Cleaning composition

Abstract

To provide a detergent composition having excellent detergency against oil stains such as denatured oil stains and to provide a method for cleaning denatured oil stains.SOLUTION: There is provided a detergent composition which comprises (a) a nonionic surfactant containing a polyoxyalkylene alkyl or alkenylamine [hereinafter referred to as (a1) component] having an alkyl or alkenyl group having 8 or more and 18 or less carbon atoms and an average addition mole number of oxyalkylene group of 1 or more and 8 or less, (b) a quaternary ammonium salt-type surfactant [hereinafter referred to as (b) component], (c) a polycarboxylic acid or a salt thereof and water, wherein the content of an anionic surfactant [hereinafter referred to as (d) component] is less than 35 mass% based on the total mass of the component (a1) and the component (b) and the content of the component (d) is 20 mass% or less based on the total surfactant.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a detergent composition and a method for cleaning denatured oily soils. [Background technology]

[0002] Generally, cleaners used in kitchens, such as those used on ranges, ovens, walls and floors around ranges, and ventilation fans, as well as cleaners used in food processing equipment, contain surfactants, solvents, and alkaline agents to remove oil stains that have deteriorated due to the effects of heat, sunlight, oxygen in the air, and other factors. However, alkaline cleaners have issues, such as being highly irritating to the skin, and require careful handling. Furthermore, the number of part-time workers and other workers who are not accustomed to handling strong alkalis is increasing. Therefore, there is a strong demand for technology that can clean stubborn, difficult-to-remove denatured oil stains with easy-to-use neutral cleaners.

[0003] Furthermore, when cleaning dishes and / or kitchen utensils, a common method is to soak a sponge containing water in detergent, rub it several times to create a lather, and then scrub the object. This method is considered necessary for removing stubborn stains such as food-derived grease stains, but it is inconvenient when cleaning small gaps that a sponge cannot reach or deep containers or utensils. To solve this inconvenience, a technology is needed that can foam the detergent using a sprayer equipped with a foam-forming mechanism, apply it to the object, and then rinse with water without scrubbing, providing high cleaning power.

[0004] Patent Document 1 discloses a neutral detergent composition containing a mono- or polyoxyethylene alkyl or alkenyl amine and a specific solvent. Patent Document 2 discloses a technique for a cleaning composition for hard surfaces that contains a mono- or polyoxyethylene alkyl or alkenylamine and a polycarboxylic acid such as citric acid as a solubilizing agent. Patent Document 3 discloses a technique for a wipe-off detergent composition containing a cationic surfactant and monooxyethylene dodecylamine or polyoxyethylene dodecylamine as a nonionic surfactant. Patent Document 4 discloses a technique for a floor cleaner composition containing polyoxyethylene (5-mol addition) palmitamine, a cationic surfactant, and ethylenediaminetetraacetic acid. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-97711 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-166409 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-282083 [Patent Document 4] Japanese Patent Application Laid-Open No. 2001-247892 Summary of the Invention [Problem to be solved by the invention]

[0006] However, there is a demand for detergent compositions that have even higher detergency against denatured oils than the detergent compositions described in these patent documents. In the present invention, the term "denatured oily stains" refers to oily stains that have been denatured by the action of heat, light, oxygen in the air, etc., and are therefore very difficult to remove.

[0007] The present invention provides a detergent composition having excellent detergency against oily stains such as denatured oily stains, and a method for cleaning denatured oily stains. [Means for solving the problem]

[0008] The present invention relates to a detergent composition comprising: (a) a nonionic surfactant [hereinafter referred to as component (a)] containing a polyoxyalkylene alkyl or alkenylamine [hereinafter referred to as component (a1)] having alkyl or alkenyl groups having from 8 to 18 carbon atoms and having an average number of moles of oxyalkylene groups added of from 1 to 8 [hereinafter referred to as component (a)]; (b) a quaternary ammonium salt surfactant [hereinafter referred to as component (b)]; (c) a polycarboxylic acid or a salt thereof [hereinafter referred to as component (c)]; and water; wherein the content of (d) anionic surfactant [hereinafter referred to as component (d)] is less than 35% by mass based on the total content of component (a1) and component (b), and the content of component (d) is 20% by mass or less based on the total amount of surfactants.

[0009] The present invention also relates to a method for cleaning denatured oily stains, which comprises contacting the detergent composition of the present invention or a cleaning liquid prepared by diluting the detergent composition with water with a hard article having oily stains, including denatured oily stains, attached thereto. [Effects of the Invention]

[0010] According to the present invention, there are provided a detergent composition having excellent detergency against oily stains such as denatured oily stains, and a method for cleaning denatured oily stains. DETAILED DESCRIPTION OF THE INVENTION

[0011] Although the mechanism of action by which the effects of the present invention are manifested has not necessarily been fully elucidated, the applicant believes that it is as follows. The component (a1) of the present invention is a neutral surfactant with high detergency against denatured oily soils. Furthermore, the optional component (a2) of the present invention, described below, can emulsify and stabilize oily soils emulsified by the component (a1) in a cleaning solution. However, when the component (a1) and an anionic surfactant coexist in a detergent composition, the component (a1) and the anionic surfactant form a complex, resulting in a problem of not being able to achieve the expected detergency against denatured oily soils. Furthermore, denatured oily soils contain large amounts of fatty acids, such as oleic acid, in addition to fats and oils. This results in the formation of a complex between the component (a1) and the fatty acid, which reduces the detergency against denatured oily soils. However, in the detergent composition of the present invention, the quaternary ammonium salt surfactant of the component (b) forms a complex with the fatty acid contained in the denatured oily soils more strongly than the component (a1), and therefore the presence of the component (b) suppresses the reduction in the detergency of the component (a1). Furthermore, the polycarboxylic acid or its salt of the component (c) is presumed to form a complex with the component (a), further improving the detergency against denatured oily soils. However, the effects of the present invention are not limited to the mechanism of action shown here.

[0012] [Cleaning composition] <Component (a)> The cleaning composition of the present invention contains, as component (a), (a1) a nonionic surfactant containing a polyoxyalkylene alkyl or alkenyl amine having alkyl or alkenyl groups having from 8 to 18 carbon atoms and having an average number of moles of oxyalkylene groups added of from 1 to 8.

[0013] The component (a1) is a polyoxyalkylene alkyl or alkenyl amine having alkyl or alkenyl groups with 8 to 18 carbon atoms and an average number of moles of oxyalkylene groups added of 1 to 8.

[0014] The number of carbon atoms in the alkyl or alkenyl group of component (a1) is 8 or more, preferably 10 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, from the viewpoint of cleaning power against denatured oily soils (hereinafter simply referred to as cleaning power). The group contained in the component (a1) is preferably an alkyl group. The oxyalkylene group is preferably an oxyalkylene group having 2 carbon atoms and / or an oxyalkylene group having 3 carbon atoms, i.e., an oxyethylene group and / or an oxypropylene group, and more preferably an oxyethylene group. Component (a1) preferably contains an oxyethylene group as the oxyalkylene group. From the viewpoint of detergency, the average number of moles of oxyalkylene groups added in the component (a1) is 1 or more, preferably 2 or more, and 8 or less, preferably 5 or less, more preferably 4 or less.

[0015] Examples of the component (a1) include alkylene oxide adducts of monoamines having alkyl or alkenyl groups with 8 to 18 carbon atoms and an average number of moles of oxyalkylene groups added of 1 to 8.

[0016] Examples of the component (a1) include compounds represented by the following general formula (a1).

[0017] [ka]

[0018] [In the formula, R 1a is an alkyl or alkenyl group having 8 to 18 carbon atoms, EO is an ethyleneoxy group, m and n are the average number of moles added and are independently a number of 0 to 5, and the sum of m and n is a number of 1 to 8.

[0019] In formula (a1), R 1a From the viewpoint of detergency, R has 8 or more carbon atoms, preferably 10 or more carbon atoms, and 18 or less carbon atoms, preferably 16 or less carbon atoms, and more preferably 14 or less carbon atoms. 1a is preferably an alkyl group. From the viewpoint of detergency, the sum of m and n is 1 or more, preferably 2 or more, and 8 or less, preferably 5 or less, more preferably 4 or less.

[0020] In addition to the component (a1), the cleanser composition of the present invention preferably contains, as component (a), one or more surfactants selected from the group consisting of (a2) amine oxide surfactants (hereinafter referred to as component (a2)), (a3) ​​alkyl glycoside surfactants (hereinafter referred to as component (a3)), and (a4) alkyl glyceryl ether surfactants (hereinafter referred to as component (a4)), from the viewpoints of detergency and aesthetic appearance, and more preferably contains the components (a2), (a3), and (a4).

[0021] The amine oxide surfactant of component (a2) is preferably a compound of the following general formula (a2):

[0022] [ka]

[0023] [In the formula, R 2a represents a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl or alkenyl group, more preferably an alkyl group; R 3a and R 4a are the same or different and represent an alkyl group having 1 to 3 carbon atoms; D represents an -NHC(=O)- group or a -C(=O)NH- group; E represents an alkylene group having 1 to 5 carbon atoms; q and p represent q=0 and p=0 or q=1 and p=1.

[0024] In the above general formula (a2), when q=1 and p=1, R 2a From the viewpoints of detergency and aesthetic appearance, and foaming ability, R is preferably a hydrocarbon group having 7 or more carbon atoms, preferably 9 or more carbon atoms, and 17 or less carbon atoms, preferably 15 or less carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group. 2a From the viewpoints of detergency, aesthetic appearance, and foaming ability, R is preferably a hydrocarbon group having 8 or more carbon atoms, preferably 10 or more carbon atoms, and 18 or less carbon atoms, preferably 16 or less carbon atoms, preferably an alkyl or alkenyl group, more preferably an alkyl group. In the present invention, it is preferable that q=0 and p=0. R 3a and R4a is preferably a methyl group having one carbon atom from the viewpoints of detergency, aesthetic appearance, and foaming ability.

[0025] Preferable specific examples of component (a2) include: (1) Alkyl (carbon number 8 to 18) dialkyl (carbon number 1 to 3) amine oxides: capryl dimethylamine oxide, caprylic dimethylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, palmityl dimethylamine oxide, stearyl dimethylamine oxide, etc. (2) Amide group-containing amine oxides (compounds in which q=1 and p=1 in the general formula (a2)): caprylic acid amidopropyl dimethylamine oxide, capric acid amidopropyl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, etc. These may be used alone or in combination of two or more.

[0026] The alkylglycoside surfactant of component (a3) ​​is preferably a compound represented by the following general formula (a3). R 5a -(OR 6a ) x G y (a3) [In the formula, R 5a R is a hydrocarbon group having 8 or more carbon atoms, preferably 10 or more carbon atoms, and 18 or less carbon atoms, preferably 16 or less carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group. 6a is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, more preferably an ethylene group; G is a residue derived from a reducing sugar; x is a number having an average value of 0 to 6; and y is a number having an average value of 1 to 10, preferably 5 or less, more preferably 2 or less.

[0027] In the compound of general formula (a3), G is a residue derived from a reducing sugar, and the reducing sugar used as the raw material for G may be either an aldose or a ketose. Examples of the reducing sugar used as the raw material for G include triose (having three carbon atoms), tetrose (having four carbon atoms), pentose (having five carbon atoms), and hexose (having six carbon atoms). Specific examples of the aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, gulose, aldose, idose, talose, and xylose. Specific examples of the ketose include fructose. Among these, the reducing sugar used as the raw material for G in the present invention is preferably an aldopentose (having five carbon atoms) or an aldohexose (having six carbon atoms), more preferably glucose, from the viewpoints of detergency, aesthetic appearance, and foaming ability.

[0028] From the viewpoints of detergency and aesthetic appearance, the alkyl glyceryl ether surfactant of component (a4) is preferably an alkyl glyceryl ether surfactant having a hydrocarbon group, preferably an alkyl or alkenyl group, more preferably an alkyl group, and even more preferably a branched alkyl group, having 6 or more, preferably 8 or more, carbon atoms and 12 or less, preferably 10 or less, carbon atoms.

[0029] <(b) Component> The cleaning composition of the present invention contains a quaternary ammonium salt surfactant as component (b). The quaternary ammonium salt surfactant of component (b) is preferably at least one selected from the group consisting of compounds represented by the following general formula (b1) and compounds represented by the following general formula (b2).

[0030] [ka]

[0031] [In the formula, R 1b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R 2bis a group selected from an aliphatic hydrocarbon group having 8 to 18 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and a hydroxyalkyl group having 1 to 3 carbon atoms, and R 3b and R 4b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms, and X - is an anion.

[0032] [ka]

[0033] [In the formula, R 5b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R 6b and R 7b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms, and X - is an anion.

[0034] In general formula (b1), R 1b From the viewpoint of detergency, the number of carbon atoms in R is preferably 9 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 16 or less. 1b is preferably an alkyl group or an alkenyl group, and is preferably an alkyl group. In general formula (b1), R 2b is a group selected from aliphatic hydrocarbon groups having 8 to 18 carbon atoms, alkyl groups having 1 to 3 carbon atoms, and hydroxyalkyl groups having 1 to 3 carbon atoms. R 2b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, R 2b From the viewpoint of detergency, is preferably an alkyl or alkenyl group having a molecular weight of 8 or more, and preferably 14 or less, more preferably 12 or less, and is preferably an alkyl group.

[0035] In general formula (b1), R 3b and R 4bare each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. 3b and R 4b are preferably each independently a group selected from alkyl groups having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of hydroxyalkyl groups having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0036] In general formula (b1), X - is an anion. Examples of anions include halogen ions such as chloride ions, bromide ions, and iodide ions. Examples of anions also include alkyl sulfate ions having 1 to 3 carbon atoms such as methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

[0037] Preferred compounds of the general formula (b1) include one or more selected from N-alkyl-N,N,N-trimethylammonium salts in which the alkyl group has 12 or more and 18 or less carbon atoms, N,N-dialkyl-N,N-dimethyl-ammonium salts in which the alkyl group has 8 or more and 16 or less carbon atoms, and N-alkyl-N,N-dimethyl-N-ethylammonium salts in which the alkyl group has 12 or more and 16 or less carbon atoms.

[0038] In general formula (b2), R 5b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms. 5b From the viewpoint of detergency, the number of carbon atoms in R is preferably 8 or more, and preferably 18 or less, more preferably 16 or less. 5b is preferably an alkyl group or an alkenyl group, and is preferably an alkyl group.

[0039] In general formula (b2), R 6b and R 7b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. 6band R 7b are preferably each independently a group selected from alkyl groups having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of hydroxyalkyl groups having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0040] In general formula (b2), X - is an anion. Examples of anions include halogen ions such as chloride ion, bromide ion, and iodide ion. Examples of anions also include alkyl sulfate ions having 1 to 3 carbon atoms such as methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion.

[0041] Specific examples of the compound of general formula (b2) include N-dodecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tridecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-dimethyl-N-benzyl ammonium salt, N-pentadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-hexadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-dodecyl-N,N-diethyl-N-benzyl ammonium salt, N-tridecyl-N,N-diethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-diethyl-N-benzyl ammonium salt, and N-hexadecyl-N,N-diethyl-N-benzylammonium salt, N-dodecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tridecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tetradecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-pentadecyl-N-methyl-N-ethyl-N-benzylammonium salt, and N-hexadecyl-N-methyl-N-ethyl-N-benzylammonium salt.

[0042] <(c) component> The cleaning composition of the present invention contains a polycarboxylic acid or a salt thereof as component (c).

[0043] From the viewpoint of detergency, the molecular weight of component (c) in terms of acid form is preferably 100 or more, more preferably 130 or more, even more preferably 150 or more, and preferably 300 or less, more preferably 270 or less, even more preferably 250 or less. From the viewpoint of detergency, the valence of the carboxylic acid of component (c) is preferably 2 or more, and preferably 4 or less, more preferably 3 or less. In the present invention, divalent or trivalent polycarboxylic acids are preferably those having a molecular weight of 130 or more and 250 or less, and tetravalent carboxylic acids are preferably those having a molecular weight of 280 or more and 300 or less.

[0044] (c) The components include citric acid (MW: 192, trivalent), malic acid (MW: 134, divalent), oxalic acid (MW: 90, divalent), malonic acid (MW: 104, divalent), succinic acid (MW: 118, divalent), tartaric acid (MW: 150, divalent), glutaric acid (MW: 132, divalent), adipic acid (MW: 146, divalent), fumaric acid (MW: 116, divalent), maleic acid (MW Examples of the carboxylic acid include one or more selected from the group consisting of ethylenediaminetetraacetic acid (EDTA) (MW: 292, tetravalent), aconitic acid (MW: 174, trivalent), ethylenediaminetetraacetic acid (EDTA) (MW: 292, tetravalent), nitrilotriacetic acid (NTA) (MW: 191, trivalent), methylglycinediacetic acid (MGDA) (MW: 205, trivalent), glutamic acid diacetic acid (GLDA) (MW: 259, tetravalent), and salts thereof. The parentheses for each component indicate the molecular weight in acid form and the valence of the carboxylic acid.

[0045] From the viewpoint of detergency, component (c) is preferably one or more selected from citric acid, malic acid, MGDA, GLDA, EDTA, succinic acid, maleic acid, adipic acid, maleic acid, fumaric acid, malonic acid, and salts thereof, more preferably one or more selected from citric acid, malic acid, MGDA, GLDA, EDTA, and salts thereof, and even more preferably one or more selected from citric acid, malic acid, EDTA, and salts thereof. In the present invention, citric acid is most preferred.

[0046] <Composition, etc.> From the viewpoint of detergency, the detergent composition of the present invention contains component (a) in an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 10% by mass or less.

[0047] In the detergent composition of the present invention, from the viewpoint of detergency, the content of component (a1) in component (a) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 100% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, and still more preferably 45% by mass or less.

[0048] From the viewpoint of detergency, the detergent composition of the present invention contains component (b) in an amount of preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, still more preferably 1% by mass or less, and still more preferably 0.7% by mass or less. In the present invention, the mass of component (b) is specified as a value converted into a chlorine salt.

[0049] In the detergent composition of the present invention, the mass ratio (a1) / (b) of the content of the component (a1) to the content of the component (b) is, from the viewpoint of detergency, preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, still more preferably 2 or more, still more preferably 3 or more, and is preferably 200 or less, more preferably 100 or less, still more preferably 50 or less, still more preferably 40 or less, and still more preferably 30 or less.

[0050] From the viewpoint of detergency, the detergent composition of the present invention contains component (c) in an amount of preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, still more preferably 2% by mass or less, and still more preferably 1.5% by mass or less. In the present invention, the mass of component (c) is defined as a value converted into an acid form.

[0051] In the detergent composition of the present invention, the mass ratio (a1) / (c) of the content of the component (a1) to the content of the component (c) is, from the viewpoint of detergency, preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, and is preferably 10 or less, more preferably 8 or less, even more preferably 4 or less.

[0052] In the detergent composition of the present invention, the mass ratio (b) / (c) of the content of the component (b) to the content of the component (c) is, from the viewpoint of detergency, preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.09 or more, and is preferably 5 or less, more preferably 2 or less, even more preferably 1 or less, and still more preferably 0.8 or less.

[0053] The detergent composition of the present invention may contain an anionic surfactant as component (d), but the content thereof is limited. Examples of anionic surfactants include alkyl sulfates, polyoxyalkylene alkyl ether sulfates, alkanesulfonates, alkylbenzenesulfonates, higher fatty acids or salts thereof, polyoxyethylene alkyl ether carboxylic acids or salts thereof, N-acylamino acids or salts thereof, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc. Examples of salts include alkali metal salts such as sodium salts and potassium salts.

[0054] In the detergent composition of the present invention, from the viewpoint of detergency and appearance transparency, the content of component (d) relative to the total content of components (a1) and (b), ((d) / ((a1)+(b)), is preferably 0 mass% or more and less than 35 mass%, more preferably 20 mass% or less, even more preferably 10 mass% or less, and still more preferably 5 mass% or less. In addition, in the detergent composition of the present invention, the content of component (d) is 20% by mass or less, preferably 10% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, based on the total mass of all surfactants, from the viewpoints of detergency and appearance transparency. In the present invention, the mass of component (d) is defined as a value converted into the sodium salt. The cleaning composition of the present invention may not contain component (d).

[0055] The detergent composition of the present invention may contain a water-miscible organic solvent as component (e) from the viewpoint of viscosity adjustment and gel prevention of the composition. The water-miscible organic solvent referred to in the present invention refers to a solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25°C.

[0056] Examples of water-miscible organic solvents include (e1) alkanols such as ethanol, 1-propanol, 2-propanol, and 1-butanol, (e2) glycols such as propylene glycol, butylene glycol, and hexylene glycol, (e3) glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol, (e4) diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerin ether, 2-methylglycerin ether, 1,3-dimethylglycerin ether, 1-ethylglycerin ether, and 1,3-dimethylglycerin ether. Examples of the alkyl ethers include ethyl glycerin ether, triethyl glycerin ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, and diethylene glycol monobutyl ether; (e5) aromatic ethers such as 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, phenoxypropylene glycol, 2-benzyloxyethanol, and diethylene glycol monobenzyl ether; and (e6) ethylene oxide and / or propylene oxide polymers having an average molecular weight of 500 to 5,000, specifically polypropylene glycol having an average molecular weight of 500 to 5,000, polyethylene glycol having a molecular weight of 500 to 5,000, and oxypropylene and oxyethylene copolymers (which may be block or random), and one or more of these may be used.

[0057] From the viewpoint of appearance transparency, component (e) is preferably one or more selected from diethylene glycol monobutyl ether, ethanol, propylene glycol, diethylene glycol, 2-phenoxyethanol, and polypropylene glycol having a molecular weight of 500 or more and 3000 or less, more preferably one or more selected from diethylene glycol monobutyl ether, ethanol, propylene glycol, and polypropylene glycol having a molecular weight of 500 or more and 3000 or less, and even more preferably one or more selected from diethylene glycol monobutyl ether and polypropylene glycol having a molecular weight of 500 or more and 3000 or less.

[0058] From the viewpoint of appearance transparency, the detergent composition of the present invention contains component (e) in an amount of preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, still more preferably 3% by mass or less, and still more preferably 2% by mass or less.

[0059] The detergent composition of the present invention may contain components such as surfactants, solvents, enzymes (protease, lipase, carbohydrate-degrading enzyme, etc.), hydrotropes, pH adjusters, thickeners, dispersants, viscosity modifiers, fragrances, colorants, antioxidants, and preservatives, provided that the components do not impair the object of the present invention (excluding components (a), (a1), (b), (c), (d), and (e)).

[0060] The cleaning composition of the present invention contains water. The water is not particularly limited, but examples thereof include tap water, well water, ion-exchanged water, and distilled water. In the present invention, water is preferably used in an amount that makes up the remainder of the composition (amount that makes the total 100% by mass). The content of water in the composition can be, for example, 50% by mass or more, further 60% by mass or more, and further 70% by mass or more.

[0061] From the viewpoint of ease of handling, the cleaning composition of the present invention has a pH at 20°C of preferably 3 or more, more preferably 5 or more, even more preferably 6 or more, and preferably 10 or less, more preferably 9 or less, even more preferably 8 or less. The pH value was determined by the glass electrode method.

[0062] The detergent composition of the present invention can be suitably used for hard articles. The detergent composition of the present invention can be used for various hard articles, but is preferably used for dishes and / or hard articles around the kitchen, and more preferably used for dishes.

[0063] Hard items around the kitchen are items used around the kitchen, specifically: (1) Storage areas for food, tableware, and cooking utensils, such as refrigerators and cupboards, (2) Food preparation areas such as drains, countertops, range hoods, sinks, gas ranges, and microwave ovens; (3) Floors and walls around the storage area and cooking area In the present invention, these are referred to as "hard kitchen items" for convenience. In addition, specifically, the tableware is: (i) Plates, bowls, and other tableware; (ii) Storage containers such as Tupperware and bottles, (iii) Cooking utensils such as knives, cutting boards, pots, frying pans, and fish grills; (iv) Food processors, mixers, and other cooking appliances In the present invention, these are referred to as "tableware" for convenience. Furthermore, the present invention preferably applies to an item selected from tableware, storage containers, cooking utensils, and cooking appliances, and more preferably applies to an item selected from plates, bowls, Tupperware, bottles, knives, cutting boards, pots, frying pans, fish grills, food processors, and mixers.

[0064] The materials of the hard articles targeted by the present invention include plastics (including silicone resins), metals, ceramics, wood, and combinations thereof. The detergent composition of the present invention can effectively remove oily stains from these hard articles.

[0065] <How to clean hard items> The present invention provides a method for cleaning denatured oily stains, which comprises contacting a hard article having oily stains, including denatured oily stains, with the detergent composition of the present invention or a cleaning liquid prepared by diluting the detergent composition with water. The features described for the detergent composition of the present invention can be appropriately applied to the method for cleaning denatured oily stains of the present invention.

[0066] In the method for cleaning denatured oily soils of the present invention, the detergent composition of the present invention can be foamed and then contacted with a hard article. For example, the detergent composition of the present invention can be foamed with a sponge or a sprayer equipped with a foam-forming mechanism and then contacted with the hard article. Alternatively, the detergent composition of the present invention can be contacted with the hard article by spraying, applying, immersing, or the like.

[0067] In the cleaning method for denatured oil stains of the present invention, a cleaning liquid (hereinafter simply referred to as cleaning liquid) prepared by diluting the detergent composition of the present invention with water may be foamed and brought into contact with hard articles, or the cleaning liquid may be brought into contact with hard articles by spraying, applying, immersing, or the like. In the present invention, the detergent composition may be diluted before use, but excessive dilution may impair the effect, so the detergent composition of the present invention is preferably diluted with water at a ratio of 80 times or less, more preferably 40 times or less. The detergent composition of the present invention can also be used in its undiluted form.

[0068] The hard articles that can be treated with the method for cleaning denatured oily soils of the present invention include those described above for the detergent composition of the present invention, and tableware is one of the preferred hard articles.

[0069] In the method for cleaning denatured oily soils of the present invention, the soils adhered to hard articles may be oily soils containing denatured oily soils, or may even be denatured oily soils.

[0070] In the method for cleaning denatured oil stains of the present invention, the cleaning agent composition or cleaning solution of the present invention may be brought into contact with a hard article having oil stains or the like containing denatured oil, particularly heat-denatured oil, by immersing the composition in the composition. However, from the viewpoint of efficiently increasing the cleaning power, a method in which the composition is sprayed or applied and brought into contact with the hard article having oil stains or the like containing denatured oil, particularly heat-denatured oil, is preferred. The method for contacting the cleaning composition or cleaning solution of the present invention with hard articles having oily stains or the like attached thereto is preferably spraying or applying, and more preferably spraying in the form of droplets or applying in the form of foam. Specifically, for example, a spray means is used for contacting the cleaning composition or cleaning solution of the present invention with hard articles. That is, in the present invention, it is preferable to use a hard article cleaner obtained by filling the cleaning composition or cleaning solution of the present invention in a container equipped with a sprayer.

[0071] Examples of the method for applying the foam include a method in which air is entrained into the detergent composition or cleaning liquid of the present invention using the nozzle of a sprayer to generate foam, and a method in which the detergent composition or cleaning liquid of the present invention is impregnated into a sponge or a fiber article for cleaning, and then the sponge or the fiber article for cleaning is rubbed several times to generate foam.

[0072] The present invention provides a cleaning agent in a spray container, which is obtained by filling the cleaning composition or cleaning liquid of the present invention into a container equipped with a sprayer.

[0073] Examples of the container equipped with the sprayer in the spray-container cleaner of the present invention include manual spray devices that do not use a propellant, such as trigger-type spray containers and pump-type spray containers, and aerosols that use a propellant. The container equipped with the sprayer is preferably a trigger-type spray that can spray or apply the contents in the form of droplets or foam, and more preferably a trigger-type spray equipped with a mechanism for spraying the contents in the form of droplets or a mechanism for forming foam (foam-forming mechanism).

[0074] When a trigger-type sprayer equipped with a mechanism for spraying the cleaning composition or cleaning liquid of the present invention in droplets is used in the spray-bottled cleaner of the present invention, the nozzle diameter of the spray container containing the composition is preferably 0.1 mm or more, more preferably 0.3 mm or more, and preferably 2 mm or less, more preferably 1 mm or less, so as to facilitate spraying, to prevent the sprayed droplets from being rough, from being sprayed in a straight line, and to prevent the spray area from being extremely narrow. When using a trigger-type sprayer equipped with a mechanism for spraying droplets, the spray-contained cleaner of the present invention sprays preferably 0.1 mL or more, more preferably 0.3 mL or more, and preferably 5 mL or less, more preferably 2 mL or less of the composition in one operation.

[0075] When using a trigger-type spray equipped with a foam-forming mechanism, the spray-contained cleaner of the present invention sprays preferably 0.5 mL or more, more preferably 1 mL or more, and preferably 30 mL or less, more preferably 15 mL or less, and even more preferably 5 mL or less of the composition in one operation.

[0076] In the cleaning method for denatured oil stains of the present invention, the cleaning agent composition or cleaning solution of the present invention is brought into contact with a hard article to clean it. In the cleaning method of the present invention, the stains can be removed from the hard article and cleaned by, for example, soaking the hard article in the cleaning agent composition of the present invention, leaving it in an applied state, rubbing it with a sponge or textile product, rinsing it with running water, or the like. Thereafter, the hard article can be rinsed with running water, etc. The cleaning method of the present invention may be a hand-washing method, and hard articles such as tableware can be hand-washed in accordance with known techniques. [Example]

[0077] The detergent compositions shown in Tables 1 to 3 were prepared using the ingredients listed below. The detergent compositions shown in Tables 1 to 3 were prepared by adding components (a), (b), (c), (d), and (e) in the amounts shown in the tables and dissolving them at room temperature (20°C). After blending, the pH was adjusted to the value shown in the tables using sodium hydroxide. The pH was measured using a glass electrode method. The mass percentages of the ingredients in Tables 1 to 3 are all values ​​based on the active ingredients.

[0078] <Composition ingredients> (a) Ingredients Amit 102: polyoxyethylene (2.1) laurylamine, component (a1), in general formula (a1), R 1a is an alkyl group with 12 carbon atoms, m+n is 2.1, manufactured by Kao Corporation Amit 105: Polyoxyethylene (4) cocoalkylamine, component (a1), in general formula (a1), R 1a is an alkyl group having 8 to 18 carbon atoms, and m+n is 4, manufactured by Kao Corporation Amit 302: polyoxyethylene (2.1) alkyl (C14-18) amine, component (a1), in general formula (a1), R 1a is an alkyl group having 14 to 18 carbon atoms, and m+n is 2.1, manufactured by Kao Corporation Amphitol 20N: lauryldimethylamine oxide, component (a2), in general formula (a2), R 2a is an alkyl group having 12 carbon atoms, R 3a and R 4a Compound with methyl group, q=0, and p=0, manufactured by Kao Corporation Amphitol 40N: Myristyldimethylamine oxide, component (a2), in general formula (a2), R 2a is an alkyl group having 14 carbon atoms, R 3a and R 4a Compound with methyl group, q=0, and p=0, manufactured by Kao Corporation Amphitol 08N: Capryldimethylamine oxide, component (a2), in general formula (a2), R 2a is an alkyl group having 8 carbon atoms, R 3a and R 4a Compound with methyl group, q=0, and p=0, manufactured by Kao Corporation AG-124: alkyl polyglycoside, component (a3), in general formula (a3), R 5a is an alkyl group having 10 to 14 carbon atoms, G is a residue derived from glucose, x is 0, and y is 1.3. GE-EH: 2-ethylhexyl glyceryl ether, component (a4), manufactured by Kao Corporation

[0079] (b) Component Sanizol B-50: benzyl-alkyl(C12-16)dimethylammonium chloride, in the general formula (b2), R 5b is an alkyl group having 12 to 16 carbon atoms (60% by mass of C12, 30% by mass of C14, and 10% by mass of C16), R 6b and R 7b is a methyl group, X - is a chloride ion, manufactured by Kao Corporation Levenol RK: benzyl-alkyl(C8-18)dimethylammonium chloride, where R 5b is an alkyl group having 8 to 18 carbon atoms (80% by mass of C10), R 6b and R 7b is a methyl group, X - is a chloride ion, manufactured by Kao Corporation Sanizol 08: benzyl-octyldimethylammonium chloride, in the general formula (b2), R 5b is an alkyl group having 8 carbon atoms, R 6b and R 7b is a methyl group, X - is a chloride ion, manufactured by Kao Corporation QUARTAMINE 60W: Cetyltrimethylammonium chloride, in the general formula (b1), R 1b is an alkyl group having 16 carbon atoms, R 2b , R 3b and R 4b is a methyl group, X - is a chloride ion, manufactured by Kao Corporation

[0080] (c) Component Citric acid: molecular weight 192, tricarboxylic acid, manufactured by Sanfu Chemical Co., Ltd. Malic acid: molecular weight 134, dicarboxylic acid, manufactured by Fuso Chemical Co., Ltd. MGDA: Methylglycine diacetic acid, molecular weight 205, tricarboxylic acid, manufactured by Tokyo Chemical Industry Co., Ltd. GLDA: Glutamic acid diacetic acid, molecular weight 259, tetracarboxylic acid, manufactured by Tokyo Chemical Industry Co., Ltd. EDTA: Ethylenediaminetetraacetic acid, molecular weight 292, tetracarboxylic acid, manufactured by Tokyo Chemical Industry Co., Ltd.

[0081] (d) Ingredients Neopelex G-25: Sodium alkylbenzenesulfonate (soft type), alkyl group carbon number 10-14, manufactured by Kao Corporation (e) Component BDG: Diethylene glycol monobutyl ether, manufactured by Chunichi Synthetic Chemical PPG-1000: Polypropylene glycol, molecular weight 1000, manufactured by AGC Co., Ltd.

[0082] <Cleaning power against denatured oil stains 1> The protective film was removed from a SUS304 test piece (1.0 mm × 25 mm × 70 mm) manufactured by Engineering Test Service Co., Ltd., and the piece was sponge washed and rinsed (once with tap water and twice with ion-exchanged water) using a neutral dishwashing detergent, and then dried at 80°C in an electric dryer to obtain a pretreated SUS plate. The mass of the pretreated SUS plate was weighed using a four-digit balance and defined as the initial mass (X). A modified oil / chloroform solution was prepared by mixing 20 g of modified oil with 60 ml of chloroform. The modified oil was prepared by heating rapeseed oil (Fujifilm Wako Pure Chemical Industries, Ltd.) at 180°C for 8 hours. A denatured oil / chloroform solution was applied at 1 mg / cm2 to an area of ​​25 mm x 50 mm on one side of the pretreated SUS plate. 2 The oil was poured onto the plate once using a dropper so that the oil-adhered surface was facing upwards and left to dry flat overnight to prepare a SUS plate for cleaning. The mass of the SUS plate for cleaning was measured using a balance with a four-digit scale and this was taken as the mass before cleaning (Y). Three SUS cleaning plates were used for evaluation for each type of cleaning composition listed in Tables 1 to 3. Three SUS cleaning plates were arranged on a balance dish BD-3 (140 x 140 x 25 mm), immersed in 40 ml of a cleaning solution prepared by diluting the cleaning composition listed in Tables 1 to 3 20 times with water, and left to stand at 25°C for 20 minutes. The plates were then rinsed with tap water for 1 minute using a Lenauts tester at 300 rpm, and then left to dry flat overnight. The mass of the dried SUS cleaning plate was weighed using a four-digit balance and recorded as the post-cleaning mass (Z). The cleaning rate was calculated from the initial mass (X), the mass before cleaning (Y), and the mass after cleaning (Z) using the following formula. The results are shown in Tables 1 to 3. Cleaning rate (%) = [mass before cleaning (Y) - mass after cleaning (Z)] / [mass before cleaning (Y) - initial mass (X)] x 100

[0083] <Cleaning power against denatured oil stains 2> The protective film was removed from a SUS304 test piece (1.0 mm × 25 mm × 70 mm) manufactured by Engineering Test Service Co., Ltd., and the piece was sponge washed and rinsed (once with tap water and twice with ion-exchanged water) using a neutral dishwashing detergent, and then dried at 80°C in an electric dryer to obtain a pretreated SUS plate. The mass of the pretreated SUS plate was weighed using a four-digit balance and defined as the initial mass (X). A modified oil / chloroform solution was prepared by mixing 20 g of modified oil with 60 ml of chloroform. The modified oil was prepared by heating rapeseed oil (Fujifilm Wako Pure Chemical Industries, Ltd.) at 180°C for 8 hours. A denatured oil / chloroform solution was applied at 1 mg / cm2 to an area of ​​25 mm x 50 mm on one side of the pretreated SUS plate. 2 The oil was poured onto the plate once using a dropper so that the oil-adhered surface was facing upwards and left to dry flat overnight to prepare a SUS plate for cleaning. The mass of the SUS plate for cleaning was measured using a balance with a four-digit scale and this was taken as the mass before cleaning (Y). Three SUS cleaning plates were used for evaluation for each type of detergent composition listed in Table 3. Three SUS cleaning plates were arranged on a balance dish BD-3 (140 x 140 x 25 mm), and the detergent composition listed in Table 3 was filled into a Biore U Foaming Hand Soap spray container (a container that had been emptied of its contents, washed with water several times, and dried) and foamed with the spray. The foam was applied to cover the entire SUS cleaning plate, and the plate was left to stand at 25°C for 20 minutes. The plate was then rinsed with tap water for 1 minute at 300 rpm using a Lenauts tester, and then left to dry flat overnight. The mass of the dried SUS cleaning plate was weighed using a four-digit balance and recorded as the post-cleaning mass (Z). The cleaning rate was calculated from the initial mass (X), the mass before cleaning (Y), and the mass after cleaning (Z) using the following formula. The results are shown in Table 3. Cleaning rate (%) = [mass before cleaning (Y) - mass after cleaning (Z)] / [mass before cleaning (Y) - initial mass (X)] x 100

[0084] <Appearance evaluation> 40 mL of each prepared detergent composition was filled into a 50 mL sample bottle (No. 6 wide-mouth standard bottle, glass, cylindrical, 40 mm in diameter, 80 mm in height, with evaluation confirmation characters printed on the periphery of the bottle), the bottle was capped, and then allowed to stand in a thermostatic chamber at 25°C for 1 hour. After standing, the appearance of the composition was visually observed and rated according to the following criteria. The results are shown in Tables 1 to 3. Transparent: No turbidity and the text can be clearly seen through the sample bottle Cloudy and viscous: Cloudy and viscous, making it impossible to see the text through the sample bottle.

[0085] [Table 1]

[0086] [Table 2]

[0087] [Table 3]

Claims

1. 1. A cleaning agent composition comprising: (a) a nonionic surfactant [hereinafter referred to as component (a)] containing a polyoxyalkylene alkyl or alkenylamine [hereinafter referred to as component (a1)] having an alkyl or alkenyl group having from 8 to 18 carbon atoms and an average number of moles of oxyalkylene groups added of from 1 to 8 [hereinafter referred to as component (a)]; (b) a quaternary ammonium salt surfactant [hereinafter referred to as component (b)]; (c) a polycarboxylic acid or a salt thereof [hereinafter referred to as component (c)]; and water; wherein the content of (d) anionic surfactant [hereinafter referred to as component (d)] is less than 35% by mass based on the total content of component (a1) and component (b), and the content of component (d) is 20% by mass or less based on the total amount of surfactants.

2. 2. The cleaning composition according to claim 1, wherein the content of the component (a1) in the component (a) is 10% by mass or more and 100% by mass or less.

3. 3. The cleaning composition according to claim 1, wherein the component (c) is a divalent to tetravalent polycarboxylic acid or a salt thereof, having a molecular weight of 100 to 300 in terms of acid form.

4. 4. The cleaning composition according to claim 1, wherein a mass ratio (b) / (c) of the content of the component (b) to the content of the component (c) is 0.01 or more and 5 or less.

5. 5. The cleaning composition according to claim 1, wherein the mass ratio (a1) / (b) of the content of the component (a1) to the content of the component (b) is 0.1 or more and 200 or less.

6. 5. The cleaning composition according to claim 1, wherein a mass ratio (a1) / (c) of the content of the component (a1) to the content of the component (c) is 0.1 or more and 10 or less.

7. The hard article cleaning composition according to any one of claims 1 to 6, comprising, as component (a), one or more surfactants selected from (a2) an amine oxide surfactant, (a3) ​​an alkyl glycoside surfactant, and (a4) an alkyl glyceryl ether surfactant.

8. The cleaning composition according to any one of claims 1 to 7, which is for use on hard articles.

9. A method for cleaning denatured oily stains, comprising contacting the cleaning agent composition according to any one of claims 1 to 8 or a cleaning liquid obtained by diluting the same with water with a hard article on which oily stains, including denatured oily stains, are attached.

10. The method for cleaning denatured oily soils according to claim 9, wherein the cleaning composition is foamed and then contacted with the hard article.

11. The method for cleaning denatured oily soils according to claim 10, wherein the cleaning composition is foamed with a sponge or a sprayer equipped with a foam-forming mechanism and then contacted with the hard article.

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