprayer, is preferably used.

[0064] In step 1, it is preferable to spray the cleaning agent in a foam form without intermittence. Here, spraying "without intermittence" means, for example, using a foam cleaner, spraying the cleaning agent in a foam form continuously (for example, for 5 seconds or more) while the tap is opened with a lever, switch, or the like, and this is distinguished from "intermittent" spraying, for example, spraying when a lever is pulled with a hand sprayer such as a trigger sprayer or foam sprayer, and spraying stops instantly.

[0065] The embodiment of continuously spraying foam using a foam washer is particularly effective when the food processing equipment and / or cooking equipment to be cleaned has a large area or size.

[0066] When a foam washer is used, the foaming ratio (ratio of foam volume (mL) / foam mass (g)) is preferably 3 to 50 times, more preferably 5 to 40 times, and even more preferably 10 to 40 times. The pressure (gauge pressure) during spraying is preferably 0.1 to 1 MPa, more preferably 0.2 to 0.8 MPa, and even more preferably 0.2 to 0.5 MPa. When a hand sprayer such as a trigger sprayer or a foam sprayer is used, the foaming ratio is preferably 2 to 30 times, more preferably 2 to 20 times, and even more preferably 3 to 10 times.

[0067] Step 2 is a step in which the diluted solution of the foaming cleaning agent composition of the present invention in step 1 is sprayed in the form of foam, which is then attached to food processing equipment and / or cooking equipment, and the foam is maintained for a certain period of time. The time for which the foam is maintained in step 2 is preferably 1 minute or more from the viewpoints of the mechanism and operability of each device, and from the same viewpoints, is preferably 60 minutes or less, more preferably 45 minutes or less, even more preferably 30 minutes or less, still more preferably 20 minutes or less, still more preferably 15 minutes or less, still more preferably 10 minutes or less, and still more preferably 5 minutes or less. Moreover, the time for which the foam is retained in step 2 is, from the viewpoint of cleaning ability, preferably 10 minutes or more, more preferably 15 minutes or more, and even more preferably 20 minutes or more, and from the same viewpoint, is preferably 60 minutes or less, more preferably 45 minutes or less, and even more preferably 30 minutes or less.

[0068] The time for which the foam is maintained in step 2 varies depending on the dilution ratio of the foaming cleaning composition in the diluted solution obtained by diluting the foaming cleaning composition and the scene of use, and is not particularly limited. For example, when the dilution ratio is 2 to 50 times (preferably 5 to 50 times), the time for which the foam is maintained is 1 to 60 minutes, and when the dilution ratio is 50 to 200 times, it is preferable to stably maintain the foam for 1 to 10 minutes.

[0069] It is preferable to leave the mixture as it is while maintaining the foam in step 2, but it is also possible to add a small amount of water or the like.

[0070] After the foam is maintained for a certain period of time, in step 3, the food processing equipment and / or cooking equipment is rinsed with water. The temperature of the rinsing water is preferably 10 to 70°C, more preferably 20 to 70°C. Tap water can be used as the rinsing water, and it may be heated to adjust the water temperature to the above-mentioned preferred temperature. Generally, rinsing is performed manually using a hose or the like. The foaming detergent composition of the present invention has excellent foam-removal properties during rinsing, and requires less rinsing water than conventional detergent compositions, which is economically advantageous and also significantly contributes to reducing the workload (work time and number of workers) and environmental load. EXAMPLES

[0071] Components (a), (b), (c), (d), (e), (f) and (g) used in the examples, comparative examples and formulation examples are shown below.

[0072] <Component (a)> Me-ISA-K: Potassium hydroxide neutralized isostearic acid synthesized by the following method Isoarachidic acid EC-K: Isoarachidic acid EC (Nissan Chemical Industries, Ltd.), a potassium hydroxide neutralized product of a fatty acid represented by the following general formula (a1): Isostearic acid TK: Isostearic acid T (Nissan Chemical Co., Ltd.), a mixture of fatty acids represented by the following general formulas (a2-1) and (a2-2) neutralized with potassium hydroxide.

[0073] [ka]

[0074] Synthesis method of Me-ISA-K 400g of fatty acid mixture (Lunac SO-90L, Kao Corporation, composition: palmitic acid 1%, linoleic acid 3%, octadecenoic acid (oleic acid) 89%, hexadecenoic acid 2%, stearic acid 1%, others), 32g of H-mordenite type zeolite (HSZ-620HOA, Tosoh Corporation: SiO2 / Al2O3 [molar ratio] = 15, average pore size 6.7-7Å) and 8g of water were placed in an autoclave, the atmosphere in the container was replaced with nitrogen, and then the mixture was stirred. The inside of the autoclave was heated to 280°C and 18kgf / cm was applied. 2 The mixture was kept under steam at 1000° C. for 6 hours. The reaction mixture was cooled and taken out, after which the zeolite was filtered off. The mixture was distilled under reduced pressure to obtain 347.6 g of monomer acid (branched unsaturated fatty acid). This monomer acid and 3.5g of 5% Pd / C were placed in an autoclave, heated to 150°C under a hydrogen atmosphere of 20kgf / cm2, and reacted for 3 hours. After the reaction was completed, the mixture was cooled and the catalyst was filtered off. The crude branched fatty acid thus obtained was subjected to a solvent fractionation method according to a conventional method, that is, hexane was added in an amount about twice the weight of the crude branched fatty acid, cooled to -15°C, and the crystals were filtered off. The hexane was then distilled off from the mother liquor to purify the mixture, and 276.7g of methylheptadecanoic acid (hereinafter sometimes referred to as methylheptadecanoic acid) was obtained, in which a methyl group was branched from a linear primary heptadecanoic acid. The obtained methylheptadecanoic acid is a monocarboxylic acid having a main chain of 16 and one side chain with one carbon atom in a branched chain hydrocarbon group, and is a mixture of those in which the branching positions of the side chain are distributed from the 3rd to 15th positions of the main chain. The acid value (AV), saponification value (SV) and iodine value (IV) based on JIS K3331 were as follows: AV=162.7, SV=177.7, IV=9.1

[0075] <(b) Component> C8FA-K: Caprylic acid (Lunac 8-98(E), Kao Corporation) neutralized with potassium hydroxide <(c) component> LAS-K: Linear secondary dodecylbenzenesulfonic acid (Neopelex GS, Kao Corporation) neutralized with potassium hydroxide <(d) component> KOH: Potassium hydroxide (manufactured by Toagosei Co., Ltd.) <(e) component> PBTC-5K: 2-phosphonobutane-1,2,4-tricarboxylic acid (PH-430, manufactured by Chelest Co., Ltd.) neutralized with potassium hydroxide Tripolyphosphate-5Na: pentasodium tripolyphosphate (manufactured by Shimonoseki Mitsui Co., Ltd.) · Trisodium citrate: Trisodium citrate (manufactured by Fuso Chemical Co., Ltd.) MGDA-3Na: Trisodium methylglycine diacetate (Trilon M, manufactured by BASF Ltd.) <Component (f)> ·NaOCl: Sodium hypochlorite (manufactured by Tosoh Corporation) <(g) component> PTS-K: Paratoluenesulfonic acid (manufactured by Meiyu Sangyo Co., Ltd.) neutralized with potassium hydroxide

[0076] (1) Method for producing foaming cleaning agent composition A stirrer piece and purified water were placed in a beaker, and while stirring the purified water, components (a), (b), (c) and (e) were added in that order in the amounts shown in Table 1, followed by stirring, and then component (g) was added. Next, component (d) was added to this mixture, and stirring was continued until the mixture reached room temperature, and component (f) was added as necessary to produce a foaming detergent composition. The pH at 25°C of the foaming detergent compositions of each Example and Comparative Example was as shown in Table 1.

[0077] (2) Rinseability evaluation 200 g of the foaming cleaning agent composition of Tables 1 and 2 was put into the tank of a foam washer ("Foam iT", manufactured by C.B.S. Co., Ltd.), and city water (2.5° dH) was further put into the tank to prepare 10 kg of diluted solution. The spray pressure of the foam washer was adjusted to 4.8 MPa, and the foam was sprayed in foam form for 15 seconds into a stainless steel kitchen sink (40 cm wide x 90 cm long x 30 cm deep) with a 4 cm diameter drainage outlet located at a position 15 cm long x 15 cm wide from one corner of the bottom surface, and the foam was evenly filled in the kitchen sink. Then, using a 5 m watering hose equipped with a water pressure spray nozzle connected to a faucet, city water (2.5° dH) was sprayed directly onto the foam from a height of 30 cm from the bottom surface of the kitchen sink at a flow rate of 15 L / min to rinse the foam, and the time until the foam in the kitchen sink completely disappeared to the part where it could be visually confirmed by the drainage outlet was measured. The results are shown in Table 1. The shorter the time it took for the bubbles to disappear, the better; completion within 90 seconds was considered a pass.

[0078] (2) Foaming (specific foam volume) evaluation 200 g of the foaming cleaning agent composition in Table 1 was placed in the tank of a foam washer ("Foam iT", manufactured by C.B.S. Co., Ltd.), and city water (2.5°dH) was further added to the tank to prepare 10 kg of diluted solution. The spray pressure of the foam washer was adjusted to 4.8 MPa, and the foam was sprayed in foam form into a plastic bucket (Eco Poly Veil round type 60 L, manufactured by Sekisui Techno Molding Co., Ltd.) for 5 seconds. The foam was immediately scooped up into a 500 mL disposable cup, the weight of the 500 mL was measured, and the foam specific volume (g / mL) was calculated. The results are shown in Table 1.

[0079] (3) Storage stability 80 mL of the foaming detergent composition shown in Table 1 was placed in a 100 mL polypropylene bottle (Good Boy: AS ONE) and stored for 3 days under an environment of -5°C. After storage, a visual inspection was performed, and a transparent foaming detergent composition was marked with an ◯, and a cloudy foaming detergent composition was marked with an X. The results are shown in Table 1.

[0080] [Table 1]

[0081] In Table 1, the foaming cleaning agent composition of Comparative Example 4 became cloudy during preparation and could not be blended, so the storage stability was evaluated as "Cannot be blended" and the rinsing ability and foaming ability were not evaluated.

[0082] <Combination example> Formulation examples of the foaming cleaning agent composition of the present invention are shown in Table 2. All formulation examples have good storage stability under low temperature conditions simulating winter, and when used diluted, they have excellent foaming properties and excellent foam rinsing properties.

[0083] [Table 2]

Claims

1. A foaming detergent composition containing the following components: (a) in an amount of 0.005% to 5% by mass, (b) in an amount of 0.01% to 15% by mass, (c) in an amount of 0.01% to 15% by mass, (d) in an amount of 0.01% to 15% by mass, (e) in an amount of 0.05% to 10% by mass, and water, wherein the mass ratio of the content of component (b) to the content of component (c), (b) / (c), is 1 / 10 to 10 / 1. (a) Components: Carboxylic acids and / or salts thereof having chain-like branched hydrocarbon groups with a total of 11 to 23 carbon atoms. (b) Components: Fatty acids having 8 to 10 carbon atoms and / or salts thereof (c) Component: Anionic surfactant (excluding components (a) and (b)) (d) Ingredients: Alkaline agent (e) Ingredients: Metal ion chelating agent

2. (c) The foaming agent composition according to claim 1, wherein component (c) is one or more selected from alkylbenzene sulfonic acid or a salt thereof, alkane sulfonic acid or a salt thereof, alkyl or alkenyl sulfate ester or a salt thereof, polyoxyalkylene alkyl or alkenyl sulfate ester or a salt thereof, and fatty acid having an oxyalkylene group or a salt thereof.

3. (e) The foaming agent composition according to claim 1 or 2, wherein the component is phosphonic acid or a salt thereof.

4. Furthermore, the foaming detergent composition according to claim 1 or 2, further comprising 0.1% by mass or more and 10% by mass or less of an oxidizing halogen acid or a salt thereof as component (f).

5. Furthermore, the foaming detergent composition according to claim 1 or 2 further contains, as component (g), one or more hydrotropes selected from p-toluenesulfonic acid, metaxylenesulfonic acid, and salts thereof.

6. A method for cleaning a hard surface, comprising mixing the foaming cleaning agent composition according to claim 1 or 2 with water to obtain a diluted solution, which is then foamed and brought into contact with the hard surface.