Cleaning composition for hard objects

Abstract

This invention relates to a cleaning composition for hard materials, comprising (a), (b), and (c) below, wherein the mass ratio of the content of (a) to the content of (c), i.e., (a) / (c), is 0.40 to 5.0, and optionally contains (d) one or more surfactants selected from betaine-type surfactants and amide-type nonionic surfactants [hereinafter referred to as (d) component], wherein the content of (d) component is less than 10% by mass relative to the total amount of surfactants in the composition. (a) Component: an alkyl or alkenyl amine having 6 to 20 carbon atoms and an average addition mole number of oxyalkylene groups of 1 to 5; (b) Component: one or more surfactants selected from nonionic surfactants and anionic surfactants (except for (a) component and amide-type nonionic surfactants); (c) Component: a solvent.

Description

Technical Field

[0001] This invention relates to a cleaning agent composition for hard objects and a cleaning method for hard objects. Prior Technology

[0002] Generally speaking, kitchen cleaning agents used around the kitchen, such as stoves, ovens, walls or floors around the stove, and exhaust fans, or cleaning agents used for food processing equipment, use cleaning agents containing surfactants, solvents, and alkalis to remove various types of dirt, such as dirt from food and dirt from ingredients used in cooking.

[0003] Japanese Patent Application Publication No. 2020-97711 discloses a liquid cleaning composition containing, under specified conditions, (a) an amine oxide surfactant having a hydrocarbon group having 7 to 18 carbon atoms, (b) a nonionic surfactant having an HLB (Hydrophile Lipophile Balance) of 1 to 10, and (c) a compound represented by a specific general formula (c1) having an alkyl group having 1 to 5 carbon atoms. Japanese Patent Application Publication No. 2020-90606 discloses a cleaning composition comprising at least one of (A) anionic surfactant, (B) nonionic surfactant, and (C) dihydroxyethylglycine and its salt, wherein the amount of at least one of (C) dihydroxyethylglycine and its salt is 0.1 to 50 parts by weight relative to a total of 100 parts by weight of (A) anionic surfactant and (B) nonionic surfactant. Japanese Patent Application Publication No. 2019-210475 discloses a liquid cleaning agent composition for tableware and / or hard items around the kitchen, which contains (a) a nonionic surfactant with an HLB of 10.5 or less (except for (b)), (b) a glycoside having a hydrocarbon group with 8 to 18 carbons and a glycosidic 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. The content of (a) in the total surfactant is 30% to 95% by mass, the mass ratio of the content of (c) to the content of (a), i.e., (c) / (a), is 2 to 8, and the viscosity at 20°C is 20 mPa·s or less. Japanese Patent Application Publication No. 2020-15863 discloses a liquid cleaning agent composition for hard surfaces, which contains a surfactant, including (A) a nonionic surfactant and (B) an amphoteric surfactant as the surfactant. In the surfactant, the proportion of (A) is 60% by mass or more, and (A1) is an alkyl mono- or dialkylolamine or its alkyl oxide adduct (the alkyl oxide has 2 or 3 carbons) with an alkyl group having 10 to 18 carbons. In the total of (A) and (B), the proportion of (A1) is 0.5% by mass or more and 20% by mass or less. Japanese Patent Application Publication No. 2020-200420 discloses a liquid antibacterial cleaning agent composition containing (A) an anionic surfactant, (B) a long-chain alkyl di-short-chain alkyl hydroxyethyl ammonium 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. Summary of the Invention

[0004] Grease adhering to tableware or cooking utensils is modified by heat, light, and oxygen in the air, becoming a very difficult-to-remove stain (modified grease). Therefore, tableware or cooking utensil cleaners are required to have high cleaning power against grease.

[0005] Furthermore, when cleaning stains attached to tableware or cooking utensils, sometimes the cleaning agent is foamed up using a sponge or spray to adhere to the object. In addition to adhering to the stains and improving cleaning efficiency, the foam of the cleaning agent also allows the operator to perceive the progress and continuity of the cleaning work.

[0006] The present invention provides a cleaning composition for hard objects with excellent cleaning power for oil stains and excellent foam persistence in one embodiment.

[0007] As mentioned above, the grease adhering to tableware or cooking utensils is modified by heat, light, and oxygen in the air, becoming a very difficult-to-remove stain (modified grease). Therefore, tableware or cooking utensil cleaners are required to have excellent cleaning power against modified grease.

[0008] In another embodiment of the present invention, a cleaning agent composition for hard articles with excellent cleaning power for oil stains such as modified oil stains is provided.

[0009] This invention relates, in one embodiment, to a cleaning composition for hard objects [hereinafter also referred to as cleaning composition for hard objects (I)], which contains component (a), component (b), and component (c) described below, and The mass ratio of the content of component (a) to the content of component (c), i.e., (a) / (c), is 0.40 to 5.0. The composition contains (d) one or more surfactants selected from betaine-type surfactants and acetamide-type nonionic surfactants [hereinafter referred to as (d) component], wherein the content of (d) component is less than 10% by mass relative to the total amount of surfactants in the composition. (a) Ingredients: Polyoxyalkylene alkylene or alkenylamine having an alkyl or alkenyl group with 6 to 20 carbon atoms and an average addition mole number of alkylene oxide of 1 to 5. (b) Ingredients: Surfactants selected from one or more of nonionic and anionic surfactants (except for ingredient (a) and acetamide-type nonionic surfactants). (c) Components: Solvent

[0010] Furthermore, the present invention relates to a cleaning method for a hard article by bringing the above-described cleaning agent composition (I) for hard articles of the present invention into contact with a hard article with dirt attached [hereinafter, also referred to as the cleaning method (I) for hard articles].

[0011] In another aspect, the present invention relates to a cleaning composition for hard objects [hereinafter also referred to as cleaning composition for hard objects (II)], which contains the following (ax) components and the following (bx) components, and the overall hydrophilicity-lipophilicity index of the composition is 9 or more and 14.2 or less. (ax) Components: Polyoxyalkylene alkylene or alkenylamine having an alkyl or alkenyl group with 8 to 18 carbon atoms and an average addition mole number of oxyalkylene groups of 1 to 5. (bx) component: nonionic surfactant (except for (ax) component and amide-type nonionic surfactants)

[0012] Furthermore, the present invention relates to a cleaning method for a hard article by bringing the cleaning agent composition (II) of the present invention into contact with a hard article with dirt attached [hereinafter also referred to as the cleaning method (II) for hard articles].

[0013] According to one aspect of the present invention, a cleaning agent composition for hard objects is provided that exhibits excellent cleaning power for oil stains and excellent foam persistence.

[0014] According to another aspect of the present invention, a cleaning agent composition for hard articles with excellent cleaning power for oil stains such as modified oil stains is provided. Implementation

[0015] <Cleaning Composition for Hard Items (I)> The mechanism by which the effects of this invention are manifested may not be fully elucidated, but the applicant has considered the following. Modified grease, particularly that adhering to cooking utensils or equipment, undergoes increased modification due to thermal processes. To facilitate removal from the object during cleaning, using a detergent with relatively high hydrophobicity is considered advantageous. However, such detergents generally have low foaming properties, and when cleaning less modified grease such as tableware, the low-modification grease exhibits defoaming behavior, resulting in insufficient foaming and reduced cleaning efficiency, thus decreasing the amount of tableware that can be cleaned. Furthermore, if foaming is prioritized for cleaning tableware with relatively hydrophilic and less modified grease, the cleaning effectiveness on countertops or stovetops with more highly modified grease will be reduced. In the case where components (a) and (b) of the hard-material cleaning agent composition (I) of the present invention are adsorbed onto modified oil stains, for example via alkyl groups that are hydrophobic, it is believed that component (a) adsorbs near the adsorption interface or extends horizontally relative to the adsorption interface at a location far from the adsorption interface due to the smaller addition molar number of the oxyalkyl portion that is a hydrophilic group. Component (b) adsorbs with relative freedom in the vertical direction relative to the adsorption interface due to the hydrophilic portion, such as the oxyalkyl portion. Component (c) rapidly promotes aggregation in the formation of the molecular aggregates of components (a) and (b), and coexists in the molecular aggregates of components (a) and (b). Furthermore, component (c) changes the hydrophobicity of the dirt surface by pre-adsorbing onto the dirt surface or existing near the dirt surface. Based on this behavior, it is speculated that component (c) has the effect of imparting an oleophilic / hydrophilic balance to the surface of modified oil stains, etc., making them easily adsorbed. Even if the hydrophilicity and hydrophobicity of components (a) and (b) with this adsorption property are adjusted separately as individual structures, they cannot meet the performance requirements for highly modified and unmodified oils. When components (a) and (b) coexist, it is predicted that the density of hydrophilic groups near the hydrophobic group will be higher, resulting in a molecular aggregate with a wide area of ​​hydrophilic region far from the dirt interface. In the case of this surfactant forming molecular aggregate, even if the molecular aggregate is easily adsorbed onto highly modified oil with relatively high hydrophobicity and easily detached from it, the strong structure of the hydrophilic group means that even if the relatively hydrophilic unmodified oil component is dispersed and stabilized, it is not easy to generate a defoaming effect from the oil. Therefore, it is believed that it can maintain cleaning performance for highly modified oils and, even for unmodified oils, is not prone to defoaming and can maintain cleaning foam, thus maintaining cleaning power. On the other hand, it is believed that betaine-type or amide-type surfactants can affect the lipophilic / hydrophilic balance of component (c), reducing its adsorption capacity for modified oil stains. Furthermore, it is believed that component (d), due to its betaine or amide groups, readily interacts with component (a), thus hindering the effectiveness of component (a). Therefore, caution is needed when component (d) is present. Furthermore, the effects of this invention are not limited to the mechanism of action shown herein.

[0016] (a) The component is a polyoxyalkyl alkyl or alkenyl amine having an alkyl or alkenyl group with 6 to 20 carbon atoms and an average addition mole number of oxyalkyl group of 1 to 5.

[0017] From the viewpoint of maintaining a certain cleaning power and increasing the amount of cleaning that can be done by the persistence of foam (hereinafter referred to as "the persistence of cleaning foam"), (a) the alkyl or alkenyl group of the component has 6 or more carbons, preferably 8 or more, more preferably 10 or more, and 20 or less, preferably 18 or less. (a) The group of the component is preferably alkyl. The oxoalkyl group is preferably an oxoalkyl group with two carbon atoms and / or an oxoalkyl group with three carbon atoms, i.e., oxoethyl and / or oxopropyl, and more preferably oxoethyl. (a) The component preferably contains oxoethyl as an oxoalkyl group. From the point of view of cleanliness, (a) the average addition mole number of oxyalkylene groups of component is 1 to 5, preferably 1.5 or more, more preferably 2 or more, and even more preferably 4.5 or less.

[0018] As component (a), examples include alkyl or alkenyl groups having 6 or more carbon atoms, and 20 or less, and 18 or less, and the average addition mole number of the alkyl group being 1 or more and 5 or less.

[0019] As a component (a), for example, compounds represented by the following general formula (a1) can be cited.

[0020] [Chemistry 1]

[0021] [In the formula, R is an alkyl or alkenyl group with 6 to 20 carbon atoms, EO is an ethoxy group, m and n are the average addition moles, and are independently 0 to 5, and the sum of m and n is 1 to 5.]

[0022] In formula (a1), R has 6 or more carbon atoms, more than 8 or more, more than 10 or more, and less than 20 or more than 18. R is preferably an alkyl group. The sum of m and n is preferably 1.5 or more, more preferably 2 or more, and more preferably 4.5 or less.

[0023] From the viewpoint of ease of acquisition and persistence of cleaning foam, the HLB of component (a) is preferably 9 or higher, more preferably 9.5 or higher, and more preferably 14.2 or lower, more preferably 13.0 or lower. The HLB of component (a) is proposed by Griffin. Furthermore, in this invention, the HLB values ​​of the Griffin method equivalent measured in the following examples can be regarded as the HLB values ​​using the Griffin method. This also applies to the HLB of other surfactants such as component (b).

[0024] From the viewpoint of the persistence of cleaning foam, the cleaning composition (I) for hard articles of the present invention may contain, for example, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and even more preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less of component (a).

[0025] From the viewpoint of the persistence of cleaning foam, the hard-article cleaning composition (I) of the present invention may contain, for example, more preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 10% by mass or more, and more preferably 60% by mass or less, more preferably 55% by mass or less, and more preferably 50% by mass or less, relative to the total amount of surfactant in the composition. The total amount of surfactant is the total amount of components (a), (b), and any other surfactants, such as any component (d), contained in the hard-article cleaning composition (I). The hard-article cleaning composition (I) of the present invention is a composition containing surfactants, or it may be a composition containing components (a), (b), and any component (d) as a surfactant.

[0026] (b) The component is selected from one or more of the following surfactants: (b1) nonionic surfactant [hereinafter referred to as component (b1)] and (b2) anionic surfactant [hereinafter referred to as component (b2)] (except for component (a) and acetamide-type nonionic surfactants).

[0027] As component (b1), examples include one or more nonionic surfactants selected from (b11) polyoxyalkylene alkyl ethers [hereinafter referred to as component (b11)], (b12) alkyl (poly)glycosides [hereinafter referred to as component (b12)], (b13) polyoxyalkylene fatty acid esters [hereinafter referred to as component (b13)], (b14) polyglycerol fatty acid esters [hereinafter referred to as component (b14)], and (b15) (poly)oxyalkylene sorbitan fatty acid esters [hereinafter referred to as component (b15)]. When the hard article cleaning composition (I) of the present invention contains component (b1), the composition preferably contains one or more nonionic surfactants selected from components (b11) and (b12) as component (b1), and more preferably contains one or more nonionic surfactants selected from component (b12) as component (b1).

[0028] The oxoalkyl group of component (b11) is preferably a 2-carbon oxoalkyl group and / or a 3-carbon oxoalkyl group, i.e., oxoethyl and / or oxopropyl, more preferably oxoethyl. From the viewpoint of the persistence of cleaning foam, the average addition mole number of the oxoalkyl group of component (b11) is preferably 0 or more, more preferably 1 or more, and more preferably 25 or less, more preferably 23 or less. (b11) The ingredient preferably contains an oxyethyl group as an oxyalkyl group. From the viewpoint of the persistence of cleaning foam, the alkyl group of ingredient (b11) preferably has 3 or more carbon atoms, more preferably 4 or more, and more preferably 30 or less, more preferably 24 or less. The alkyl group of ingredient (b11) can be straight-chain or branched, but from the viewpoint of the persistence of cleaning foam, it is preferably straight-chain. The alkyl group of ingredient (b11) can be saturated or unsaturated, but from the viewpoint of the persistence of cleaning foam, it is preferably saturated.

[0029] From the viewpoint of the persistence of cleaning foam, the alkyl group of component (b12) preferably has 3 or more carbon atoms, more preferably 4 or more, and more preferably 30 or less, and more preferably 24 or less. Furthermore, from the viewpoint of the persistence of cleaning foam, the average degree of condensation of the sugars such as glucose in component (b12) preferably has 1 or more, and more preferably 10 or less, and more preferably 5 or less. Component (b12) is preferably an alkyl (poly)glucoside whose structural sugar is glucose. As component (b12), it is preferably an alkyl (poly)glucoside having an alkyl group having 3 or more carbon atoms, more preferably 4 or more, and more preferably 30 or less, and more preferably 24 or less, and the average degree of condensation of glucose being 1 or more, 10 or less, and more preferably 5 or less.

[0030] From the viewpoint of ease of acquisition and cleanliness, the HLB of component (b1) is preferably 9 or higher, more preferably 9.5 or higher, and preferably 17.4 or lower, more preferably 16.9 or lower. The HLB of component (b1) is obtained by the Griffin method. As mentioned above, the hydrophilicity-lipophilicity index measured by the prescribed method can be regarded as the HLB of component (b) obtained by the Griffin method.

[0031] Examples of components (b2) 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) sulfates, alkyl (preferably with 2 to 24 carbon atoms) phosphates, polyoxyalkyl (preferably polyoxyethyl) alkyl (preferably with 8 to 18 carbon atoms) sulfates, polyoxyalkyl (preferably polyoxyethyl) alkyl (preferably with 8 to 18 carbon atoms) carboxylates, or alkyl (preferably with 6 to 18 carbon atoms) sulfosuccinates, etc. Examples of salts include alkali metal salts such as sodium salts and potassium salts.

[0032] From the viewpoint of the persistence of cleaning foam, the cleaning composition (I) for hard articles of the present invention may contain, for example, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass or less (b).

[0033] From the viewpoint of the persistence of cleaning foam, the cleaning agent composition (I) for hard articles of the present invention may contain, for example, more preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, and more preferably 90% by mass or less, more preferably 80% by mass or less, and more preferably 70% by mass or less, relative to the total amount of surfactant in the composition, component (b).

[0034] Regarding the cleaning agent composition (I) for hard objects of the present invention, from the viewpoint of the persistence of cleaning foam, the mass ratio of the content of component (a) to the content of component (b), i.e., (a) / (b), is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, further preferably 0.15 or more, further preferably 0.18 or more, and preferably 3 or less, more preferably 2 or less, further preferably 1 or less, further preferably 0.5 or less, further preferably 0.3 or less, further preferably 0.23 or less.

[0035] (c) The component is a solvent. As component (c), one or more solvents selected from (c1) glyceryl ether [hereinafter referred to as component (c1)], (c2) glycol ether [hereinafter referred to as component (c2)], and (c3) polypropylene glycol [hereinafter referred to as component (c1)] may be cited.

[0036] The glycerol ether used as component (C1) is preferably an alkyl glycerol ether having an alkyl group having 5 or more carbon atoms, and further having 6 or more carbon atoms, and further having 10 or fewer carbon atoms, and further having 9 or fewer carbon atoms. The aforementioned alkyl glycerol ether is preferably a monoalkyl glycerol ether. 2-Ethylhexyl glycerol ether is preferred as component (C1).

[0037] The glycol ether as component (C2) is preferably a mono-, di-, or tri-ethylene glycol monoalkyl ether, or a mono-, di-, or tri-propylene glycol monoalkyl ether, wherein the alkyl group has 1 to 8 carbon atoms or more, and preferably 2 to 6 carbon atoms. Diethylene glycol butyl ether is preferred as component (C2).

[0038] The polypropylene glycol used as component (c3) is preferably a polypropylene glycol with a weight average molecular weight of 500 or more, further 600 or more, further 700 or more, and also 5000 or less, further 3000 or less, and further 2000 or less. The polypropylene glycol used as component (c3) is preferably a polypropylene glycol with a weight average molecular weight of 700 or more, 2000 or less, for example, 1000.

[0039] From the viewpoint of the persistence of cleaning foam, component (c) is preferably component (c1). From the viewpoint of the persistence of cleaning foam, the hard article cleaning composition (I) of the present invention preferably contains component (c1) as component (c).

[0040] From the viewpoint of the persistence of cleaning foam, the cleaning agent composition (I) for hard articles of the present invention may contain, for example, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 10% by mass or less, and more preferably 8% by mass or less (c).

[0041] Regarding the cleaning agent composition (I) for hard objects of the present invention, from the viewpoint of the persistence of cleaning foam, the mass ratio of the content of component (a) to the content of component (c), i.e., (a) / (c), is 0.40 or more, preferably 0.50 or more, more preferably 0.60 or more, and is 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less, more preferably 2.5 or less, more preferably 2 or less, more preferably 1.5 or less, more preferably 1.0 or less, more preferably 0.85 or less, and more preferably 0.78 or less.

[0042] When the cleaning composition (I) for hard articles of the present invention contains component (c1) as component (c), from the viewpoint of the persistence of cleaning foam, (a) / (c) is 0.40 or more, preferably 0.50 or more, more preferably 0.60 or more, and is 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less, more preferably 2.5 or less, more preferably 2.0 or less, more preferably 1.5 or less, more preferably 1.0 or less, more preferably 0.85 or less, more preferably 0.78 or less. When the cleaning composition (I) for hard articles of the present invention contains component (c1) as component (c), from the viewpoint of the persistence of cleaning foam, the mass ratio of the content of component (a) to the content of component (c1), i.e., (a) / (c1), is preferably 0.40 or more, more preferably 0.50 or more, and even more preferably 0.60 or more, and preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, even more preferably 2.5 or less, even more preferably 2.0 or less, even more preferably 1.5 or less, even more preferably 1.0 or less, even more preferably 0.85 or less, and even more preferably 0.78 or less.

[0043] Furthermore, when the cleaning composition (I) for hard articles of the present invention contains component (c2) and / or component (c3) as component (c), from the viewpoint of the persistence of cleaning foam, (a) / (c) is preferably 0.60 or more, more preferably 1.0 or more, and 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less, and more preferably 2.0 or less. When the cleaning composition (I) for hard articles of the present invention contains component (c2) and / or component (c3) as component (c), from the viewpoint of the persistence of cleaning foam, the mass ratio of the content of component (a) to the total content of components (c2) and (c3), i.e., (a) / [(c2)+(c3)], is preferably 0.60 or more, more preferably 1.0 or more, and preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.0 or less, and more preferably 2.0 or less.

[0044] Furthermore, when the cleaning composition (I) for hard articles of the present invention contains component (c1), component (c2) and / or component (c3) as component (c), from the viewpoint of the persistence of cleaning foam, the mass ratio of the content of component (c1) to the total content of components (c2) and (c3), i.e., (c1) / [(c2)+(c3)], is preferably 0.1 or more, more preferably 0.3 or more, more preferably 0.6 or more, and preferably 10 or less, more preferably 6 or less, more preferably 4 or less, and more preferably 3 or less.

[0045] In the cleaning agent composition (I) for hard articles of the present invention, without prejudice to the purpose of the present invention, surfactants, enzymes (protein-degrading enzymes, lipase-degrading enzymes, saccharide-degrading enzymes, etc.), water-soluble additives, pH adjusters, thickeners, dispersants, viscosity modifiers, fragrances, colorants, antioxidants, preservatives, and other ingredients other than ingredients (a) and (b) may be formulated.

[0046] The cleaning composition (I) for hard surfaces of the present invention contains, in any way, one or more surfactants selected from betaine-type surfactants and amide-type nonionic surfactants as component (d). From the viewpoint of foam persistence, the content of component (d) relative to the total amount of surfactants in the composition is 10% by mass, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less, with a lower limit of 0% by mass or more. The content of component (d) in the cleaning composition (I) for hard surfaces of the present invention can be 0% by mass.

[0047] (d) The betaine-type surfactant in the composition is a surfactant having a betaine structure. Examples of betaine-type surfactants include: alkyl (e.g., 8 to 18 carbon atoms) dimethylaminoacetic acid betaine, alkyl (e.g., 8 to 18 carbon atoms) propylamino betaine, alkyl (e.g., 8 to 18 carbon atoms) hydroxysulfonyl betaine, and alkyl (preferably 8 to 18 carbon atoms) carboxymethyl hydroxyethyl imidazolium betaine. In this invention, the content of the betaine-type surfactant can 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) propylamino betaine, alkyl (8 to 18 carbon atoms) hydroxysulfonyl betaine, and alkyl (8 to 18 carbon atoms) carboxymethyl hydroxyethyl imidazolium betaine in the hard article cleaning agent composition (I).

[0048] Examples of amide-type nonionic surfactants in component (d) include amide compounds of fatty acids having 8 to 18 carbon atoms and alkylamines having 1 to 6 hydroxyl groups. As alkylamines, those with 1 or more carbon atoms, and more preferably 2 to 8 carbon atoms, are preferred. Specifically, examples include monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, reduced glucosamine, N-methylglucosamine, and N-methylethanolamine. In this invention, component (d) may contain one or more amide-type nonionic surfactants selected from fatty acid (8 to 18 carbon atoms) diethanolamide, fatty acid (8 to 18 carbon atoms) N-methylethanolamide, and fatty acid (8 to 18 carbon atoms) N-methylglucosamine. In this invention, the content of amide-type nonionic surfactants can be the total content of amide-type nonionic surfactants selected from fatty acid (8 to 18 carbon atoms) diethanolamide, fatty acid (8 to 18 carbon atoms) N-methylethanolamide and fatty acid (8 to 18 carbon atoms) N-methylglucosamide in the hard article cleaning agent composition (I).

[0049] Regarding the cleaning agent composition (I) for hard articles of the present invention, from the viewpoint of the persistence of cleaning foam, the total amount of surfactant in the composition is preferably 1% by mass or more, more preferably 2.5% by mass or more, and even more preferably 5% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The cleaning agent composition (I) for hard articles of the present invention is a composition containing surfactants, or it may be a composition containing component (a), component (b), and optionally component (d) as surfactants, and the total amount of surfactants is within the above-mentioned range.

[0050] From the viewpoint of stability and workability, the hard-material cleaning composition (I) of the present invention preferably contains water. The water is not particularly limited and examples include tap water, well water, ion-exchanged water, and distilled water. In the present invention, the water is preferably used in a surplus amount of the composition (totaling 100% by mass). Regarding the water content, for example, it can be set to 50% by mass or more in the hard-material cleaning composition (I), further to 60% by mass or more, and further to 70% by mass or more. The hard-material cleaning composition (I) of the present invention can be a liquid composition.

[0051] The pH value of the cleaning composition (I) for hard articles of the present invention at 20°C is preferably 5 or higher, more preferably 5.5 or higher, more preferably 6 or higher, and more preferably 11 or lower, more preferably 9 or lower, and more preferably 8.5 or lower.

[0052] The cleaning composition (I) for hard objects of the present invention can be used on various hard objects, but is preferably used on tableware and / or hard objects around the kitchen, and even more preferably on tableware.

[0053] Hard objects around the kitchen refer to items used in the area around the kitchen, specifically as follows: (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 stoves, and microwave ovens; and (3) The floor or walls around the above-mentioned storage area or cooking area. In this invention, for convenience, these are referred to as "hard objects around the kitchen". Furthermore, as tableware, specifically, the following components or utensils that come into contact with food can be listed: (i) Plates, bowls, and other tableware; (ii) Storage containers such as lunch boxes and bottles; (iii) Cooking utensils such as kitchen knives or cutting boards, pots, frying pans, and fish grills; (iv) Food processors, blenders and other cooking appliances. In this invention, for convenience, these are referred to as "tableware". Furthermore, the present invention preferably includes items selected from tableware, storage containers, cooking utensils, and cooking appliances, and more preferably includes items selected from plates, bowls, lunch boxes, bottles, knives, cutting boards, pots, frying pans, fish grills, food processors, and mixers.

[0054] Examples of materials that can be used to make hard articles include plastics (including silicone resins, etc.), metals, ceramics, wood, and combinations thereof. Furthermore, the cleaning agent composition (I) for hard articles of the present invention can effectively clean oil stains adhering to such hard articles.

[0055] As mentioned above, oil stains adhering to hydrophobic materials such as plastics become more difficult to remove due to modification. However, in this invention, even oil stains adhering to hard plastic articles exhibit excellent cleaning effects, and the foam persistence is also excellent. This invention is also suitable for cleaning hard plastic articles. Examples of plastics include polypropylene, polyethylene and other polyolefins, polymethyl methacrylate, polycarbonate, ABS (acrylonitrile-butadiene-styrene) resin, polyethylene terephthalate, etc.

[0056] Cleaning Methods for Hard Items (I) This invention provides a cleaning method (I) for hard articles, which involves bringing the cleaning agent composition (I) of this invention into contact with a hard article covered with dirt. In the cleaning method (I) of this invention, the properties described in the cleaning agent composition (I) of this invention can be appropriately applied.

[0057] In the cleaning method (I) for hard articles of the present invention, it is preferable to foam the cleaning agent composition (I) for hard articles of the present invention and bring it into contact with the hard article. For example, the cleaning agent composition (I) for hard articles of the present invention can be foamed by a sponge or by a spraying device having a foam forming mechanism and brought into contact with the hard article.

[0058] Examples of hard articles that are the target of the cleaning method (I) for hard articles of the present invention include those described in the cleaning agent composition (I) for hard articles of the present invention. Tableware is one of the suitable hard articles.

[0059] In the cleaning method (I) for hard articles of the present invention, the dirt adhering to the hard article may be oil stains, or more specifically, dirt containing oil stains.

[0060] In this invention, hard items, such as tableware, can be hand-washed using the hard surface cleaning agent composition (I) of this invention, followed by rinsing with water. As a specific hand-washing method, a cleaning method for hard items can be exemplified as follows: using a flexible material coated with a cleaning liquid containing the hard surface cleaning agent composition (I) of this invention, the hard items such as tableware are hand-washed, followed by rinsing with water. For example, a flexible material such as a sponge containing water can be coated with the hard surface cleaning agent composition (I) of this invention and kept clean with the cleaning liquid, while rubbing it several times by hand to create foam, and then scrubbing the hard items such as tableware. Regarding higher foaming properties and foam persistence, the combined concentration of components (a) and (b) in the cleaning solution retained by the flexible material is preferably 1,000 ppm or more, more preferably 2,000 ppm or more, and preferably 70,000 ppm or less, more preferably 50,000 ppm or less, and even more preferably 30,000 ppm or less. After cleaning, water is added for rinsing. For example, in this invention, 3.3 to 133 parts by weight of rinsing water are used relative to 1 part by weight of the hard surface cleaning agent composition (I) used for cleaning to fully eliminate the foam, thus quickly completing the rinsing. The amount of rinsing water is about 2 / 3 to 1 / 10 of that used when using the previous hand-washing cleaning agent composition.

[0061] Furthermore, in the cleaning method (I) for hard articles of the present invention, the cleaning agent composition (I) for hard articles of the present invention is made into droplets or foam, preferably into foam, so that it can come into contact with hard articles with oil stains or the like. In this method, a spray device can be used. That is, in the present invention, a cleaning agent for hard articles can be used by filling the cleaning agent composition (I) for hard articles of the present invention into a container equipped with a spray device. The present invention provides a cleaning agent for hard articles contained in a spray container, which is made by filling the cleaning agent composition (I) for hard articles of the present invention into a container equipped with a spray device.

[0062] The container equipped with a spraying device in the cleaning agent for hard objects contained in the spray container of the present invention can be exemplified by a trigger-type spray container, a pump-type spray container, or other manual spraying device that does not use a spray agent; or an aerosol that uses a spray agent. The container equipped with the spraying device is preferably a trigger-type sprayer that can spray or coat the contents into droplets or foam, more preferably a trigger-type sprayer equipped with a mechanism for spraying the contents into droplets or a trigger-type sprayer equipped with a mechanism for forming foam (foam forming mechanism).

[0063] In the case of the hard article cleaning agent contained in the spray container of the present invention, when using a trigger-type sprayer equipped with a mechanism for spraying the hard article cleaning agent composition (I) of the present invention in the form of droplets, in order to facilitate spraying or avoid coarse sprayed droplets, the spray is in a straight line and the sprayable area is very narrow. The nozzle diameter of the spray container containing the above composition is preferably 0.1 mm or more, more preferably 0.3 mm or more, and more preferably 2 mm or less, more preferably 1 mm or less. When using a trigger-type sprayer with a mechanism for spraying droplets, the hard article cleaning agent composition (I) of the present invention, which contains a hard article cleaning agent in a spray container, is preferably sprayed at a rate of 0.1 mL or more, more preferably 0.3 mL or more, and more preferably 5 mL or less, and more preferably 2 mL or less in a single operation.

[0064] When using a trigger-type sprayer equipped with a foam-forming mechanism, the hard-article cleaner composition (I) of the present invention, which contains a hard-article cleaner in a spray container, is preferably sprayed at a rate of 0.5 mL or more, more preferably 1 mL or more, and more preferably 30 mL or less, more preferably 15 mL or less, and even more preferably 5 mL or less in a single operation.

[0065] <Cleaning Composition for Hard Items (II)> The mechanism by which the effects of this invention are manifested may not be fully elucidated, but the applicant has considered the following. Modified grease, particularly that adhering to cooking utensils or equipment, undergoes increased modification due to thermal processes. To facilitate removal from the object during cleaning, using a detergent with relatively high hydrophobicity is considered advantageous. However, such detergents generally have low foaming properties, and when cleaning less modified grease such as tableware, the low-modification grease exhibits defoaming behavior, resulting in insufficient foaming and reduced cleaning efficiency, thus decreasing the amount of tableware that can be cleaned. Furthermore, if foaming is prioritized for cleaning tableware with relatively hydrophilic and less modified grease, the cleaning effectiveness on countertops or stovetops with more highly modified grease will be reduced. When the (ax) and (bx) components of this invention are adsorbed onto modified oil stains, for example via alkyl groups that are hydrophobic, it is believed that the (ax) component, due to the smaller addition molar number of the oxyalkyl group that is a hydrophilic group, adsorbs near the adsorption interface or extends horizontally relative to the adsorption interface at a location far from the adsorption interface. The (bx) component, on the other hand, adsorbs with relative freedom in the vertical direction relative to the adsorption interface due to the hydrophilic group, such as the oxyalkyl group. Even if the hydrophilicity and hydrophobicity of the (ax) and (bx) components with these adsorption characteristics are adjusted using a single structure, it is impossible to meet the performance requirements for highly modified and low-modified oils. When the (ax) and (bx) components coexist, it is predicted that a higher density of hydrophilic groups will be formed near the hydrophobic group, resulting in a molecular aggregate with a wide hydrophilic region far from the dirt interface. When the molecular aggregates of this type of surfactant in the entire cleaning system have a specific hydrophilic-lipophilic index, it is believed that it effectively adsorbs highly modified oil stains with relatively high hydrophobicity. The structure of the hydrophilic portion is also robust, thus promoting the stripping and dispersion of difficult-to-clean highly modified oil stains without reducing foaming properties. Furthermore, due to the wider hydrophilic group region, it is believed that there will be no reduction in foaming properties. Furthermore, the effects of this invention are not limited to the mechanism of action shown herein.

[0066] (ax) components are polyoxyalkyl alkyl or alkenyl amines having an alkyl or alkenyl group with 8 to 18 carbon atoms and an average addition mole number of oxyalkyl groups of 1 to 5.

[0067] From the viewpoint of the cleanliness of highly modified oils (hereinafter referred to as "cleanliness"), the alkyl or alkenyl groups of the (ax) component have 8 or more carbon atoms, preferably 10 or more, and 18 or less, preferably 16 or less. The (ax) component preferably has an alkyl group. The oxoalkyl group is preferably a 2-carbon oxoalkyl group and / or a 3-carbon oxoalkyl group, i.e., oxoethyl and / or oxopropyl, more preferably oxoethyl. The (ax) component preferably contains oxoethyl as an oxoalkyl group. From the point of view of cleanliness, the average addition mole of the oxoalkyl group of the (ax) component is 1 to 5, preferably 1.5 or more, more preferably 2 or more, and more preferably 4.5 or less, more preferably 3 or less.

[0068] Examples of (ax) components include alkyl or alkenyl groups having 8 to 18 carbon atoms and an average addition mole number of alkyl groups of oxyalkyl groups of 1 to 5.

[0069] As a component of (ax), for example, compounds represented by the general formula (a x1) can be cited.

[0070] [Chemistry 2]

[0071] [In the formula, R is an alkyl or alkenyl group with 8 to 18 carbon atoms, EO is an ethoxy group, m and n are the average addition moles, and are independently 0 to 5, and the sum of m and n is 1 to 5.]

[0072] In formula (a x1), the number of carbon atoms in R can be 8 or more, more often 10 or more, and less than 18, more often 16 or less. R is preferably an alkyl group. The sum of m and n is preferably 1.5 or more, more preferably 2 or more, and more preferably 4.5 or less, more preferably 3 or less.

[0073] The HLB of component (ax) is not particularly limited as long as it does not deviate from the overall hydrophilicity and oleophilicity index range of the hard article cleaning composition (II) of the present invention. However, from the viewpoint of ease of acquisition and the cleaning properties of the modified oil, it is preferably 9 or higher, more preferably 9.5 or higher, and more preferably 14.2 or lower, and more preferably 13.0 or lower. The HLB of component (ax) is proposed by Griffin. Furthermore, in the present invention, in the method of <Determination of Hydrophilicity and Oleophilicity Index of Hard Article Cleaning Composition (II)> described in this specification, the hydrophilicity and oleophilicity index measured by replacing the hard article cleaning composition (II) with a mixture containing the surfactant of the test object at a concentration of 5% by mass and the remainder being water can be regarded as the HLB obtained by the Griffin method. This is also the same for the HLB of other surfactants such as component (bx).

[0074] From the viewpoint of cleanliness, the cleaning composition (II) for hard articles of the present invention may contain, for example, 0.01% by mass or more, more than 0.05% by mass, more than 0.1% by mass, and less than 50% by mass, less than 30% by mass, and less than 15% by mass of (ax) components.

[0075] From a cleanliness point of view, the hard article cleaning composition (II) of the present invention may contain, for example, more preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 25% by mass or more, more preferably 30% by mass or more, and more preferably 95% by mass or less, more preferably 90% by mass or less, and more preferably 85% by mass or less, relative to the total amount of surfactant in the composition. The total amount of surfactant is the total content of (ax) component, (bx) component, any (cx) component, and any other surfactant, such as any (dx) component and any (d'x) component, contained in the composition. The hard article cleaning composition (II) of the present invention is a composition containing surfactant, and may also be a composition containing (ax) component and (bx) component as surfactant.

[0076] (bx) is a nonionic surfactant (except for (ax) and acetamide-type nonionic surfactants).

[0077] Furthermore, the (bx) component of the present invention is a nonionic surfactant having a hydrocarbon group having 10 or more carbon atoms, more preferably 11 or more carbon atoms, and more preferably 18 or less carbon atoms, and more preferably 16 or less carbon atoms.

[0078] Furthermore, in this invention, hydrocarbon groups having 10 or more carbon atoms can be used as nonionic surfactants. Therefore, the content of nonionic surfactants included in the total amount of surfactants in the composition, such as component (bx) and component (dx) below, can be the content of nonionic surfactants having hydrocarbon groups having 10 or more carbon atoms in the composition. For example, nonionic compounds having hydrocarbon groups having 9 or fewer carbon atoms are not nonionic surfactants and can be excluded from the total amount of surfactants in the composition.

[0079] As a component (bx), examples include one or more nonionic surfactants selected from (b x1) polyoxyalkylene alkyl ethers [hereinafter referred to as component (b x1)], (b x2) alkyl (poly)glycosides [hereinafter referred to as component (b x2)], (b x3) polyoxyalkylene fatty acid esters [hereinafter referred to as component (b x3)], (b x4) polyglycerol fatty acid esters [hereinafter referred to as component (b x4)], and (b x5) (poly)oxyalkylene sorbitan fatty acid esters [hereinafter referred to as component (b x5)]. Component (bx) may be a nonionic surfactant selected from alkoxylated nonionic surfactants and alkyl glycoside surfactants. Component (bx1) is an example of an alkoxylated nonionic surfactant. Also, component (bx2) is an example of an alkyl glycoside surfactant.

[0080] The oxyalkylene group of component (b x1) is preferably a 2-carbon oxyalkylene group and / or a 3-carbon oxyalkylene group, i.e., oxyalkylene ethylene and / or oxyalkylene propylene, more preferably oxyalkylene ethylene. From the viewpoint of cleanliness, the average addition mole number of the oxyalkylene group of component (b x1) is preferably 0 or more, more preferably 1 or more, and more preferably 25 or less, more preferably 23 or less. From a cleanliness perspective, component (b x1) preferably contains an oxyethyl group as an oxyalkyl group. From a cleanliness perspective, the alkyl group of component (b x1) preferably has 10 or more carbon atoms, more preferably 12 or more, and more preferably 30 or less, more preferably 24 or less, further preferably 18 or less, and further preferably 16 or less. The alkyl group of component (b x1) can be straight-chain or branched, but is preferably straight-chain. The alkyl group of component (b x1) can be saturated or unsaturated, but is preferably saturated.

[0081] Regarding the (b x 2) component, from a cleanliness perspective, the number of carbon atoms in the alkyl group is preferably 10 or more, more preferably 12 or more, and preferably 30 or less, more preferably 24 or less, further preferably 18 or less, and further preferably 16 or less. Also, from a cleanliness perspective, the average degree of condensation of sugars such as glucose in the (b x 2) component is preferably 1 or more, and preferably 10 or less, and further preferably 5 or less. From a cleanliness perspective, the (b x 2) component is preferably an alkyl (poly)glycoside whose structural sugar is glucose.

[0082] The cleaning composition (II) for hard articles of the present invention preferably contains one or more nonionic surfactants selected from components (b x1) and (b x2) as component (bx), and more preferably contains one or more nonionic surfactants selected from component (b x1) as component (bx).

[0083] The HLB of component (bx) is not particularly limited as long as it does not deviate from the overall hydrophilicity and oleophilicity index range of the hard article cleaning composition (II) of the present invention. However, from the viewpoint of ease of acquisition and the cleaning properties of the modified oil, it is preferably 9 or higher, more preferably 9.5 or higher, and more preferably 17.4 or lower, more preferably 16.9 or lower. The HLB of component (bx) is obtained by the Griffin method. As mentioned above, the hydrophilicity and oleophilicity index measured by the prescribed method can be regarded as the HLB of component (bx) obtained by the Griffin method.

[0084] Regarding component (bx), from the viewpoint of cleanliness, it is preferable to be a nonionic surfactant with an HLB of 9 to 17.4 selected from one or more alkoxylated nonionic surfactants and alkyl glycoside nonionic surfactants; more preferably, it is a nonionic surfactant with an HLB of 9 to 17.4 selected from one or more components (bx1) and (bx2); and even more preferably, it is a nonionic surfactant with an HLB of 9 to 17.4 selected from one or more components (bx1).

[0085] From the viewpoint of cleanliness, the cleaning composition (II) for hard articles of the present invention may contain, for example, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 1% by mass or more, and more preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass or less (bx) component.

[0086] From the viewpoint of cleanliness, the cleaning composition (II) for hard articles of the present invention contains, for example, more preferably 8% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, and more preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, and more preferably 68% by mass or less of the (bx) component relative to the total amount of surfactant in the composition; more preferably (bx) component with an HLB of 9 or more and 17.4 or less; more preferably nonionic surfactants selected from one or more of alkoxylated nonionic surfactants and alkyl glycoside surfactants with an HLB of 9 or more and 17.4 or less; more preferably nonionic surfactants selected from one or more of (bx1) component and (bx2) component with an HLB of 9 or more and 17.4 or less; and more preferably nonionic surfactants selected from one or more of (bx1) component with an HLB of 9 or more and 17.4 or less.

[0087] Regarding the cleaning composition (II) for hard articles of the present invention, from the viewpoint of cleaning performance, the mass ratio of the content of component (ax) to the content of component (bx), i.e., (ax) / (bx), is preferably 0.01 or more, more preferably 0.04 or more, further preferably 0.08 or more, further preferably 0.1 or more, and preferably 30 or less, more preferably 20 or less, further preferably 13 or less, further preferably 10 or less.

[0088] In the cleaning composition (II) for hard materials of the present invention, without prejudice to the purpose of the present invention, surfactants, solvents, enzymes (protein-degrading enzymes, lipase-degrading enzymes, saccharide-degrading enzymes, etc.), water-soluble additives, pH adjusters, thickeners, dispersants, viscosity modifiers, fragrances, colorants, antioxidants, preservatives, and other components other than components (ax) and (bx) may be formulated.

[0089] The cleaning composition (II) for hard objects of the present invention may optionally contain the following (cx) components. (cx) Ingredients: Anionic surfactants

[0090] Examples of (cx) 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) sulfates, alkyl (preferably with 2 to 24 carbon atoms) phosphates, polyoxyalkyl (preferably polyoxyethyl) alkyl (preferably with 8 to 18 carbon atoms) sulfates, polyoxyalkyl (preferably polyoxyethyl) alkyl (preferably with 8 to 18 carbon atoms) carboxylates, and alkyl (preferably with 6 to 18 carbon atoms) sulfosuccinates. Examples of salts include sodium salts, potassium salts, and other alkali metal salts.

[0091] From the viewpoint of cleanliness, the cleaning composition (II) for hard articles of the present invention may contain, for example, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and more preferably 5% by mass or less, more preferably 3.5% by mass or less, and more preferably 2.4% by mass or less (cx) component.

[0092] Regarding the cleaning composition (II) for hard articles of the present invention, from the viewpoint of cleaning properties, the content of component (cx) relative to the total amount of surfactant in the composition is preferably 0% by mass or more, more preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 50% by mass or less, more preferably 25% by mass or less, more preferably 22% by mass or less, more preferably 20% by mass or less, and more preferably 18.5% by mass or less. The content of component (cx) in the cleaning composition (II) for hard articles of the present invention can be 0% by mass.

[0093] The cleaning composition (II) for hard articles of the present invention may optionally contain the following (dx) component. From the viewpoint of cleaning properties, the content of the (dx) component relative to the total amount of surfactant in the composition is preferably less than 10% by mass, more preferably 2% by mass or less, more preferably 1% by mass or less, more preferably 0.5% by mass or less, and the lower limit may be 0% by mass or more. The content of the (dx) component in the cleaning composition (II) for hard articles of the present invention may be 0% by mass in the composition. (dx) Ingredients: Acetamide-type nonionic surfactant

[0094] Examples of alkylamine compounds containing fatty acids having 8 or more carbon atoms, and further, 11 or more carbon atoms but less than 18 carbon atoms, and alkylamines having 1 or more hydroxyl groups but less than 6 hydroxyl groups are possible components of (dx). Preferably, the alkylamine contains 1 or more carbon atoms, and further, 2 or more carbon atoms but less than 8 carbon atoms. Specifically, examples include monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, reduced glucosamine, N-methylglucosamine, and N-methylethanolamine. In this invention, fatty acid (8 or more carbon atoms, and further, 11 or more carbon atoms but less than 18) diethanolamine, fatty acid (8 or more carbon atoms, and further, 11 or more carbon atoms but less than 18) N-methylethanolamine, and fatty acid (8 or more carbon atoms, and further, 11 or more carbon atoms but less than 18) N-methylglucosamine may be included as components of (dx). In this invention, the content of (dx) component can be the total content of amide-type nonionic surfactants selected from fatty acids (with 8 or more carbon atoms, and further 11 or more carbon atoms but less than 18), fatty acids (with 8 or more carbon atoms, and further 11 or more carbon atoms but less than 18), and fatty acids (with 8 or more carbon atoms, and further 11 or more carbon atoms but less than 18) N-methylethanolamide in the composition.

[0095] The cleaning composition (II) for hard articles of the present invention may optionally contain the following (d'x) component. From the viewpoint of cleaning properties, the content of the (d'x) component relative to the total amount of surfactant in the composition 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, and the lower limit can be 0% by mass or more. The content of the (d'x) component in the cleaning composition (II) for hard articles of the present invention can be 0% by mass in the composition. (d'x) Ingredients: Betaine-type surfactant

[0096] The (d'x) component is a surfactant having a betaine structure. Examples of the (d'x) component include: alkyl (e.g., 8 to 18 carbon atoms) dimethylaminoacetic acid betaine, alkyl (e.g., 8 to 18 carbon atoms) propylamino betaine, alkyl (e.g., 8 to 18 carbon atoms) hydroxysulfonyl betaine, and alkyl (preferably 8 to 18 carbon atoms) carboxymethyl hydroxyethyl imidazolium betaine. In this invention, the content of the (d'x) component can 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) propylamino betaine, alkyl (8 to 18 carbon atoms) hydroxysulfonyl betaine, and alkyl (8 to 18 carbon atoms) carboxymethyl hydroxyethyl imidazolium betaine in the composition.

[0097] Regarding the cleaning composition (II) for hard articles of the present invention, from the viewpoint of cleaning and workability, the total amount of surfactant in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 2.5% by mass or more, more preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 15% by mass or less. The cleaning composition (II) for hard articles of the present invention may be a composition containing surfactants, or it may be a composition containing (ax) component and (bx) component as surfactants, and the total amount of surfactant is within the above-mentioned range.

[0098] The cleaning composition (II) for hard articles of the present invention may optionally contain the following (ex) components. However, since the (ex) components tend to increase the hydrophilicity and hydrophobicity index of the composition, which may affect the cleaning performance, care should be taken when they are contained. Regarding the cleaning composition (II) for hard articles of the present invention, from the viewpoint of cleaning performance, the content of the (ex) component relative to the total amount of surfactant in the composition is preferably 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, more preferably 2% by mass or less, and the lower limit can be 0% by mass or more. For the purpose of adjusting the viscosity and other properties of the composition, it can be 0.5% by mass or more, and more preferably 0.1% by mass or more. The content of the (ex) component in the cleaning composition (II) for hard articles of the present invention can be 0% by mass in the composition. (ex) Composition: A hydrophilic solvent with a hydrocarbon group having 9 or fewer carbon atoms, having a solubility of 5 g / 100 g or more in water at 25°C.

[0099] As an ingredient (ex), examples include one or more hydrophilic solvents selected from monohydric alcohols, glycols, trihydric alcohols, mono- / di- or tri-alkyl glycol monoethers, and mono- / di- or tri-alkyl glycol diethers. Examples of ingredients (ex) may include those containing alkyl groups. The alkyl group may be selected from alkyl groups with various carbon numbers. Preferably, the alkyl group has 1 or more carbons, more preferably 3 or more, and more preferably less than 10, more preferably less than 8. As an ingredient (ex), from the viewpoint of formulation stability and cleaning power, it is preferably a hydrophilic solvent selected from one or more of methanol, ethanol, 1-propanol, 2-propanol, 1,2-hexanediol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether, more preferably a hydrophilic solvent selected from one or more of ethanol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether, and even more preferably diethylene glycol monobutyl ether.

[0100] From the viewpoint of stability and workability, the hard-material cleaning composition (II) of the present invention preferably contains water. The water is not particularly limited and examples include tap water, well water, ion-exchanged water, and distilled water. In the present invention, the water is preferably used in the remainder of the composition (totaling 100% by mass). Regarding the water content, for example, it can be set to 50% by mass or more in the hard-material cleaning composition (II), further to 60% by mass or more, and further to 70% by mass or more. The hard-material cleaning composition (II) of the present invention can be a liquid composition.

[0101] Regarding the cleaning composition (II) for hard objects of the present invention, from the viewpoint of cleaning properties, the overall hydrophilicity-lipophilicity index of the composition is 9 or more and 14.2 or less. Regarding the hydrophilicity and oleophilicity index of the cleaning composition (II) for hard articles of the present invention, from the viewpoint of cleaning performance, it may be 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, even more preferably 10 or more, even more preferably 10.0 or more, and preferably 14.2 or less, preferably 14.0 or less, even 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, even more preferably 11.0 or less. In this invention, the hydrophilicity and oleophilicity index of the hard-material cleaning agent composition (II) of this invention is determined by the following method. This determination method is based on the view described in Japanese Patent Application Publication No. 2020-38061, that is, an oil component and a phase change probe can be added to an aqueous sample, and the physical properties of the aqueous sample containing surfactant and water can be inferred based on the amount of the phase change probe when the phase structure of the mixture changes.

[0102] <Method for Determining the Hydrophilicity and Oleophilicity Index of Cleaning Composition (II) for Hard Items> (1) Creation of calibration curve Prepare multiple polyoxyethylene lauryl ethers with different HLB values ​​for the griffin. When the concentration (mmol / kg, the same below) of the surfactant in the cleaning agent composition for hard articles to be tested is unknown, its concentration shall be measured first. A precursor sample was prepared by mixing water and polyoxyethylene lauryl ether (of the specified HLB) to a concentration of polyoxyethylene lauryl ether equal to the concentration of surfactant in the hard-material cleaning agent composition. A standard sample was prepared by adding 2 g of oil (isoalkanes with an average carbon number of 16) and 5 g of solvent (diethylene glycol butyl ether) to the precursor sample. A phase change probe (diethylene glycol monooctyl ether) was added to the standard sample to quantify the amount of probe required for the phase change before the phase structure of the standard sample changed. This quantification was performed on multiple polyoxyethylene lauryl ethers with different HLB values ​​under the same conditions to obtain multiple quantitative values. A calibration curve was constructed based on these quantitative values ​​and the HLB values ​​of the surfactants contained in the standard samples for which these quantitative values ​​were given. (2) Calculation of hydrophilicity and oleophilicity index The test sample was prepared by adding 2 g of oil (isoalkanes with an average carbon number of 16) and 5 g of solvent (diethylene glycol butyl ether) to a cleaning agent composition for hard objects. A phase change probe (diethylene glycol monooctyl ether) is added to the test sample to quantify the amount of the probe required for the phase change before the phase structure of the test sample changes. The quantitative value of the probe used to determine the phase transition of the sample is applied to the calibration curve, and the HLB value of the corresponding calibration curve is used as the hydrophilicity and oleophilicity index of the cleaning agent composition for hard materials. Furthermore, in each of the operations described in (1) and (2) above, the temperature of each sample is set to 25°C.

[0103] The hydrophilicity and oleophilicity index of the hard article cleaning composition (II) of the present invention can be set to a specified range, for example, by adjusting the type or amount of the (ax) component, (bx) component, or any other component. In the present invention, in order to make the hydrophilicity index within a specified range, the following methods are suitable for use alone or in combination. 1: Adjust the mass ratio of (ax) / (bx) components. Regarding the mass ratio of the (ax) / (bx) component, as described above, it is preferably set to 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, even more preferably 20 or less, even more preferably 13 or less, even more preferably 10 or less. 2: Adjust the content of (cx) component as a hydrophilic surfactant. Regarding the content of component (cx), for example as described above, relative to the total amount of surfactant in the composition, it is preferably set to 0% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 3% by mass or more, and preferably 50% by mass or less, more preferably 25% by mass or less, further preferably 22% by mass or less, further preferably 20% by mass or less, and further preferably 18.5% by mass or less. 3: Adjust the content of (d'x) component as a hydrophilic surfactant. Regarding the content of component (d'x), for example as described above, it is set to less than 10% by mass relative to the total amount of surfactant in the composition, then to 5% by mass or less, then to 3% by mass or less, then to 1.5% by mass or less, and also to 0% by mass or more, or the content of component (d'x) in the composition is set to 0% by mass. 4: Adjust the content of hydrophobic surfactants, such as (dx) components. Regarding the content of the (dx) component, for example as described above, it is set to less than 10% by mass relative to the total amount of surfactant in the composition, then to 2% by mass or less, then to 1% by mass or less, then to 0.5% by mass or less, and also to 0% by mass or more, or the content of the (dx) component in the composition is set to 0% by mass. 5: Adjust the content of (ex) ingredients. Regarding the content of component (ex), as described above, relative to the total amount of surfactant in the composition, it is set to less than 50% by mass, then to less than 10% by mass, then to less than 5% by mass, then to less than 3% by mass, then to less than 2% by mass, and further set to more than 0% by mass, then to more than 0.1% by mass, then to more than 0.5% by mass, or the content of component (ex) in the composition is set to 0% by mass.

[0104] Regarding the cleaning composition (II) for hard articles of the present invention, from the viewpoint of cleaning performance, the pH value at 20°C is preferably 5 or higher, more preferably 5.5 or higher, and even more preferably 6 or higher, and preferably 11 or lower, more preferably 9 or lower, and even more preferably 8.5 or lower.

[0105] The cleaning composition (II) for hard objects of the present invention can be used on a variety of hard objects, but is preferably used on tableware and / or hard objects around the kitchen, and even more preferably on tableware.

[0106] Hard objects around the kitchen refer to items used in the area around the kitchen, specifically as follows: (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 stoves, and microwave ovens; and (3) The floor or walls around the above-mentioned storage area or cooking area. In this invention, for convenience, these are referred to as "hard objects around the kitchen". Furthermore, as tableware, specifically, the following components or utensils that come into contact with food can be listed: (i) Plates, bowls, and other tableware; (ii) Storage containers such as lunch boxes and bottles; (iii) Cooking utensils such as kitchen knives or cutting boards, pots, frying pans, and fish grills; (iv) Food processors, blenders and other cooking appliances. In this invention, for convenience, these are referred to as "tableware". Furthermore, the present invention preferably includes items selected from tableware, storage containers, cooking utensils, and cooking appliances, and more preferably includes items selected from plates, bowls, lunch boxes, bottles, knives, cutting boards, pots, frying pans, fish grills, food processors, and mixers.

[0107] Examples of materials that can be used to make hard articles include plastics (including silicone resins, etc.), metals, ceramics, wood, and combinations thereof. Furthermore, the cleaning composition (II) for hard articles of the present invention can effectively clean oil stains adhering to such hard articles.

[0108] As mentioned above, modified oil stains adhering to hydrophobic materials such as plastics are difficult to remove. However, this invention exhibits excellent cleaning effects even on modified oil stains adhering to hard plastic articles. This invention is also suitable for cleaning hard plastic articles. Examples of plastics include polypropylene, polyethylene and other polyolefins, polymethyl methacrylate, polycarbonate, ABS resin, polyethylene terephthalate, etc.

[0109] Cleaning Methods for Hard Items (II) This invention provides a cleaning method (II) for hard articles by bringing the cleaning agent composition (II) of this invention into contact with a hard article with dirt. In the cleaning method (II) of this invention, the properties described in the cleaning agent composition (II) of this invention can be appropriately applied.

[0110] In the cleaning method (II) for hard articles of the present invention, the cleaning agent composition (II) for hard articles of the present invention can be foamed and brought into contact with the hard article. For example, the cleaning agent composition (II) for hard articles of the present invention can be foamed by a sponge or by a spraying device equipped with a foam forming mechanism and brought into contact with the hard article. Alternatively, the cleaning agent composition (II) for hard articles of the present invention can be brought into contact with the hard article by spraying, coating, impregnation, etc.

[0111] Examples of hard articles that are the target of the cleaning method (II) for hard articles of the present invention include those described in the cleaning agent composition (II) for hard articles of the present invention. Tableware is one of the suitable hard articles.

[0112] In the cleaning method (II) for hard articles of the present invention, the dirt adhering to the hard articles may be modified oil stains or other oil stains, and may also be modified oil stains.

[0113] In the cleaning method (II) for hard articles of the present invention, hard articles with oil stains, especially heat-modified oil, attached to them can be immersed in the above composition to bring them into contact with the cleaning agent composition (II) for hard articles of the present invention. However, from the viewpoint of efficiently improving cleaning power, it is preferable to spray or coat the above composition to bring it into contact with the hard articles with oil stains, especially heat-modified oil, attached to them. The method of bringing the cleaning composition (II) for hard articles of the present invention into contact with hard articles with oil stains or the like is preferably by spraying or coating, and more preferably by spraying in droplets or coating in foam form. Specifically, regarding the contact of the cleaning composition (II) for hard articles of the present invention with hard articles, a spraying device may be used, for example. That is, in the present invention, it is preferable to use a cleaning agent for hard articles prepared by filling the cleaning composition (II) for hard articles of the present invention into a container equipped with a spraying device.

[0114] As a method of applying foam, examples include: a method of foaming the hard article cleaning agent composition (II) of the present invention by entraining air in the nozzle part of the spraying device; and a method of foaming the hard article cleaning agent composition (II) of the present invention by rubbing it several times after containing it in a sponge or cleaning fiber article.

[0115] The present invention provides a hard article cleaner of the present invention packaged in a spray container, which is formed by filling the hard article cleaner composition (II) of the present invention into a container equipped with a spraying device.

[0116] The container equipped with a spraying device in the cleaning agent for hard objects contained in the spray container of the present invention can be exemplified by a trigger-type spray container, a pump-type spray container, or other manual spraying device that does not use a spray agent; or an aerosol that uses a spray agent. The container equipped with the spraying device is preferably a trigger-type sprayer that can spray or coat the contents into droplets or foam, more preferably a trigger-type sprayer equipped with a mechanism for spraying the contents into droplets or a trigger-type sprayer equipped with a mechanism for forming foam (foam forming mechanism).

[0117] In the case of the hard article cleaning agent contained in the spray container of the present invention, when using a trigger-type sprayer equipped with a mechanism for spraying the hard article cleaning agent composition (II) of the present invention in droplet form, in order to facilitate spraying or avoid coarse sprayed droplets, the spray is in a straight line and the sprayable area is very narrow. The nozzle diameter of the spray container containing the above 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. When using a trigger-type sprayer with a mechanism for spraying droplets, the composition of the hard article cleaner contained in the spray container of the present invention preferably sprays 0.1 mL or more, more preferably 0.3 mL or more, and more preferably 5 mL or less, and more preferably 2 mL or less in one operation.

[0118] When using a trigger-type sprayer equipped with a foam-forming mechanism, the composition of the hard-article cleaner contained in the spray container of the present invention is preferably sprayed at a rate of 0.5 mL or more, more preferably 1 mL or more, and more preferably 30 mL or less, more preferably 15 mL or less, and even more preferably 5 mL or less in a single operation.

[0119] In the cleaning method (II) for hard articles of the present invention, the cleaning agent composition (II) for hard articles of the present invention is brought into contact with the hard article for cleaning. In the cleaning method (II) for hard articles of the present invention, for example, the article can be immersed in the cleaning agent composition (II) for hard articles of the present invention, placed in a coated state, wiped with a sponge or fibrous product, and rinsed with running water, thereby removing dirt from the hard article and cleaning it. Furthermore, it can be rinsed with running water. The cleaning method (II) for hard articles of the present invention can be a hand washing cleaning method, and hard articles such as tableware can be hand-washed according to known methods.

[0120] Example The cleaning compositions for hard materials listed in Tables 1-3 were prepared using the following formulation ingredients, and their cleaning power against oil stains was evaluated as follows. The results are shown in Tables 1-3. The adjustment amounts in the tables refer to the amounts used to adjust the pH value of the composition to the values ​​shown in the tables. Furthermore, the (d) / total surfactant (mass %) in the tables refers to the content of component (d) relative to the mass % of the total surfactant in the composition. The (d) / total surfactant ratio for the compositions in Tables 1 and 2 is 0 by mass.

[0121] <Formulation Ingredients> (a)Ingredients • AMIET 102: Average addition mole number of polyoxyethylene laurylamine and oxyethylated 2.1, HLB 9.1 (equivalent measured value by Griffin method*1), Kao Corporation, AMIET 102 • AMIET 302: Polyoxyethylene stearylamine, average addition mole number of oxyethyl 2.1, HLB 7.4 (equivalent measured value by Griffin method*1), Kao Corporation, AMIET 302 • AMIET 105: Average addition mole number of polyoxyethylene laurylamine and oxyethylated 4.2, HLB 10.4 (equivalent measured value by Griffin method*1), Kao Corporation, AMIET 105

[0122] (b) Components (b1) Components AG-124: Alkyl polyglucan, HLB 11.5 (equivalent to measured value by Griffin method*1), Kao Corporation, AG-124 • E120: Polyoxyethylene lauryl ether, average addition mole number of oxyethyl 13.2, HLB 15.3 (Griffin process *2), Kao Corporation, Emulgen 120 • E707: Polyoxyethylene alkyl ether, average addition mole number of oxyethylated ether 7, HLB 12.1 (Griffin process *2), Kao Corporation, Emulgen 707

[0123] (b2) Components • Emal 20C: Sodium polyoxyethylene dodecyl sulfate, average addition mole number of oxyethylated 3, HLB 13.4 (equivalent measured value by Griffin method*1), Kao Corporation, Emal 20C Neopelex G-25: Sodium dodecylbenzenesulfonate, HLB 11.6 (Griffin method equivalent measured value*1), Kao Corporation, Neopelex G-25

[0124] (b') Component ((b) Component Comparison Component) Quartamin 60W: 30% aqueous solution of hexadecyltrimethylammonium chloride, HLB 13.8 (Griffin method equivalent measured value*1), Kao Corporation, Quartamin 60W. The amounts added in the table are based on hexadecyltrimethylammonium chloride.

[0125] *1 The HLB equivalent to the Griffin method is determined according to the following method. Prepare multiple polyoxyethylene lauryl ethers with different HLB values ​​for griffin. Using the component to be tested and water, prepare a composition with a surfactant concentration of 5% by mass, and calculate the molar concentration (mmol / kg) of the surfactant. Water and polyoxyethylene lauryl ether (of the specified HLB type) are mixed to prepare a precursor sample with the same concentration of polyoxyethylene lauryl ether as the molar concentration of the surfactant mentioned above. A standard sample was prepared by adding 2 g of oil (isoalkanes with an average carbon number of 16) and 5 g of solvent (diethylene glycol butyl ether) to the precursor sample. A phase change probe (diethylene glycol monooctyl ether) was added to the standard sample to quantify the amount of the probe required for the phase change before the phase structure of the standard sample changed. Multiple polyoxyethylene lauryl ethers with different HLB values ​​were quantified under the same conditions to obtain multiple quantitative values. A calibration curve was constructed based on these quantitative values ​​and the HLB values ​​of the polyoxyethylene lauryl ethers for which these quantitative values ​​were given. The test sample was prepared by adding 2 g of oil (isoalkanes with an average carbon number of 16) and 5 g of solvent (diethylene glycol butyl ether) to a surfactant composition obtained from the component to be tested and water. A phase change probe (diethylene glycol monooctyl ether) is added to the test sample to quantify the amount of the probe required for the phase change before the phase structure of the test sample changes. The quantitative value of the probe used to determine the phase transition of the sample is applied to the calibration curve, and the HLB value of the corresponding calibration curve is set as the HLB of the Griffin method equivalent of the component being measured. *2 The HLB figure based on the Griffin process is calculated using the average addition mole number of oxyethylated esters.

[0126] (c) Components ·GE-EH: 2-Ethylhexyl monoglyceride ·BDG: Diethylene glycol butyl ether • PPG-1000: Polypropylene glycol, weight average molecular weight 1000

[0127] (d) Components • Acetamide-type nonionic surfactants: Kao Corporation, AMINON PK-02S, palm kernel oil fatty acid diethanolamide • Betaine-type surfactants: Kao Corporation, Amphitol 20HD, lauryl hydroxysulfonyl betaine

[0128] <The persistence of cleaning foam> Apply 1 g of oil (tallow oil / rapeseed oil = 1 / 1, by mass) to a ceramic dish (23 cm in diameter). After applying the oil, place the ceramic dish at 25°C for 2 hours to serve as the evaluation contaminated dish. Prepare several evaluation contaminated dishes. Soak a sponge (manufactured by KIKULON Co., Ltd.) in a cleaning agent composition for hard objects and 30 g of tap water (30°C), rub it several times to create foam, and then use it to clean a soiled evaluation plate. Cleaning is considered complete when the sponge no longer feels sticky to the touch. After cleaning, without replacing the sponge (or soaking it in new composition), create foam again and use it to clean a new soiled evaluation plate. Repeat this cleaning process until cleaning is no longer possible. The persistence of the cleaning foam is evaluated by the number of soiled evaluation plates that can be cleaned while still producing foam.

[0129] [Table 1] Example Comparative example 1a-1 1a-2 1a-3 1a-4 1a-5 1a-6 1a-7 1a-8 1a-9 1a-1 1a-2 1a-3 1a-4 Cleaning composition for hard objects Blending ingredients (mass %) (a) AMIET 102 6 4 2 4 4 4 4 3 2 4 4 4 (b) AG-124 6 8 10 8 8 6 5 8 8 8 8 (b') Quartamin 60W 8 (c) GE-EH 3 3 3 5 7 5 6 4 5 3 3 3 Citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water Remainder Remainder margin margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 100 100 100 (a) / (b) (mass ratio) 1 0.5 0.2 0.5 0.5 0.67 0.8 0.38 0.25 0 - 0.5 0.5 (a) / (c) (mass ratio) 2.0 1.3 0.67 0.80 0.57 0.80 0.67 0.75 0.40 0 1.3 - 1.3 pH value (20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 Appearance White discharge White discharge White discharge White discharge White discharge White discharge White discharge White discharge White discharge White discharge Separation transparent transparent Duration of cleaning foam (cleaning quantity) 4 4 6 5 5 4 4 6 5 3 0 3 2

[0130] [Table 2] Example 2a-1 2a-2 2a-3 2a-4 2a-5 2a-6 2a-7 2a-8 Cleaning composition for hard objects Blending ingredients (mass %) (a) AMIET 102 4 4 4 4 4 4 AMIET 302 4 AMIET 105 4 (b) (b1) AG-124 8 8 8 8 E120 8 E707 8 (b2) Emal 20C 8 Neopelex G-25 8 (c) GE-EH 3 3 3 3 3 3 BDG 3 PPG-1000 3 Citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water Remainder Remainder margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 (a) / (b) (mass ratio) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 (a) / (c) (mass ratio) 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 pH value (20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 Appearance transparent transparent White discharge transparent transparent transparent gel White discharge Duration of cleaning foam (cleaning quantity) 5 5 5 6 5 5 7 4

[0131] [Table 3] Example Comparative example Example Comparative example Example Comparative example 3a-1 3a-1 3a-2 3a-2 3a-3 3a-3 Cleaning composition for hard objects Blending ingredients (mass %) (a) AMIET 102 4.0 4.0 4.0 4.0 4.0 4.0 (b) (b1) AG-124 8.0 8.0 8.0 8.0 8.0 8.0 (c) BDG 3.0 11 GE-EH 5 5 5 5 (d) Acetamide-type nonionic surfactants 2 betaine-type surfactants 1 5 Citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin total 100 100 100 100 100 100 (a) / (c) (mass ratio) 1.3 0.36 0.80 0.80 0.80 0.80 (d) / Total amount of surfactant (mass%) 0.00 0.00 0.00 14 7.7 29 (a) / (b) (mass ratio) 0.50 0.50 0.50 0.50 0.50 0.50 pH value (20℃) 7.1 7.1 7.1 7.1 7.1 7.1 Appearance transparent transparent White discharge White discharge transparent transparent Duration of cleaning foam (cleaning quantity) 5 2 4 2 5 3

[0132] <Distribution Example> Table 4 shows examples of the formulation of the cleaning composition (I) for hard articles of the present invention.

[0133] [Table 4] Mixing Example 4a-1 4a-2 4a-3 4a-4 4a-5 4a-6 4a-7 4a-8 4a-9 4a-10 4a-11 Cleaning composition for hard objects Blending ingredients (mass %) (a) AMIET 102 2 2 2 2 2 2 2 2 4 4 4 (b) (b1) AG-124 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 8 8 8 (c) (c1) GE-EH 1 1 1.5 2 3 1 3.5 0.5 3 3 3 (c2) BDG 1 0.5 0.5 1 1.5 0.5 3 (c3) PPG-1000 1 1 1.5 0.5 (d) Acetamide-type nonionic surfactants 0.5 0.3 0.1 Citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 100 (a) / (b) (mass ratio) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 (a) / (c) (mass ratio) 1.0 1.0 1.0 0.80 0.40 0.50 0.44 0.57 1.3 1.3 1.3 (a) / (c1) (mass ratio) 2.0 2.0 1.3 1.0 0.67 2.0 0.57 4.0 1.3 1.3 1.3 (a) / [(c2)+(c3)](mass ratio) 2.0 2.0 4.0 4.0 1.0 0.67 2.0 0.67 - - - (c1) / [(c2)+(c3)](mass ratio) 1.0 1.0 3.0 4.0 1.5 0.33 3.5 0.17 - - - (d) / Total amount of surfactant (mass%) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4 2.4 0.83 pH value (20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1

[0134] The cleaning compositions for hard materials listed in Tables 5-7 were prepared using the following formulation ingredients. Their cleaning properties against modified oil stains were evaluated using the following method. The results are shown in Tables 5-7. The hydrophilicity / lipophilicity index in the tables is the value of the overall composition measured at 25°C using the method described above. Furthermore, the adjustment amount in the tables refers to the amount used to adjust the pH value of the composition to the value shown in the table.

[0135] <Formulation Ingredients> (ax) component • AMIET 102: Average addition mole number of polyoxyethylene laurylamine and oxyethylated 2.1, HLB 9.1 (equivalent measured value by Griffin method*1), Kao Corporation, AMIET 102

[0136] (bx) component E102-KG: Polyoxyethylene lauryl ether, average addition mole number of oxyethylated 2, HLB 6.42 (Griffin process *2), Kao Corporation, Emulgen 102KG E105: Polyoxyethylene lauryl ether, average addition mole number of oxyethylated 3.8, HLB 9.7 (Griffin process *2), Kao Corporation, Emulgen 105 E108: Polyoxyethylene lauryl ether, average addition mole number of oxyethylated ether 5.6, HLB 12.1 (Griffin process *2), Kao Corporation, Emulgen 108 • E120: Polyoxyethylene lauryl ether, average addition mole number of oxyethyl 13.2, HLB 15.3 (Griffin process *2), Kao Corporation, Emulgen 120 E121: Polyoxyethylene lauryl ether, average addition mole number of oxyethylated 21, HLB 16.65 (Griffin process *2), Kao Corporation, Emulgen 121 E705: Polyoxyethylene alkyl ether, with an average addition mole number of 5 for the oxyethyl group, and the alkyl group being a secondary alkyl group with 11-15 carbon atoms, HLB 10.5 (Griffin process *2), Kao Corporation, Emulgen 705 E707: Polyoxyethylene alkyl ether, with an average addition mole number of 7 for the oxyethyl group, and the alkyl group being a secondary alkyl group with 11-15 carbon atoms, HLB 12.1 (Griffin process *2), Kao Corporation, Emulgen 707 AG-124: Alkyl polyglucoside, alkyl group is a primary alkyl group with 12-16 carbon atoms, average degree of sugar condensation 1-2, HLB 11.5 (equivalent to measured value by Griffin method*1), Kao Corporation, AG-124

[0137] (cx) component • Emal 20C: Sodium polyoxyethylene dodecyl sulfate, average addition mole number of oxyethylated 3, HLB 13.4 (equivalent measured value by Griffin method*1), Kao Corporation, Emal 20C

[0138] (dx) ingredient • Acetamide-type nonionic surfactants: Kao Corporation, AMINON PK-02S, palm kernel oil fatty acid diethanolamide

[0139] (d'x) component • Betaine-type surfactants: Kao Corporation, Amphitol 20HD, lauryl hydroxysulfonyl betaine

[0140] (ex) components Diethylene glycol butyl ether: readily soluble in water (solubility in water at 25°C is greater than 5 g / 100 g).

[0141] *1 The equivalent measured value of the Griffin method is the hydrophilicity and lipophilicity index of each surfactant as described in the <Method for Determining the Hydrophilicity and Lipophilicity Index of a Cleaning Composition for Hard Items> in this specification. The determination is carried out at 25°C using a mixture containing the surfactant of the test object at a concentration of 5% by mass and the remainder being water as the cleaning composition for hard items. *2 The HLB figure based on the Griffin process is calculated using the average addition mole number of oxyethylated esters.

[0142] Cleaning power against modified oil stains The protective film on a SUS (Steel Use Stainless, Japanese standard) 304 test piece (1.0 mm × 25 mm × 70 mm) manufactured by Engineering Test Service was peeled off. The piece was then cleaned and rinsed with a sponge using a neutral dishwashing detergent (once with tap water, twice with deionized water). It was then dried in an electric dryer at 80°C to prepare a pre-treated SUS plate. The mass of the pre-treated SUS plate was measured using a 4-digit balance and taken as the initial mass (X). A modified oil / chloroform solution was prepared by mixing 20 g of modified oil with 60 mL of chloroform. Here, the modified oil was prepared by heating rapeseed oil (from Fujifilm and Koichi Pure Chemical Industries Co., Ltd.) after standing at 180°C for 8 hours. Using a dropper, the modified oil / chloroform solution was poured once onto a single 25 mm × 50 mm area of ​​a pretreated SUS plate at a concentration of 1 mg / cm². The plate was laid flat overnight with the oil-coated side facing up to dry, thus creating a cleaning SUS plate. The mass of the cleaning SUS plate was measured using a 4-position balance and recorded as the initial mass (Y). Each hard-material cleaning composition in the table was evaluated using three SUS cleaning plates. Three SUS cleaning plates were arranged on a BD-3 balance pan (140×140×25 mm), immersed in 40 mL of the hard-material cleaning composition, and placed at 25°C for 20 minutes. Afterward, they were rinsed with tap water for 1 minute using a Leenets testing machine at 300 rpm, and then laid flat to dry overnight. The mass of the dried SUS cleaning plates was measured using a four-position balance and recorded as the post-cleaning mass (Z). The cleaning rate is calculated based on the initial quality (X), the quality before cleaning (Y), and the quality after cleaning (Z) using the following formula. Cleanliness rate (%) = [Pre-cleaning quality (Y) - Post-cleaning quality (Z)] / [Pre-cleaning quality (Y) - Initial quality (X)] × 100

[0143] [Table 5] Example 1b 2b 3b 4b 5b 6b 7b 8b 9b 10b Cleaning composition for hard objects Blending ingredients (mass %) (ax) AMIET 102 6 8 6 8 8 4 6 8 6 8 (bx) E102-KG E105 6 4 E108 6 4 E120 4 8 E121 E705 6 4 E707 6 4 AG-124 (cx) Emal 20C Citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 pH value (20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 Hydrophilicity and lipophilicity index of the composition 9.4 9.3 10.6 10.1 11.2 13.2 9.8 9.6 10.6 10.1 Cleaning rate of modified oil stains (%) 26.8 32.8 42.4 44.9 40.0 41.7 46.8 35.4 48.0 61.3 Appearance White discharge White discharge transparent transparent transparent transparent White discharge White discharge transparent transparent

[0144] [Table 6] Example Comparative example 11b 12b 13b 14b 15b 16b 17b 18b 1b 2b 3b 4b 5b 6b 7b Cleaning composition for hard objects Blending ingredients (mass %) (ax) AMIET 102 6 4 3.8 3.6 3.4 10 10 10 6 8 4 2 10 2 2 (bx) E102-KG 6 4 8 10 2 E105 E108 E120 2 10 E121 2 10 E705 E707 2 AG-124 6 8 7.6 7.2 6.4 (cx) Emal 20C 0.6 1.2 2.2 Citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 pH value (20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 Hydrophilicity and lipophilicity index of the composition 10.3 10.7 10.8 11.0 11.2 10.13 10.36 9.6 7.76 8.21 7.31 6.87 8.65 14.27 15.39 Cleaning rate of modified oil stains (%) 48.8 57.0 57.54 66.67 67.47 56.0 50.7 24.5 6.1 6.4 3.0 2.7 13.2 19.0 14.0 Appearance White discharge transparent transparent transparent transparent transparent transparent White discharge White discharge White discharge White discharge White discharge White discharge transparent transparent

[0145] [Table 7] Example 19b 20b 21b 22b Cleaning composition for hard objects Blending ingredients (mass %) (ax) AMIET 102 6 6 6 6 (bx) AG-124 6 6 6 6 (dx) Acetamide-type nonionic surfactants 2 (d' x) betaine-type surfactants (ex) Diethylene glycol butyl ether 3 8 Citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin total 100 100 100 100 pH value (20℃) 7.1 7.1 7.1 7.1 (d) / Total amount of surfactant (mass%) 0.00 0.00 0.00 14 (d') / Total amount of surfactant (mass%) 0.00 0.00 0.00 0.00 (e) / Total amount of surfactant (mass%) 25 67 0.00 0.00 (e) / (a) (mass ratio) 2.00 0.75 0.00 0.00 Hydrophilicity and lipophilicity index of the composition 11.3 13.3 10.3 9.6 Cleaning rate of modified oil stains (%) 49.2 31.8 48.8 27.1 Appearance White discharge transparent White discharge White discharge

Claims

1. A cleaning composition for hard objects, comprising the following components (a), (b), and (c), wherein the mass ratio of the content of component (a) to the content of component (c), i.e., (a) / (c), is 0.60 to 5.0, and comprising (d) one or more surfactants selected from betaine-type surfactants and amide-type nonionic surfactants [hereinafter referred to as component (d)], wherein the content of component (d) is 0% to 1.5% by mass relative to the total amount of surfactants in the composition, wherein (a) is an alkyl or alkenyl amine having 6 to 20 carbon atoms and having an average addition mole number of oxyalkylene groups of 1 to 5; (b) is a surfactant selected from one or more surfactants selected from nonionic surfactants and anionic surfactants, except for component (a) and amide-type nonionic surfactants; and (c) is a solvent.

2. The hard object cleaning composition of claim 1, wherein the mass ratio of the content of component (a) to the content of component (b), i.e., (a) / (b), is more than 0.01 and less than 3.

3. The cleaning composition for hard objects as claimed in item 1 or 2, has a pH value of 5 or higher and 11 or lower at 20°C.

4. The cleaning composition for hard articles as claimed in claim 1 or 2, wherein component (c) is a solvent selected from one or more of glycerol ether, glycol ether and polypropylene glycol.

5. The cleaning composition for hard objects as claimed in claim 1 or 2, which contains 0.01% by mass and 30% by mass of ingredient (a).

6. The cleaning composition for hard articles as claimed in claim 1 or 2, wherein component (b) is a nonionic surfactant selected from one or more of (b11) polyoxyalkylene alkyl ethers and (b12) alkyl (poly)glycosides.

7. A method for cleaning hard articles, wherein a hard article cleaning composition as claimed in any one of claims 1 to 6 is brought into contact with a hard article to which dirt is attached.

8. The cleaning method for hard articles as described in claim 7, wherein the cleaning agent composition foams the hard article and brings it into contact with the hard article.

9. The cleaning method for hard articles as described in claim 8, wherein the cleaning agent composition for the hard articles is foamed by a sponge or by a spraying device having a foam-forming mechanism and comes into contact with the hard articles.

10. A cleaning method for hard objects as described in any of the requests 7 to 9, wherein the hard object is tableware.