Detergent composition for hard articles

Abstract

To provide a detergent composition for hard articles that has high detergency on stains of oil such as denatured oil.SOLUTION: The present invention discloses a detergent composition for hard articles, the detergent composition containing component (a) and component (b). The composition has a total hydrophilic and lipophilic index of 9 or more and 14.2 or less. Component (a): polyoxyalkylene alkyl or alkenyl amine having a C8-18 alkyl group or alkenyl group and moreover having an average number of added mol of oxyalkylene groups of 1-5. Component (b): non-ionic surfactants (excluding component (a) and amide-type non-ionic surfactants).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a cleaning agent composition for hard articles and a method for cleaning hard articles.

Background Art

[0002] Generally, as cleaning agents used for kitchen appliances such as ranges, ovens, walls and floors around ranges, and ventilation fans, and for food processing equipment, cleaning agents containing surfactants, solvents, alkalis, etc. are used to remove various stains such as food-derived stains and stains derived from components used in cooking.

[0003] Patent Document 1 discloses a liquid cleaning agent composition containing (a) an amine oxide surfactant having a hydrocarbon group with 7 to 18 carbon atoms, (b) a nonionic surfactant with an HLB of 1 to 10, and (c) a compound represented by a specific general formula (c1) having an alkyl group with 1 to 5 carbon atoms under predetermined conditions. Patent Document 2 discloses a cleaning agent composition containing (A) an anionic surfactant, (B) a nonionic surfactant, and (C) at least one of dihydroxyethylglycine and its salts, wherein (C) dihydroxyethylglycine and its salts are 0.1 to 50 parts by mass with respect to a total of 100 parts by mass of (A) anionic surfactant and (B) nonionic surfactant. Patent Document 3 discloses a liquid cleaning agent composition for hard articles around dishes and / or in the kitchen, containing (a) a nonionic surfactant with an HLB of 10.5 or less (excluding (b)), (b) a glycoside having a hydrocarbon group with 8 to 18 carbon atoms and a glycoside group with an average degree of condensation of 0.5 to 3, and (c) an organic solvent with a logPow of 0 to 1.5, wherein the content of (a) in all surfactants is 30% to 95% by mass, the mass ratio (c) / (a) of the content of (c) to the content of (a) is 2 to 8, and the viscosity at 20°C is 20 mPa·s or less. Patent Document 4 discloses a liquid cleaning agent composition for hard surfaces containing a surfactant, wherein the surfactant contains (A) a nonionic surfactant and optionally (B) an amphoteric surfactant, with (A) accounting for 60% by mass or more of the total surfactant, and (A) contains (A1) an alkyl mono or dialkanolamine or its alkylene oxide adduct (the alkylene oxide has 2 or 3 carbon atoms), wherein the alkyl group has 10 to 18 carbon atoms and the alkanol group has 2 or 3 carbon atoms, and the proportion of (A1) in the total of (A) and (B) is 0.5% by mass or more and 20% by mass or less. Patent Document 5 discloses a liquid disinfectant detergent composition containing (A) an anionic surfactant, (B) a long-chain alkyl di-short-chain alkyl hydroxyethylammonium salt, (C) a nonionic surfactant compound having a specific structure, (D) at least one selected from nonionic surfactants other than (C) and amphoteric surfactants, (E) a solvent, and (F) water. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-97711 [Patent Document 2] Japanese Patent Publication No. 2020-90606 [Patent Document 3] Japanese Patent Publication No. 2019-210475 [Patent Document 4] Japanese Patent Publication No. 2020-15863 [Patent Document 5] Japanese Patent Publication No. 2020-200420 [Overview of the project] [Problems that the invention aims to solve]

[0005] Among the types of dirt that adhere to dishes and cooking utensils, oil stains are modified by the action of heat, light, and oxygen in the air, becoming extremely difficult to remove (modified oil stains). Therefore, dish and cooking utensil cleaning agents need to have excellent cleaning power against modified oil stains.

[0006] The present invention provides a cleaning agent composition for hard articles that exhibits excellent cleaning power against oily stains such as modified oil stains. [Means for solving the problem]

[0007] The present invention relates to a cleaning agent composition for hard articles containing the following component (a) and component (b), wherein the hydrophilic-lipophilic index of the entire composition is 9 or more and 14.2 or less. (a) Components: Polyoxyalkylene alkyl or alkenylamine having an alkyl or alkenyl group with 8 to 18 carbon atoms, and an average number of added moles of oxyalkylene groups of 1 to 5. (b) Components: Nonionic surfactants (excluding components (a) and amide-type nonionic surfactants)

[0008] Furthermore, the present invention relates to a method for cleaning hard articles, comprising bringing the cleaning agent composition for hard articles of the present invention into contact with a hard article to which dirt is attached. [Effects of the Invention]

[0009] The present invention provides a cleaning agent composition for hard articles that exhibits excellent cleaning power against oily stains such as modified oil stains. [Modes for carrying out the invention]

[0010] Although the mechanism by which the effects of this invention are realized has not been fully elucidated, the applicant believes it to be as follows. Among modified oil stains, those adhering to cookware and cooking equipment become highly modified due to their heat history, and it is considered advantageous to use relatively hydrophobic detergents to remove them from the object during cleaning. However, such detergents generally have low foaming properties, and when cleaning relatively low-degree-modified oil stains on dishes, the low-degree-modified oil stains exhibit foam-breaking properties, resulting in insufficient foaming, a reduction in the amount of dishes that can be cleaned, and decreased efficiency. Furthermore, if foaming is considered to prioritize cleaning dishes, which are relatively hydrophilic and have a low degree of modification, the cleaning performance of countertops and ranges, which often have highly modified stains, will decrease. When components (a) and (b) of the present invention are adsorbed onto modified oil stains, for example, via hydrophobic alkyl groups, component (a) is adsorbed near the adsorption interface or spreads horizontally relative to the adsorption interface at a location away from the adsorption interface, due to the small number of moles of the hydrophilic oxyalkylene group portion. Component (b) is adsorbed with relatively free movement perpendicular to the adsorption interface, due to the hydrophilic portion, such as the oxyalkylene group portion. Components (a) and (b), possessing such adsorption characteristics, cannot satisfy the required performance for highly modified oils and low-modified oils by adjusting the hydrophilicity of each individual structure. When components (a) and (b) coexist, it is expected that the density of hydrophilic groups will be high near the hydrophobic groups, and that the hydrophilic region will be broad, away from the stain interface, forming molecular aggregates. When such a surfactant molecular assembly has a specific hydrophilic-lipophilic index throughout the entire cleaning system, adsorption occurs effectively to highly hydrophobic, modified oil stains. Furthermore, because the hydrophilic group structure is robust, it is thought that the removal and dispersion of difficult-to-clean, highly modified oil stains can be promoted without reducing foaming properties. Additionally, because the hydrophilic group region is broad, a decrease in foaming properties is not expected. Furthermore, the effects of this invention are not limited to the mechanisms of action described herein.

[0011] <Cleaning agent composition for hard articles> (Component (a) is a polyoxyalkylene alkyl or alkenylamine having an alkyl or alkenyl group with 8 to 18 carbon atoms and an average addition molar number of oxyalkylene groups of 1 to 5.)

[0012] (From the viewpoint of detergency for highly denatured oil (hereinafter referred to as "detergency"), the number of carbon atoms of the alkyl or alkenyl group possessed by component (a) is 8 or more, preferably 10 or more, and 18 or less, preferably 16 or less.) (The group possessed by component (a) 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, that is, an oxyethylene group and / or an oxypropylene group, and more preferably an oxyethylene group. Component (a) preferably contains an oxyethylene group as the oxyalkylene group.) (From the viewpoint of detergency, the average addition molar number of oxyalkylene groups of component (a) is 1 to 5, preferably 1.5 or more, more preferably 2 or more, and preferably 4.5 or less, more preferably 3 or less.)

[0013] (Examples of component (a) include alkylene oxide adducts of monoamines having an alkyl or alkenyl group with 8 to 18 carbon atoms and an average addition molar number of oxyalkylene groups of 1 to 5.)

[0014] (Examples of component (a) include compounds represented by the following general formula (a1).)

[0015] [Chemical formula]

[0016] [In the formula, R is an alkyl or alkenyl group having 8 to 18 carbon atoms, EO is an ethyleneoxy group, m and n are average addition molar numbers, independently numbers of 0 or more and 5 or less, and the sum of m and n is 1 or more and 5 or less.]

[0017] In formula (a1), R may have 8 or more, further 10 or more, and 18 or less, further 16 or less carbon atoms. R is preferably an alkyl group. The total of m and n is preferably 1.5 or more, more preferably 2 or more, and preferably 4.5 or less, more preferably 3 or less.

[0018] (a) The HLB of the component is not particularly limited as long as it does not deviate from the range of the hydrophilic-lipophilic balance of the entire cleaning composition for hard articles of the present invention. However, from the viewpoints of easy availability and modified oil detergency, for example, it may be preferably 9 or more, more preferably 9.5 or more, and preferably 14.2 or less, more preferably 13.0 or less. The HLB of the (a) component is by Griffin's method. In the present invention, the hydrophilic-lipophilic balance measured by the method of <Method for Measuring the Hydrophilic-Lipophilic Balance of the Cleaning Composition for Hard Articles> described in this specification, provided that the hydrophilic-lipophilic balance measured by replacing the cleaning composition for hard articles with a mixture containing 5% by mass of the surfactant to be measured and the remainder being water can be regarded as the HLB by the Griffin method. This is the same for the HLB of other surfactants such as the (b) component.

[0019] From the viewpoint of detergency, the cleaning composition for hard articles of the present invention can contain the (a) component, for example, 0.01% by mass or more, further 0.05% by mass or more, further 0.1% by mass or more, and 50% by mass or less, further 30% by mass or less, further 15% by mass or less.

[0020] From the viewpoint of cleaning performance, the cleaning agent composition for hard articles of the present invention may contain, for example, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 30% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, relative to the total amount of surfactants in the composition. The total amount of surfactants is the total amount of components (a), (b), an arbitrary (c), and any other surfactants contained in the composition, such as any (d) and any (d'). The cleaning agent composition for hard articles of the present invention is a composition containing surfactants, and may be a composition containing components (a) and (b) as surfactants.

[0021] (b) Component is a nonionic surfactant (excluding component (a) and amide-type nonionic surfactants).

[0022] Furthermore, component (b) of the present invention is a nonionic surfactant having hydrocarbon groups preferably with 10 or more carbon atoms, more preferably with 11 or more carbon atoms, and preferably with 18 or fewer carbon atoms, and more preferably with 16 or fewer carbon atoms.

[0023] In this invention, substances having hydrocarbon groups with 10 or more carbon atoms can be considered nonionic surfactants. Therefore, the content of nonionic surfactants included in the total amount of surfactants in the composition, such as component (b) and component (d) described later, may be the content of nonionic surfactants having hydrocarbon groups with 10 or more carbon atoms in the composition. For example, nonionic compounds having hydrocarbon groups with 9 or fewer carbon atoms are not considered nonionic surfactants, and therefore do not need to be included in the total amount of surfactants in the composition.

[0024] (b) The component may be one or more nonionic surfactants selected from (b1) polyoxyalkylene alkyl ether [hereinafter referred to as component (b1)], (b2) alkyl(poly)glycoside [hereinafter referred to as component (b2)], (b3) polyoxyalkylene fatty acid ester [hereinafter referred to as component (b3)], (b4) polyglycerin fatty acid ester [hereinafter referred to as component (b4)], and (b5) (poly)oxyalkylene sorbitan fatty acid ester [hereinafter referred to as component (b5)]. (b) Component may be a nonionic surfactant selected from alkoxylate-type nonionic surfactants and alkyl glycoside-type surfactants. Component (b1) is an example of an alkoxylate-type nonionic surfactant. Component (b2) is an example of an alkyl glycoside-type surfactant.

[0025] The oxyalkylene group of component (b1) is preferably a carbon 2 oxyalkylene group and / or a carbon 3 oxyalkylene group, i.e., an oxyethylene group and / or an oxypropylene group, with an oxyethylene group being more preferred. From the viewpoint of washability, the average number of moles of oxyalkylene groups added to component (b1) is preferably 0 or more, more preferably 1 or more, and preferably 25 or less, and more preferably 23 or less. (b1) Component (b1) preferably contains an oxyethylene group as an oxyalkylene group from the viewpoint of cleanability. The number of carbon atoms in the alkyl group of component (b1) is preferably 10 or more, more preferably 12 or more, preferably 30 or less, more preferably 24 or less, even more preferably 18 or less, and even more preferably 16 or less from the viewpoint of cleanability. The alkyl group of component (b1) may be linear or branched, but linear is preferred. The alkyl group of component (b1) may be saturated or unsaturated, but saturated is preferred.

[0026] (b2) From the viewpoint of cleanability, the number of carbon atoms in the alkyl group of component (b2) is preferably 10 or more, more preferably 12 or more, preferably 30 or less, more preferably 24 or less, even more preferably 18 or less, and even more preferably 16 or less. Also, from the viewpoint of cleanability, the average degree of condensation of sugars such as glucose in component (b2) is preferably 1 or more, 10 or less, and even more preferably 5 or less. From the viewpoint of cleanability, alkyl(poly)glycosides in component (b2) whose constituent sugar is glucose are preferred.

[0027] The cleaning agent composition for hard articles of the present invention preferably contains, as component (b), one or more nonionic surfactants selected from components (b1) and (b2), and further one or more nonionic surfactants selected from component (b1).

[0028] The HLB of component (b) is not particularly limited as long as it does not deviate from the range of the hydrophilic-lipophilic index of the entire hard article cleaning agent composition of the present invention, but from the viewpoint of availability and modified oil cleaning ability, it may be, for example, preferably 9 or more, more preferably 9.5 or more, and preferably 17.4 or less, and more preferably 16.9 or less. The HLB of component (b) is determined by the Griffin method, and as described above, the hydrophilic-lipophilic index measured by a predetermined method can be considered as the HLB of component (b) by the Griffin method.

[0029] (b) Component is preferably one or more nonionic surfactants selected from alkoxylate-type nonionic surfactants and alkyl glycoside-type surfactants with an HLB of 9 to 17.4, from the viewpoint of cleaning performance, more preferably one or more nonionic surfactants selected from components (b1) and (b2) with an HLB of 9 to 17.4, and more preferably one or more nonionic surfactants selected from component (b1) with an HLB of 9 to 17.4.

[0030] From the viewpoint of cleaning performance, the cleaning agent composition for hard articles of the present invention may contain component (b) in, for example, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0031] From the viewpoint of cleaning performance, the cleaning agent composition for hard articles of the present invention may contain, for example, preferably 8% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and even more preferably 68% by mass or less, relative to the total amount of surfactants in the composition, component (b), further component (b) with an HLB of 9 or more and 17.4 or less, one or more nonionic surfactants with an HLB of 9 or more and 17.4 or less selected from component (b1) and component (b2), and even more preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and even more preferably 68% by mass or less.

[0032] From the viewpoint of cleaning performance, the cleaning agent composition for hard articles of the present invention may have a mass ratio (a) / (b) of the content of component (a) to the content of component (b), for example, preferably 0.01 or more, more preferably 0.04 or more, even more preferably 0.08 or more, even more preferably 0.1 or more, and preferably 30 or less, more preferably 20 or less, even more preferably 13 or less, and even more preferably 10 or less.

[0033] The cleaning agent composition for hard articles of the present invention may contain, to the extent that it does not impair the objectives of the present invention, surfactants other than component (a) and component (b), solvents, enzymes (such as proteolytic enzymes, oleolytic enzymes, and carbohydrate-degrading enzymes), hydrotropes, pH adjusters, thickeners, dispersants, viscosity modifiers, fragrances, colorants, antioxidants, and preservatives.

[0034] The cleaning agent composition for hard articles of the present invention may optionally contain the following component (c). (c) Ingredients: Anionic surfactant

[0035] (c) Examples of components include fatty acid salts (preferably with 8 to 24 carbon atoms), alkyl (preferably with 8 to 24 carbon atoms) sulfonates, alkyl (preferably with 8 to 18 carbon atoms) benzenesulfonates, alkyl (preferably with 8 to 24 carbon atoms) sulfate esters, alkyl (preferably with 2 to 24 carbon atoms) phosphate esters, polyoxyalkylene (preferably polyoxyethylene) alkyl (preferably with 8 to 18 carbon atoms) sulfate esters, polyoxyalkylene (preferably polyoxyethylene) alkyl (preferably with 8 to 18 carbon atoms) carboxylates, alkyl (preferably with 6 to 18 carbon atoms) sulfosuccinates, etc. Examples of salts include alkali metal salts such as sodium salts and potassium salts.

[0036] The cleaning agent composition for hard articles of the present invention may contain component (c) in an amount that is, for example, 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 5% by mass or less, more preferably 3.5% by mass or less, and even more preferably 2.4% by mass or less, from the viewpoint of cleaning performance.

[0037] From the viewpoint of cleaning performance, the cleaning agent composition for hard articles of the present invention may contain, for example, preferably 0% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 3% by mass or more, and preferably 50% by mass or less, more preferably 25% by mass or less, even more preferably 22% by mass or less, even more preferably 20% by mass or less, and even more preferably 18.5% by mass or less, relative to the total amount of surfactants in the composition. The cleaning agent composition for hard articles of the present invention may contain 0% by mass of component (c) in the composition.

[0038] The cleaning agent composition for hard articles of the present invention may optionally contain component (d) below, but from the viewpoint of cleaning performance, it is preferable that the content of component (d) is less than 10% by mass, more preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass or less, relative to the total amount of surfactants in the composition, and the lower limit may be 0% by mass or more. The cleaning agent composition for hard articles of the present invention may contain 0% by mass of component (d) in the composition. (d) Ingredients: Amide-type nonionic surfactant

[0039] (d) Component may include amide compounds of a fatty acid having 8 or more carbon atoms, and moreover 11 to 18 carbon atoms, and an alkylamine having 1 to 6 hydroxyl groups. Preferably, the alkylamine has 1 or more carbon atoms, and moreover 2 to 8 carbon atoms. Specifically, examples include monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, glucamine, N-methylglucamine, and N-methylethanolamine. In the present invention, component (d) may contain fatty acid (8 or more carbon atoms, and moreover 11 to 18 carbon atoms) diethanolamide, fatty acid (8 or more carbon atoms, and moreover 11 to 18 carbon atoms) N-methylethanolamide, and fatty acid (8 or more carbon atoms, and moreover 11 to 18 carbon atoms) N-methylglucamide. In the present invention, the content of component (d) may be the total content in the composition of an amide-type nonionic surfactant selected from fatty acid (8 or more carbon atoms, further 11 to 18 carbon atoms) diethanolamide, fatty acid (8 or more carbon atoms, further 11 to 18 carbon atoms) N-methylethanolamide, and fatty acid (8 or more carbon atoms, further 11 to 18 carbon atoms) N-methylglucamide.

[0040] The cleaning agent composition for hard articles of the present invention may optionally contain the following component (d'), but from the viewpoint of cleaning performance, the content of component (d') is preferably less than 10% by mass, more preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 1.5% by mass or less, with a lower limit of 0% by mass or more, relative to the total amount of surfactants in the composition. The cleaning agent composition for hard articles of the present invention may contain 0% by mass of component (d') in the composition. (d') Ingredients: Betaine-type surfactant

[0041] Component (d') is a surfactant having a betaine structure. Examples of component (d') include alkyl (e.g., 8 to 18 carbon atoms) dimethylaminoacetic acid betaine, alkyl (e.g., 8 to 18 carbon atoms) amidopropyl betaine, alkyl (e.g., 8 to 18 carbon atoms) hydroxysulfobetaine, and alkyl (preferably 8 to 18 carbon atoms) carboxymethyl hydroxyethyl imidazolium betaine. In the present invention, the content of component (d') may be the total content of betaine-type surfactants selected from alkyl (8 to 18 carbon atoms) dimethylaminoacetic acid betaine, alkyl (8 to 18 carbon atoms) amidopropyl betaine, alkyl (8 to 18 carbon atoms) hydroxysulfobetaine, and alkyl (8 to 18 carbon atoms) carboxymethyl hydroxyethyl imidazolium betaine in the composition.

[0042] From the viewpoint of cleaning performance and workability, the total amount of surfactant in the hard article cleaning agent composition of the present invention may be, for example, preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2.5% by mass or more, even more preferably 5% by mass or more, even more preferably 8% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 15% by mass or less. The hard article cleaning agent composition of the present invention is a composition containing a surfactant, and may contain component (a) and component (b) as surfactants, with the total amount of surfactants within the above range.

[0043] The cleaning agent composition for hard articles of the present invention may optionally contain component (e) below, however, component (e) tends to increase the hydrophilicity-hydrophobicity index of the composition and may affect the cleaning performance, so caution is required when including it. From the viewpoint of cleaning performance, the cleaning agent composition for hard articles of the present invention preferably contains component (e) at a rate of less than 50% by mass, more preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 2% by mass or less, relative to the total amount of surfactants in the composition, and the lower limit may be 0% by mass or more, but for the purpose of adjusting properties such as the viscosity of the composition, it may be 0.5% by mass or more, and more preferably 0.1% by mass or more. The cleaning agent composition for hard articles of the present invention may contain 0% by mass of component (e) in the composition. (e) Components: Hydrophilic solvent having hydrocarbon groups with 9 or fewer carbon atoms and a solubility in water of 5 g / 100 g or more at 25°C.

[0044] (e) Component may be one or more hydrophilic solvents selected from monohydric alcohols, diols, triols, mono-, di- or tri-alkylene glycol monoethers, and mono-, di- or tri-alkylene glycol diethers. Component (e) may have an alkyl group. The alkyl group can be selected from alkyl groups with various numbers of carbon atoms. The number of carbon atoms of the alkyl group is preferably 1 or more, more preferably 3 or more, preferably less than 10, and more preferably 8 or less. (e) As for the component, from the viewpoint of formulation stability and cleaning power, specifically, one or more hydrophilic solvents selected from methanol, ethanol, 1-propanol, 2-propanol, 1,2-hexanediol, ethylene glycol mono-methyl ether, diethylene glycol mono-methyl ether, triethylene glycol mono-methyl ether, ethylene glycol mono-butyl ether, diethylene glycol mono-butyl ether, and triethylene glycol mono-butyl ether are preferred, one or more hydrophilic solvents selected from ethanol, ethylene glycol mono-butyl ether, diethylene glycol mono-butyl ether, and triethylene glycol mono-butyl ether are more preferred, and diethylene glycol mono-butyl ether is even more preferred.

[0045] The cleaning agent composition for hard articles of the present invention preferably contains water from the viewpoint of composition stability and workability. The water is not particularly limited, but examples include tap water, well water, deionized water, and distilled water. In the present invention, it is preferable that water is used in an amount equal to the remainder of the composition (totaling 100% by mass). The water content can be, for example, 50% by mass or more, more specifically 60% by mass or more, and more specifically 70% by mass or more in the composition. The cleaning agent composition for hard articles of the present invention may be a liquid composition.

[0046] From the viewpoint of cleaning performance, the hydrophilic-lipophilic index of the hard article cleaning agent composition of the present invention is 9 or more and 14.2 or less for the entire composition. From the viewpoint of cleaning performance, the hydrophilic-lipophilic index of the hard article cleaning agent composition of the present invention may be, for example, 9 or more, preferably 9.5 or more, more preferably 9.6 or more, even more preferably 9.7 or more, even more preferably 9.8 or more, even more preferably 9.9 or more, more preferably 10 or more, even more preferably 10.0 or more, and 14.2 or less, preferably 14.0 or less, more preferably 13.9 or less, even more preferably 13.8 or less, even more preferably 13.7 or less, even more preferably 13.6 or less, even more preferably 13.5 or less, even more preferably 13.4 or less, even more preferably 13.3 or less, even more preferably 13.2 or less, even more preferably 12 or less, even more preferably 12.0 or less, even more preferably 11 or less, and even more preferably 11.0 or less. In this invention, the hydrophilic-lipophilic index of the cleaning agent composition for hard articles of the present invention was measured by the following method. This measurement method is based on the finding described in Japanese Patent Application Publication No. 2020-38061 that the physical properties of an aqueous sample containing a surfactant and water can be estimated by adding an oil component and a phase change probe to the aqueous sample, and measuring the amount of phase change probe when the phase structure of the mixture changes.

[0047] <Method for measuring the hydrophilicity and lipophilicity index of cleaning agent compositions for hard articles> (1) Creation of a calibration curve Prepare several polyoxyethylene lauryl ethers with different HLB values ​​for Griffin. If the concentration of surfactant (mmol / kg, hereinafter the same) in the hard article cleaning agent composition to be measured is unknown, measure its concentration beforehand. A precursor sample is prepared by mixing water with polyoxyethylene lauryl ether (of a specified HLB) such that the concentration of polyoxyethylene lauryl ether is the same as the concentration of the surfactant in the hard article cleaning agent composition. A standard sample is prepared by adding 2 g of oil (isoparaffin with an average of 16 carbon atoms) and 5 g of solvent (butyl diglycol) to the precursor sample. A phase change probe (2-ethylhexyl diglycol) is then added to the standard sample to quantify the amount of phase change probe required for the phase structure of the standard sample to change. This quantification is performed under the same conditions for multiple polyoxyethylene lauryl ethers with different HLB values, and multiple quantitative values ​​are obtained. A calibration curve is then created from these quantitative values ​​and the HLB values ​​of the surfactants contained in the standard samples that yield these quantitative values. (2) Calculation of the hydrophilic-lipophilic index To prepare the sample for measurement, 2 g of oil (isoparaffin with an average of 16 carbon atoms) and 5 g of solvent (butyl diglycol) were added to a cleaning agent composition for hard articles. A phase-change probe (2-ethylhexyl diglycol) is added to the sample, and the amount of the phase-change probe required to change the phase structure of the sample is quantified. The quantitative values ​​obtained from the phase-change probe for the measurement sample are applied to a calibration curve, and the HLB value of the corresponding calibration curve is taken as the hydrophilic-lipophilic index of the hard article cleaning agent composition. In addition, the temperature of each sample in each of the operations described in (1) and (2) above shall be 25°C.

[0048] The hydrophilic-lipophilic index of the cleaning agent composition for hard articles of the present invention can be set to a predetermined range by adjusting, for example, the type and amount of component (a), component (b), and any optional component. In the present invention, in order to set the hydrophilic index to a predetermined range, it is preferable to employ, for example, the following methods, either individually or in combination. 1: Adjust the mass ratio of components (a) / (b). The mass ratio of component (a) / (b) is, for example, preferably 0.01 or more, more preferably 0.04 or more, even more preferably 0.08 or more, even more preferably 0.1 or more, and preferably 30 or less, more preferably 20 or less, even more preferably 13 or less, and even more preferably 10 or less. 2: Adjust the content of component (c), which is a hydrophilic surfactant. (c) The content of component (c) is preferably 0% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 3% by mass or more, and preferably 50% by mass or less, more preferably 25% by mass or less, even more preferably 22% by mass or less, even more preferably 20% by mass or less, and even more preferably 18.5% by mass or less, relative to the total amount of surfactant in the composition. 3. Adjust the content of component (d'), which is a hydrophilic surfactant. The content of component (d') may be, for example, less than 10% by mass, 5% by mass or less, 3% by mass or less, 1.5% by mass or less, and 0% by mass or more, relative to the total amount of surfactants in the composition, or the content of component (d') in the composition may be 0% by mass. 4. Adjust the content of hydrophobic surfactants, such as component (d). (d) The content of component (d) may be, for example, less than 10% by mass, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, and 0% by mass or more, relative to the total amount of surfactants in the composition, or the content of component (d) in the composition may be 0% by mass. 5: (e) Adjust the content of the ingredients. The content of component (e) is as described above, less than 50% by mass, 10% by mass or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, and 0% by mass or more, 0.1% by mass or more, and 0.5% by mass or more, relative to the total amount of surfactants in the composition, or the content of component (e) in the composition is 0% by mass.

[0049] From the viewpoint of cleaning performance, the cleaning agent composition for hard articles of the present invention may have a pH at 20°C that is, for example, preferably 5 or higher, more preferably 5.5 or higher, even more preferably 6 or higher, and preferably 11 or lower, more preferably 9 or lower, and even more preferably 8.5 or lower.

[0050] The cleaning agent composition for hard articles of the present invention can be used for various hard articles, but is preferably for tableware and / or hard articles around the kitchen, and more preferably for tableware.

[0051] Hard materials used around the kitchen are items used in the vicinity of the kitchen, and specifically, (1) Refrigerators, cupboards, and other storage places for food, dishes, and cooking utensils, (2) Drains, countertops, range hoods, sinks, gas ranges, microwave ovens and other food preparation areas, (3) Floors, walls, etc. surrounding the storage area and the cooking area. In this invention, these are referred to as "hard articles for kitchen use" for convenience. Also, as for tableware, specifically, (i) Dishes such as plates and bowls, (ii) Storage containers such as Tupperware and glass jars, (iii) Cooking utensils such as knives, cutting boards, pots, frying pans, and fish grills, (iv) Cooking appliances such as food processors and blenders, etc. These include components and utensils that come into contact with the food ingredients. For convenience, in this invention, these will be referred to as "tableware." Furthermore, the present invention preferably covers articles selected from tableware, storage containers, cooking utensils, and cooking appliances, and more preferably covers articles selected from plates, bowls, Tupperware, bottles, knives, cutting boards, pots, frying pans, fish grills, food processors, and mixers.

[0052] The materials of the hard articles targeted by the present invention include plastics (including silicone resins), metals, ceramics, wood, and combinations thereof. The cleaning agent composition for hard articles of the present invention can effectively clean oily stains adhering to these hard articles.

[0053] As mentioned above, modified oil stains adhering to hydrophobic materials such as plastics are difficult to remove, but the present invention exhibits excellent cleaning effects even on modified oil stains adhering to hard plastic articles. The present invention is also suitable for cleaning hard plastic articles. Examples of plastics include polyolefins such as polypropylene and polyethylene, polymethacrylate, polycarbonate, ABS resin, and polyethylene terephthalate.

[0054] <Method for cleaning hard materials> The present invention provides a method for cleaning hard articles, which involves bringing the cleaning agent composition for hard articles of the present invention into contact with the hard article to which dirt is attached. The matters described in the cleaning agent composition for hard articles of the present invention can be appropriately applied to the cleaning method for hard articles of the present invention.

[0055] In the cleaning method for hard articles of the present invention, the cleaning agent composition for hard articles of the present invention can be foamed and brought into contact with the hard article. For example, the cleaning agent composition for hard articles of the present invention can be foamed using a sponge or a sprayer equipped with a foam-forming mechanism and brought into contact with the hard article. Alternatively, the cleaning agent composition for hard articles of the present invention can be brought into contact with the hard article by spraying, coating, immersion, etc.

[0056] The hard articles targeted by the cleaning method for hard articles of the present invention include those described in the cleaning agent composition for hard articles of the present invention. Tableware is one of the suitable hard articles.

[0057] In the cleaning method for hard articles of the present invention, the dirt adhering to the hard article may be oily dirt such as modified oil dirt, and may further be modified oil dirt.

[0058] In the cleaning method for hard articles of the present invention, the cleaning agent composition for hard articles of the present invention may be applied to a hard article to which oil stains, including modified oil, particularly heat-modified oil, are attached, by immersion in the composition. However, from the viewpoint of efficiently increasing the cleaning power, it is preferable to spray or apply the composition to the hard article to which oil stains, including modified oil, particularly heat-modified oil, are attached, and then apply it to the hard article. The method for bringing the cleaning agent composition for hard articles of the present invention into contact with hard articles to which oil stains or the like are attached is preferably by spraying or coating, and more preferably by spraying in droplet form or coating in foam form. Specifically, for contact with hard articles of the composition of the present invention, for example, a spray means is used. That is, in the present invention, it is preferable to use a cleaning agent for hard articles in which the cleaning agent composition for hard articles of the present invention is filled into a container equipped with a sprayer.

[0059] Methods for applying the cleaning agent in a foamy state include, for example, a method of creating foam by entraining air into the hard article cleaning agent composition of the present invention using the nozzle of a sprayer, and a method of creating foam by soaking the hard article cleaning agent composition of the present invention into a sponge or cleaning fiber article, and then kneading it several times.

[0060] The present invention provides a cleaning agent for hard articles in a spray container, wherein the cleaning agent composition for hard articles of the present invention is filled into a container equipped with a sprayer.

[0061] The container equipped with the sprayer in the cleaning agent for hard articles in a spray container of the present invention includes manual spraying devices that do not use propellants, such as trigger-type spray containers and pump-type spray containers, and aerosols that use propellants. The container equipped with the sprayer is preferably a trigger-type spray that can spray or apply the contents in droplet or foam form, and more preferably a trigger-type spray equipped with a mechanism for spraying the contents in droplet form or a trigger-type spray equipped with a mechanism for forming foam (foam-forming mechanism).

[0062] In the present invention, when using a trigger-type spray equipped with a mechanism for spraying the hard article cleaning agent composition of the present invention in a droplet form, the nozzle diameter of the spray nozzle of the spray container containing the composition is preferably in the range of 0.1 mm or more, more preferably 0.3 mm or more, and preferably 2 mm or less, and more preferably 1 mm or less, in order to ensure ease of spraying, that the sprayed droplets are not rough, that the spray is not linear, and that the sprayable area does not become extremely narrow. When using a trigger-type spray equipped with a mechanism for spraying in droplet form, the cleaning agent for hard articles in a spray container of the present invention sprays preferably 0.1 mL or more, more preferably 0.3 mL or more, and preferably 5 mL or less, and more preferably 2 mL or less of the composition in a single operation.

[0063] When using a trigger-type spray equipped with a foam-forming mechanism, the cleaning agent for hard articles in a spray container of the present invention sprays, preferably 0.5 mL or more, more preferably 1 mL or more, preferably 30 mL or less, more preferably 15 mL or less, and even more preferably 5 mL or less of the composition in a single operation.

[0064] In the cleaning method for hard articles of the present invention, the hard article is cleaned by bringing the cleaning agent composition for hard articles of the present invention into contact with the hard article. In the cleaning method of the present invention, dirt can be removed from the hard article and cleaned by, for example, soaking in the cleaning agent composition for hard articles of the present invention, leaving it applied, scrubbing with a sponge or textile product, rinsing with running water, etc. Furthermore, rinsing with running water can be performed thereafter. 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 methods. [Examples]

[0065] The cleaning agent compositions for hard articles shown in Tables 1-3 were prepared using the following ingredients, and their cleaning performance against modified oil stains was evaluated using the following method. The results are shown in Tables 1-3. The hydrophilic / lipophilic index in the table is the value for the entire composition measured at 25°C using the method described above. The adjustment amount in the table refers to the amount used to adjust the pH of the composition to the value shown in the table.

[0066] <Composition ingredients> (a) component • AMIT 102: Polyoxyethylene laurylamine, average number of added oxyethylene groups 2.1, HLB 9.1 (measured value equivalent to Griffin method*1), Kao Corporation, AMIT 102

[0067] (b) Component • E102-KG: Polyoxyethylene lauryl ether, average number of moles of oxyethylene groups added: 2, HLB 6.42 (Griffin method*2), Kao Corporation, Emulgen 102KG • E105: Polyoxyethylene lauryl ether, average number of moles of oxyethylene groups added: 3.8, HLB 9.7 (Griffin method*2), Kao Corporation, Emulgen 105 E108: Polyoxyethylene lauryl ether, average number of moles of oxyethylene groups added: 5.6, HLB: 12.1 (Griffin method*2), Kao Corporation, Emulgen 108 E120: Polyoxyethylene lauryl ether, average number of added moles of oxyethylene groups 13.2, HLB 15.3 (Griffin method*2), Kao Corporation, Emulgen 120 E121: Polyoxyethylene lauryl ether, average number of added moles of oxyethylene groups: 21, HLB 16.65 (Griffin method*2), Kao Corporation, Emulgen 121 E705: Polyoxyethylene alkyl ether, average number of added moles of oxyethylene groups is 5, alkyl group is a secondary alkyl group with 11 to 15 carbon atoms, HLB 10.5 (Griffin method*2), Kao Corporation, Emulgen 705 E707: Polyoxyethylene alkyl ether, average number of added moles of oxyethylene groups is 7, alkyl group is a secondary alkyl group with 11 to 15 carbon atoms, HLB 12.1 (Griffin method*2), Kao Corporation, Emulgen 707 AG-124: Alkyl polyglucoside, alkyl group is a primary alkyl group with 12-16 carbon atoms, average sugar condensation degree 1-2, HLB 11.5 (measured value equivalent to Griffin method*1), Kao Corporation, AG-124

[0068] (c) Component • Emal 20C: Polyoxyethylene lauryl sulfate sodium, average number of moles of oxyethylene groups added: 3, HLB 13.4 (measured value equivalent to the Griffin method*1), Kao Corporation, Emal 20C

[0069] (d) Ingredients • Amide-type nonionic surfactant: Kao Corporation, Aminone PK-02S, Palm kernel oil fatty acid diethanolamide

[0070] (d') component • Betaine-type surfactants: Kao Corporation, Anchitol 20HD, Lauryl Hydroxysulfobetaine

[0071] (e) Component • Butyl diglycol: Easily soluble in water (solubility in water is 5g / 100g or more at 25°C)

[0072] *1 The Griffin method equivalent measured values ​​are the hydrophilic-lipophilic indices measured for each surfactant using the <Method for Measuring the Hydrophilic-Lipophilic Indices of Cleaning Agent Compositions for Hard Articles> described herein. The measurement was performed at 25°C using a mixture containing the surfactant to be measured at a concentration of 5% by mass, with the remainder being water, as the cleaning agent composition for hard articles. *2 HLB based on the Griffin method is a calculated value using the average number of moles of oxyethylene groups added.

[0073] <Cleaning power against modified oil stains> The protective film was removed from a SUS304 test piece (1.0 mm x 25 mm x 70 mm) manufactured by Engineering Test Service Co., Ltd., and it was washed with a sponge using a neutral dish soap and rinsed (once with tap water, twice with deionized water). It was then dried in an electric dryer at 80°C to obtain a pre-treated SUS plate. The mass of the pre-treated SUS plate was weighed using a balance with four decimal places and was determined as the initial mass (X). A modified oil / chloroform solution was prepared by mixing 20g of modified oil with 60ml of chloroform. The modified oil was prepared by heating rapeseed oil (Fujifilm Wako Pure Chemical Industries, Ltd.) at 180°C for 8 hours. A modified oil / chloroform solution was applied at a concentration of 1 mg / cm² to one side of a 25 mm x 50 mm area of ​​a pre-treated stainless steel plate. 2 The oil was poured once using a dropper to achieve the desired result. The oil-covered surface was placed facing upwards and left to dry flat overnight to prepare the stainless steel plate for cleaning. The mass of the cleaning stainless steel plate was weighed using a balance with four decimal places and was determined as the mass before cleaning (Y). Each hard material cleaning agent composition listed in the table was evaluated using three stainless steel (SUS) plates for cleaning. Three SUS plates were placed on a balance dish BD-3 (140 x 140 x 25 mm) and immersed in 40 ml of the hard material cleaning agent composition. They were left at 25°C for 20 minutes. After that, they were rinsed with tap water for 1 minute using a Reenuts tester at a mechanical force of 300 rpm, and then dried flat overnight. The mass of the dried SUS plates was weighed using a balance with four decimal places and was defined as the post-cleaning mass (Z). The cleaning efficiency was calculated from the initial mass (X), the mass before cleaning (Y), and the mass after cleaning (Z) using the following formula. Cleaning rate (%) = [Mass before cleaning (Y) - Mass after cleaning (Z)] / [Mass before cleaning (Y) - Initial mass (X)] × 100

[0074] [Table 1]

[0075] [Table 2]

[0076] Table 3

Claims

1. A hard article cleaning composition comprising the following component (a) and component (b), wherein the hydrophilic-lipophilic index of the entire composition is 9 or more and 14.2 or less: Component (a): a polyoxyalkylene alkyl or alkenyl amine having an alkyl or alkenyl group having from 8 to 18 carbon atoms and an average added mole number of oxyalkylene groups of from 1 to 5. Component (b): nonionic surfactant (excluding component (a) and amide-type nonionic surfactants)

2. 2. The hard article cleaning composition according to claim 1, wherein the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is 0.01 or more and 30 or less.

3. The cleaning composition for hard articles according to claim 1 or 2, which has a pH at 20° C. of 5 or more and 11 or less.

4. The cleaning composition for hard articles according to claim 1 or 2, which optionally contains the following component (c): Component (c): Anionic surfactant

5. The cleaning composition for hard articles according to claim 4, wherein the content of the component (c) is 50 mass % or less based on the total amount of surfactants in the composition.

6. 3. The hard article cleaning composition according to claim 1 or 2, which optionally contains the following component (d), and the content of component (d) is less than 10 mass % based on the total amount of surfactants in the composition: Component (d): Amide-type nonionic surfactant

7. 3. The hard article cleaning composition according to claim 1 or 2, which optionally contains the following component (e), and the content of component (e) is less than 50 mass% based on the total amount of surfactants in the composition: Component (e): a hydrophilic solvent having a hydrocarbon group having 9 or less carbon atoms and a solubility in water of 5 g / 100 g or more at 25° C.

8. 3. The hard article cleaning composition according to claim 1 or 2, wherein the component (b) is one or more nonionic surfactants selected from the group consisting of (b1) polyoxyalkylene alkyl ethers, (b2) alkyl (poly)glycosides, (b3) polyoxyalkylene fatty acid esters, (b4) polyglycerin fatty acid esters, and (b5) (poly)oxyalkylene sorbitan fatty acid esters.

9. 3. The hard article cleaning composition according to claim 1 or 2, wherein the component (b) is one or more nonionic surfactants selected from the group consisting of alkoxylate-type nonionic surfactants and alkylglycoside-type surfactants, and having an HLB of 9 or more and 17.4 or less.

10. A method for cleaning hard articles, comprising contacting the cleaning composition for hard articles according to claim 1 or 2 with a soiled hard article.

11. The method for cleaning hard articles according to claim 10, wherein the cleaning agent composition for hard articles is foamed and then contacted with the hard article.

12. The method for cleaning hard articles according to claim 11, wherein the cleaning agent composition for hard articles is foamed with a sponge or a sprayer equipped with a foam forming mechanism and then contacted with the hard article.

13. The method for cleaning hard articles according to claim 10, wherein the hard article is tableware.

14. The method for cleaning hard articles according to claim 10, wherein the stain is an oil stain.