Detergent composition for hard surfaces

Abstract

To provide a detergent composition for hard surfaces that offers disinfection performance, high detergency, and superior antifouling and finishing properties, and to provide a method for cleaning hard surfaces.SOLUTION: A detergent composition for hard surfaces comprises (a) an ampholytic surfactant, (b) a bactericide [Component (b)], (c) a polymer having at least one group selected from an amino group, a quaternary ammonium group and a betaine group [Component (c)], and water. The mass ratio between the content of Component (c) and the content of Component (b), (c) / (b), exceeds 1.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] In the kitchen, such as inside the sink or countertop used for washing dishes and vegetables, and around the gas range, inorganic dirt mainly composed of silicon or calcium, oily dirt from cooking or dishes, or a combination of these dirts are attached. In particular, dirt that occurs around cooking equipment is mainly oil-derived dirt, and since the heat source is close, the oil is easily degraded and very difficult to remove. Conventionally, powder or liquid cleansers containing abrasives and strong alkaline cleaning agents have been used to remove such dirt. However, although the former has excellent cleaning properties against dirt, there are problems with the labor of scrubbing and the complexity of rinsing and wiping. In addition, the latter has disadvantages such as insufficient cleaning power against inorganic dirt and rough hands due to alkali, and a simpler and safer cleaning method has been desired.

[0003] Patent Document 1 discloses a hard surface treatment composition that uses a polymer having a sulfobetaine group to hydrophilize hydrophobic hard surfaces in bathrooms, kitchens, toilets, etc., thereby imparting antifouling properties. Furthermore, Patent Document 2 discloses an antifouling cleaner composition for hard surfaces that combines a polymer in which vinyl monomers having anionic groups, cationic groups, and nonionic groups are combined in a specific molar ratio and mass ratio with specific suitable compounding agents, thereby also having an effect of preventing adhesion of dirt and is particularly suitable for cleaning and preventing dirt from being attached to bathrooms and kitchen sinks. Patent Document 3 describes a polymerizable composition comprising a monomer unit A having one or more groups selected from an amino group and a quaternary ammonium group in the molecule, and a -SO 2 and a monomer unit B represented by the formula (I)-(N-dimethylformamide), the monomer unit A is contained in an amount of 10 to 99 mol % based on the total monomer units, and the molar ratio of monomer unit B / monomer unit A is 0.01 to 1. Patent Document 4 discloses an article for hard surface treatment comprising a trigger-type spray container and a liquid composition for hard surface treatment contained in the spray container, in which the spray container is capable of spraying the liquid composition for hard surface treatment in the form of a foam, the liquid composition for hard surface treatment containing a polymer having a betaine structure and a specified surfactant, and the sprayed foam has a specific foam volume of 5 ml / g or more. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-105311 A [Patent Document 2] JP 2001-271094 A [Patent Document 3] JP 2003-313600 A [Patent Document 4] JP 2018-199771 A Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, the number of people, especially young people, who take daily preventive care to prevent kitchen stains from becoming difficult to remove over time is increasing. They are prioritizing the simplification and time-saving of housework, and want to reduce the effort required to maintain cleanliness. To meet these needs, it would be useful to have a product that can easily clean and disinfect with a single operation, while also having an anti-fouling function that makes it easy to remove dirt even if it does get on. In particular, the inside of the sink is the place that most needs cleanliness, but it is also prone to contamination due to the high frequency of contact between dirt and water, so there has been a demand for a product that has a sustained anti-fouling effect and maintains the gloss of the surface. The present invention provides a cleaning composition for hard surfaces that has disinfecting performance, high detergency, and excellent stain resistance and finish, and a method for cleaning hard surfaces. [Means for solving the problem]

[0006] The present invention relates to a cleaning composition for hard surfaces, which contains (a) an amphoteric surfactant (hereinafter referred to as component (a)), (b) a bactericide (hereinafter referred to as component (b)), (c) a polymer having one or more groups selected from an amino group, a quaternary ammonium group, and a betaine group (hereinafter referred to as component (c)), and water, in which the mass ratio (c) / (b) of the content of component (c) to the content of component (b) exceeds 1.

[0007] The present invention also relates to a method for cleaning a hard surface, which comprises contacting the above-mentioned cleaning composition for hard surfaces with the hard surface. Effect of the Invention

[0008] According to the present invention, there are provided a cleaning composition for hard surfaces which has disinfecting performance, high detergency, and excellent stain resistance and finish properties, and a method for cleaning hard surfaces. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The reason why the cleaning composition for hard surfaces of the present invention has disinfecting performance, high detergency, and excellent stain resistance and finish is not entirely clear, but is presumed to be as follows. It is presumed that the hard surface cleaning composition of the present invention, by using component (a), is able to achieve both cleaning performance, appropriate foaming, disinfecting performance, and finishing quality without adversely affecting the dissolved states of components (b) and (c). In addition, it is presumed that by using the (b) component and the (c) component in a specific ratio, it is possible to satisfy the sterilization performance and the hard surface modification effect without inhibiting the adsorption of the polymer to the hard surface. The hard surface modification effect can improve the gloss and antifouling properties. The hard surface cleaning composition and hard surface cleaning method of the present invention are not limited to the above-mentioned mechanism of action. In the present invention, the bactericide may be an agent having one or more effects selected from germicidal, disinfectant, and antibacterial effects. That is, the bactericide may be a germicidal or antibacterial agent.

[0010] <Cleaning composition for hard surfaces> The cleaning composition for hard surfaces of the present invention contains (a) an amphoteric surfactant (hereinafter referred to as component (a)), (b) a bactericide (hereinafter referred to as component (b)), (c) a polymer having one or more groups selected from an amino group, a quaternary ammonium group, and a betaine group (hereinafter referred to as component (c)), and water.

[0011] <Component (a)> The component (a) is an amphoteric surfactant. From the viewpoints of cleaning performance, foaming, and appearance during wiping, the amphoteric surfactant is preferably one or more amphoteric surfactants selected from amine oxide amphoteric surfactants and betaine amphoteric surfactants, more preferably one or more amphoteric surfactants selected from amine oxide, sulfobetaine, and carbobetaine, and even more preferably amine oxide.

[0012] As the amine oxide, a compound represented by the following general formula (a1) (hereinafter referred to as component (a1)) is preferable.

[0013] [ka]

[0014] [In the formula, R 1a represents a hydrocarbon group having 6 to 22 carbon atoms, preferably an alkyl or alkenyl group, more preferably an alkyl group; R 2a and R 3a each independently represents an alkyl group having 1 to 3 carbon atoms; D represents an -NHC(=O)- group or a -C(=O)NH- group; E represents an alkylene group having 1 to 5 carbon atoms; q and p represent q=0 and p=0 or q=1 and p=1.

[0015] In the above general formula (a1), when q=1 and p=1, R 1aFrom the viewpoints of detergency, solubility and foaming property, preferably represents a hydrocarbon group having 7 or more carbon atoms, more preferably 9 or more carbon atoms, and preferably 21 or less, more preferably 17 or less, and even more preferably 15 or less carbon atoms, preferably an alkyl or alkenyl group, and more preferably an alkyl group. Also, when q=0 and p=0, R 1a From the viewpoints of detergency, solubility and foaming property, preferably represents a hydrocarbon group having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and 22 or less, preferably 18 or less, more preferably 16 or less carbon atoms, preferably an alkyl or alkenyl group, more preferably an alkyl group. In the present invention, it is preferable that q=0 and p=0. 2a and R 3a From the viewpoints of cleaning properties and solubility, is preferably a methyl group having one carbon atom.

[0016] Preferred specific examples of the component (a1) include: (1) Alkyl (carbon number 6 to 22) dialkyl (carbon number 1 to 3) amine oxides: capryl dimethylamine oxide, capric dimethylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, palmityl dimethylamine oxide, stearyl dimethylamine oxide, etc. (2) Amide group-containing amine oxides (compounds in which q=1 and p=1 in the general formula (a1)): caprylic acid amidopropyl dimethylamine oxide, capric acid amidopropyl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, palmitic acid amidopropyl dimethylamine oxide, etc. These can be used alone or in combination of two or more. From the viewpoint of achieving both good cleaning properties and good finish, (1) alkyl (having 6 to 22 carbon atoms) dialkyl (having 1 to 3 carbon atoms) amine oxides are more preferred.

[0017] The betaine-type amphoteric surfactant is preferably a compound represented by the following general formula (a2).

[0018] [ka]

[0019] [In the formula, R 4a is an alkyl or alkenyl group having 7 to 18 carbon atoms, R 5a is an alkylene group having 1 to 6 carbon atoms; A is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, and -O-; and r is the number 0 or 1. 6a , R 7a are each independently an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms; R 8a is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. B is -SO 3 - , -OSO 3 - , -COO - is a group selected from the following:

[0020] In the general formula (a2), R 4a From the viewpoint of low substrate damage, represents an alkyl or alkenyl group, preferably an alkyl group, having 7 or more, preferably 8 or more, more preferably 10 or more carbon atoms and 18 or less, preferably 16 or less, more preferably 14 or less carbon atoms. From the viewpoint of low damage to the substrate, A is preferably -COO- or -CONH-, and more preferably -CONH-. R 5a The number of carbon atoms is preferably 2 or 3. R 6a , R 7a is preferably a methyl group. From the viewpoint of low damage to the substrate, B is preferably -SO 3 - Or -COO - and more preferably -COO - It is. r, B is -SO 3 - When B is -COO, it is preferably 0. - When , it is preferably 1. R 8a The number of carbon atoms is -SO 3 - When B is -COO, it is preferably 3. - When , it is preferably 1.

[0021] Specific examples of the betaine-type amphoteric surfactant include one or more selected from alkyl carboxy betaines, alkyl amido carboxy betaines, alkyl sulfo betaines, alkyl amido hydroxy sulfo betaines, and alkyl amino fatty acid salts. From the viewpoint of low substrate damage, preferred are alkyl amido propyl-N,N-dimethyl carboxy betaines, alkyl-N,N-dimethyl acetate betaines, N-alkyl-N,N-dimethyl-N-sulfopropyl ammonium sulfo betaines, alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl) ammonium sulfo betaines, alkanoyl amino propyl-N,N-dimethyl-N-sulfopropyl ammonium sulfo betaines, N-alkanoyl amino propyl-N,N-dimethyl-N-(2-hydroxysulfopropyl) ammonium sulfo betaines, and N-alkyl-N,N-dimethyl-N-carboxy methyl ammonium betaines, and more preferred are alkyl amido propyl-N,N-dimethyl carboxy betaines, and alkyl-N,N-dimethyl acetate betaines. These alkyl groups have 7 or more carbon atoms, preferably 8 or more, more preferably 10 or more carbon atoms, and 18 or less, preferably 16 or less, more preferably 14 or less carbon atoms.

[0022] <(b) Component> The component (b) is a bactericide. The component (b) is preferably one or more compounds selected from cationic surfactants and biguanide compounds. Examples of the cationic surfactant include quaternary ammonium salt surfactants. Examples of biguanide compounds include chlorhexidine digluconate (CHG), chlorhexidine diacetate, chlorhexidine dihydrochloride, chlorhexidine diphosphanilate, poly(hexamethylene biguanide) hydrochloride (PHMB), and chlorhexidine-2-acrylamido-2-methylpropanesulfonic acid copolymer.

[0023] The quaternary ammonium salt surfactant of the component (b) is preferably at least one selected from the group consisting of compounds represented by the following general formula (b1) and compounds represented by the following general formula (b2).

[0024] [ka]

[0025] [In the formula, R 1b and R 2b at least one selected from the group consisting of an alkyl group, an alkenyl group, or a hydroxyalkyl group having 8 to 18 carbon atoms, and the remainder each consisting of an alkyl group, a hydroxyalkyl group, or a polyoxyethylene group having 1 to 3 carbon atoms, or an average addition mole number of 10 or less; R 3b and R 4b are the same or different and each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having an average addition mole number of 10 or less, and X - is an anion.

[0026] [ka]

[0027] [In the formula, R 5b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, R 6b and R 7b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms; X - is an anion.

[0028] In the general formula (b1), when the quaternary ammonium salt is a mono-long chain alkyl type, R 1b is an alkyl group, an alkenyl group, or a hydroxyalkyl group having 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and even more preferably 14 or more, and 18 or less, preferably 16 or less; R 2b , R 3b and R 4b are the same or different and each is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group with an average added mole number of 10 or less. In the general formula (b1), when the quaternary ammonium salt is a di-long chain alkyl type, R 1b and R 2b are the same or different and each is an alkyl group, an alkenyl group, or a hydroxyalkyl group having 8 or more carbon atoms and 16 or less, preferably 14 or less, 3b and R 4b are the same or different and each is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group with an average added mole number of 10 or less.

[0029] In the general formula (b1), X - is an anion. Examples of anions include halogen ions, such as chloride, bromide, and iodide. - Examples of the anion include alkyl sulfate ions having 1 to 3 carbon atoms, such as methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion.

[0030] Preferred examples of the compound of general formula (b1) include one or more selected from N-alkyl-N,N,N-trimethylammonium salts in which the alkyl group has 12 or more and 18 or less carbon atoms, N,N-dialkyl-N,N-dimethyl-ammonium salts in which the alkyl group has 8 or more and 14 or less carbon atoms, and N-alkyl-N,N-dimethyl-N-ethylammonium salts in which the alkyl group has 12 or more and 16 or less carbon atoms.

[0031] In general formula (b2), R 5b R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms. 5b From the viewpoint of detergency, the number of carbon atoms in R is preferably 8 or more, and preferably 18 or less, more preferably 16 or less. 5b is preferably an alkyl group or an alkenyl group, and is preferably an alkyl group.

[0032] In general formula (b2), R 6b and R 7b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. 6b and R 7b are preferably each independently selected from alkyl groups having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0033] In the general formula (b2), X - is an anion. Examples of anions include halogen ions, such as chloride, bromide, and iodide. - Examples of the anion include alkyl sulfate ions having 1 to 3 carbon atoms, such as methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion.

[0034] Specific examples of the compound of general formula (b2) include N-dodecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tridecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-dimethyl-N-benzyl ammonium salt, N-pentadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-hexadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-dodecyl-N,N-diethyl-N-benzyl ammonium salt, N-tridecyl-N,N-diethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-diethyl-N-benzyl ammonium salt, and N-hexadecyl-N,N-diethyl-N-benzyl ammonium salt, N-dodecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, N-tridecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, N-tetradecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, N-pentadecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, and N-hexadecyl-N-methyl-N-ethyl-N-benzyl ammonium salt.

[0035] As the biguanide compound of the component (b), for example, a polybiguanide compound having a structural unit represented by the following general formula (b3) or a salt thereof can be used.

[0036] [ka]

[0037] The biguanide compound of the component (b) is preferably a polyalkylene biguanide compound represented by the following general formula (b3-1).

[0038] [ka]

[0039] [In the formula, R 8bis an alkylene group having 2 to 8 carbon atoms, preferably an alkylene group having 4 to 8 carbon atoms, and particularly a hexamethylene group; n is 2 to 14, preferably 10 to 14, more preferably 11 to 13, and most preferably 12; HY is an organic acid or an inorganic acid, preferably hydrochloric acid, gluconic acid, or acetic acid, and most preferably hydrochloric acid.

[0040] The biguanide compound of general formula (b3-1) may be commercially available, but can also be produced by known methods such as those described in British Patent No. 702268.

[0041] As the biguanide compound of component (b), in addition to the compounds of general formula (b3) and general formula (b3-1), bis-biguanide compounds can also be used. Specifically, 1,2-bis-(N 5 -p-Chlorophenyl-N 1 -biguanide)-ethane, 1,2-bis-(N 5 -p-Nitrophenyl-N 1 -biguanide)-ethane, 1,2-bis-(N 5 -p-Hydroxyphenyl-N 1 -biguanide)-ethane, 1,2-bis-(N 5 -p-Chlorobenzyl-N 1 -biguanide)-ethane, 1,2-bis-(N 5 -p-Bromophenyl-N 5 -Hexyl-N 1 -biguanide)-ethane, 1,2-bis-(N 5 -p-Chlorophenyl-N 5 -2-Ethylphenyl-N 1 -biguanide)-ethane, 1,2-bis-(N 5 -p-Chlorophenyl-N 5 -Ethyl-N 1 -biguanide)-ethane, 1,2-bis-(N 5 -p-Methoxyphenyl-N 1 -biguanide)-ethane, etc. can be used.

[0042] As the biguanide compound of component (b), in terms of bactericidal activity at low concentrations, R 8b is a hexamethylene group, and n is 10 or more and 14 or less, and more preferably 11 or more and 13 or less, and polyhexamethylene biguanide hydrochloride is most preferred.

[0043] <(c) component> Component (c) is a polymer having one or more groups selected from an amino group, a quaternary ammonium group, and a betaine group. Component (c) includes a polymer containing a structural unit derived from a monomer having one or more groups selected from an amino group, a quaternary ammonium group, and a betaine group.

[0044] The component (c) is preferably a polymer containing a structural unit A derived from one or more monomers A selected from a monomer (c1) represented by the following general formula (c1) and a monomer (c2) represented by the following general formula (c2):

[0045] [ka]

[0046] [In the formula, R 1c , R 2c , R 3c , R 7c , R 8c , R 9c are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. 1c , Y 1c each independently represents an alkylene group having 1 to 12 carbon atoms, -COOR 12c -,-CONHR 12c -,-OCOR 12c -, -R 13c -OCO-R 12c -, where R 12c , R 13c are each independently an alkylene group having 1 to 5 carbon atoms. 4c is an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, or R 1c R 2cC=C(R 3c )-X 1c -It is. 5c is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R 6c is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfate ester group, or a benzyl group; R 6c When is an alkyl group, a hydroxyalkyl group, or a benzyl group, Z - R indicates an anion. 6c If contains a carboxyl group, a sulfonic acid group, or a sulfate ester group, Z - does not exist, and R 6c These groups in the Z form anions. - Examples of the anion of R include a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, an aromatic sulfonate ion which may be substituted with an alkyl group having 1 to 3 carbon atoms, and a hydroxy ion. 10c is a hydrogen atom, an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, or R 7c R 8c C=C(R 9c )-Y 1c -It is. 11c is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group.

[0047] Specific preferred monomers (c1) include acryloyl (or methacryloyl) aminoalkyl (carbon number: 1 to 5)-N,N,N-trialkyl (carbon number: 1 to 3) quaternary ammonium salts, acryloyl (or methacryloyl) oxyalkyl (carbon number: 1 to 5)-N,N,N-trialkyl (carbon number: 1 to 3) quaternary ammonium salts, N-(ω-alkenyl (carbon number: 2 to 10))-N,N,N-trialkyl (carbon number: 1 to 3) quaternary ammonium salts, and N,N-di(ω-alkenyl (carbon number: 2 to 10))-N,N-dialkyl (carbon number: 1 to 3) quaternary ammonium salts, and particularly diallyldimethylammonium salt.

[0048] Specific preferred examples of the monomer (c2) include acryloyl (or methacryloyl) amino alkyl (carbon number 1 to 5)-N,N-dialkyl (carbon number 1 to 3) amines, acryloyl (or methacryloyl) oxy alkyl (carbon number 1 to 5)-N,N-dialkyl (carbon number 1 to 3) amines, N-(ω-alkenyl (carbon number 2 to 10))-N,N-dialkyl (carbon number 1 to 3) amines, N,N-di(ω-alkenyl (carbon number 2 to 10))-N-alkyl (carbon number 1 to 3) amines, allylamine, diallylmethylamine, and diallylamine, and particularly preferred are allylamine, diallylmethylamine, diallylamine, acryloyl (or methacryloyl) amino propyl-N,N-dimethylamine, and acryloyl (or methacryloyl) oxy ethyl-N,N-dimethylamine. When the component (c) contains the structural unit A, the structural unit A derived from the monomer A is contained in an amount of preferably 10 mol % or more, more preferably 20 mol % or more, even more preferably 30 mol % or more, and preferably 100 mol % or less, more preferably 99 mol % or less, even more preferably 90 mol % or less, based on all structural units of the component (c).

[0049] (c) Component is -SO 2 A polymer containing a structural unit B represented by the formula (I) is preferred. As a method for introducing such a structural unit B into a polymer, a predetermined amount of SO 2The polymerizable compound can be obtained by blowing a gas into a solution containing a monomer (c1) of general formula (c1) and / or a monomer (c2) of general formula (c2) and polymerizing the monomer using a polymerization initiator selected from benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, dilauroyl peroxide, azobisisobutyronitrile, azobisisovalernitrile, 2,2'-azobis(2-amidinopropane), t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, persulfates, and hydrogen peroxide. A solvent can be used during polymerization, specifically, water, alcohols selected from methanol, ethanol, and propanol, ketones selected from acetone and methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylimidazolidinone, acetonitrile, propionitrile, toluene, xylene, and hexane can be used. The polymerization temperature varies depending on the combination of the solvent and initiator, and is preferably from -20°C to 200°C, more preferably from -10°C to 100°C. In the present invention, polymerization can also be performed by light or radiation, and polymerization can be efficiently performed by irradiating light with a wavelength of 300 nm to 450 nm.

[0050] By including structural unit B, component (c) exhibits sufficient adhesion to hard surfaces even when the polymer concentration is low, and is also less susceptible to the effects of combined use with a cationic surfactant. When the component (c) contains structural units A and B, in the component (c), the molar ratio of the structural unit B derived from monomer B to the structural unit A derived from monomer A, (structural unit B) / (structural unit A), is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and preferably 1.0 or less, more preferably 0.75 or less, even more preferably 0.5 or less, and still more preferably 0.3 or less.

[0051] In the present invention, for the purpose of further improving the antifouling effect, it is preferable that the component (c) contains a structural unit C derived from a monomer selected from the following (i) to (iv):

[0052] (i) Acrylic acid or its salts, methacrylic acid or its salts, maleic acid or its salts, maleic anhydride, styrene sulfonate, 2-acrylamido-2-methylpropane sulfonate, allyl sulfonate, vinyl sulfonate, methallyl sulfonate, sulfopropyl methacrylate, mono-ω-methacryloyloxyalkyl phosphate (having 1 to 12 carbon atoms)

[0053] (ii) An amide group-containing compound selected from acrylamide, N,N-dimethylaminopropylacrylic (or methacrylic) amide, N,N-dimethylacrylic (or methacrylic) amide, N,N-dimethylaminoethylacrylic (or methacrylic) amide, N,N-dimethylaminomethylacrylic (or methacrylic) amide, N-vinyl-2-caprolactam, and N-vinyl-2-pyrrolidone.

[0054] (iii) An ester group-containing compound selected from alkyl acrylate (or methacrylate) (having 1 to 5 carbon atoms), 2-hydroxyethyl acrylate (or methacrylate), N,N-dimethylaminoalkyl acrylate (or methacrylate) (having 1 to 5 carbon atoms), and vinyl acetate.

[0055] (iv) Olefin compounds selected from ethylene, propylene, n-butylene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, and α-methylstyrene.

[0056] Among these, in particular from the viewpoint of the antifouling effect, the constituent units derived from the monomers (i) or (ii) are preferred, among which the constituent units derived from the monomers (i) are most preferred, and among these, acrylic acid or its sodium salt or potassium salt, methacrylic acid or its sodium salt or potassium salt, and maleic acid or its sodium salt or potassium salt are preferred. Here, the counter ion of the constituent unit derived from the monomer (i) may be the cationic group portion of the polymer contained therein.

[0057] When component (c) contains structural unit C, in the structural units constituting component (c), the molar ratio of structural unit C derived from monomer C to structural unit A derived from monomer A, (structural unit C) / (structural unit A), is, from the viewpoint of the antifouling effect, preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, and preferably 1.0 or less, more preferably 0.75 or less, even more preferably 0.5 or less.

[0058] In the component (c), the structural unit A, the structural unit B, and preferably the structural unit C may be present in either the main chain or the side chain of the polymer. These may be randomly polymerized, block polymerized, graft polymerized, or the like. In the present invention, it is preferable to use a polymer composed only of the structural unit A, the structural unit B, and the structural unit C.

[0059] Alternatively, the component (c) can be produced by reacting a compound having a cationic group with a semi-synthetic water-soluble polymer such as hydroxyethyl cellulose or soluble starch. From the viewpoints of availability and the antifouling effect due to sufficient adhesion to hard surfaces even when the polymer concentration is low, the component (c) is preferably a cationically modified polyvinyl alcohol produced by polymerizing vinyl acetate and the monomer A, or a cationically modified hydroxyethyl cellulose produced by reacting hydroxyethyl cellulose with a compound having a cationic group. An example of this cationic group is the cationic group possessed by the monomer A.

[0060] (cationic modified polyvinyl alcohol) The cation-modified polyvinyl alcohol is a polyvinyl alcohol having in its main chain or side chain a cationic group of the monomer A. The cation-modified polyvinyl alcohol is obtained by copolymerizing the raw material vinyl acetate with diallyldimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, or the like, and saponifying the resulting copolymer by a conventional method when polymerizing the raw material vinyl acetate. Alternatively, vinyl acetate may be copolymerized with another monomer having a reactive group, and after saponification, the reactive group may be used to react with a compound containing the cationic group to cationize the polyvinyl alcohol.

[0061] (cationically modified hydroxyethyl cellulose) Cationically modified hydroxyethyl cellulose can be obtained, for example, by reacting raw cellulose with ethylene oxide to obtain hydroxyethyl cellulose, and then reacting this hydroxyethyl cellulose with a cationizing agent to cationize it.

[0062] The cellulose that can be used as the raw material cellulose includes, in addition to chemically pure cellulose, various cellulose-containing raw materials, such as woods such as various wood chips; pulps such as wood pulp produced from wood; papers such as newspapers and cardboard; plant stems and leaves such as rice straw and corn stalks; and plant shells such as rice husks, palm shells, and coconut shells.

[0063] As the cationizing agent, from the viewpoint of availability, preferred are chlorides or bromides of glycidyl trimethylammonium or glycidyl triethylammonium, chlorides such as 3-chloro-2-hydroxypropyl trimethylammonium and 3-chloro-2-hydroxypropyl triethylammonium, bromides such as 3-bromo-2-hydroxypropyl trimethylammonium and 3-bromo-2-hydroxypropyl triethylammonium, more preferred are glycidyl trimethylammonium chloride or 3-chloro-2-hydroxypropyl trimethylammonium chloride, and even more preferred is 3-chloro-2-hydroxypropyl trimethylammonium chloride. These cationizing agents may be used alone or in combination of two or more.

[0064] From the viewpoint of antifouling properties, the degree of cationization of component (c) is preferably 0.25 mol% or more, more preferably 0.35 mol% or more, even more preferably 0.45 mol% or more, still more preferably 0.6 mol% or more, still more preferably 0.8 mol% or more, and from the viewpoint of antifouling properties, it is preferably 5 mol% or less, more preferably 4 mol% or less, even more preferably 3 mol% or less, and still more preferably 2 mol% or less. The degree of cationization can be determined by colloid titration using potassium polyvinyl sulfate (PVSK).

[0065] The component (c) may contain a constituent unit derived from a monomer having a betaine group. Examples of the monomer having a betaine structure include N-(3-sulfopropyl)-N-(meth)acryloyloxyethyl-N,N-dimethylammonium betaine, N-(3-sulfopropyl)-N-(meth)acryloylamidopropyl-N,N-dimethylammonium betaine, N-(3-carboxymethyl)-N-(meth)acryloylamidopropyl-N,N-dimethylammonium betaine, and N-carboxymethyl-N-(meth)acryloyloxyethyl-N,N-dimethylammonium betaine.

[0066] The component (c) is preferably a polymer having a structural unit D represented by the following general formula (c3), and more preferably (a) a copolymer containing a structural unit D represented by the following general formula (c3) and a structural unit E represented by the following general formula (c4).

[0067] [ka]

[0068] [During the ceremony, R 14c ~R 16c are the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R 17c : an alkylene group having 1 to 4 carbon atoms, or -Y 2c -OPO 3 - -Y 3c - Y 2c , Y 3c : the same or different, an alkylene group having 1 to 4 carbon atoms R 18c , R 19c : the same or different, a hydrocarbon group having 1 to 4 carbon atoms X 2c :O or NR 20c and R 20c is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X 3c : Hydrogen atom, hydrocarbon group having 1 to 4 carbon atoms, R 21c SO 3 - , or R 21c COO - Here, R 17c When is an alkylene group having 1 to 4 carbon atoms, X 3c is R 21c SO 3 - , or R 21c COO - , R 21c is an alkylene group having 1 to 4 carbon atoms, R 17c -Y 2c -OPO 3 - -Y3c -, X 3c is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0069] [ka]

[0070] [During the ceremony, R 22c ~R 24c are the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms X 4c : O or NH group R 25c : an alkylene group having 1 to 4 carbon atoms X 5c :N + R 26c R 27c R 28c X 6c or NR 29c R 30c and R 26c ~R 30c are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; X 6c is an anion Indicates the following.

[0071] [Structural unit D] In the general formula (c3), from the viewpoint of availability of the unsaturated monomer, polymerization property of the monomer, and enhancement of the antifouling performance of the component (c), R 14c and R 15c are each preferably a hydrogen atom. In general formula (c3), R 16c From the viewpoints of availability of the unsaturated monomer, polymerizability of the monomer, and enhancing the antifouling performance of the component (c), is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In the general formula (c3), X 2c is preferably O from the viewpoints of availability of the unsaturated monomer, polymerizability of the monomer, and enhancing the antifouling performance of the component (c). In general formula (c3), R 17cFrom the viewpoint of enhancing antifouling performance, is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and still more preferably an alkylene group having 2 carbon atoms. In the general formula (c3), Y 2c , Y 3c are each preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. In general formula (c3), R 18c , R 19c From the viewpoints of availability of the unsaturated monomer, polymerizability of the monomer, and enhancing the antifouling performance of component (c), each of the groups is preferably a methyl group or an ethyl group, and more preferably a methyl group. In the general formula (c3), X 3c is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R 21c SO 3 - , or R 21c COO - However, R 17c When is an alkylene group having 1 to 4 carbon atoms, X 3c is R 21c SO 3 - , or R 21c COO - and R 17c -Y 2c -OPO 3 - -Y 3c -, X 3c R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. 17c -Y 2c -OPO 3 - -Y 3c - In order to improve the antifouling performance, X 3c R is preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group. 17c When is an alkylene group having 1 to 4 carbon atoms, from the same viewpoint, X 3c is R 21c SO 3 - is preferred. Also, R 21cis preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms.

[0072] When component (c) contains structural unit D, the content of structural unit D in component (c) is, from the viewpoint of enhancing the antifouling performance of component (c), preferably 30 mol % or more, more preferably 50 mol % or more, even more preferably 70 mol % or more, still more preferably 80 mol % or more, and even more preferably 90 mol % or more, and from the same viewpoint, is preferably 99 mol % or less, more preferably 98 mol % or less, and even more preferably 95 mol % or less. Furthermore, when component (c) contains structural unit D, the content of structural unit D in component (c) is, from the viewpoint of enhancing the antifouling performance of component (c), preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and even more preferably 90% by mass or more, and from the same viewpoint, is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less.

[0073] [Structural unit E] In the general formula (c4), from the viewpoint of availability of the unsaturated monomer, polymerization property of the monomer, and enhancement of the antifouling performance of the component (c), R 22c and R 23c are each preferably a hydrogen atom. In general formula (c4), R 24c From the viewpoint of the polymerizability of the monomer and of enhancing the antifouling performance of the component (c), is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In the general formula (c4), X 4c is preferably O from the viewpoint of the polymerizability of the monomer and from the viewpoint of enhancing the antifouling performance of the component (c). In general formula (c4), R 25c From the viewpoint of the polymerizability of the monomer and of enhancing the antifouling performance of the component (c), is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. In the general formula (c4), X 5cFrom the viewpoint of enhancing the antifouling performance of the (c) component and from the viewpoint of easiness of the quaternization reaction, + R 26c R 27c R 28c X 6c or NR 29c R 30c and N + R 26c R 27c R 28c X 6c is preferred, R 26c , R 27c , R 28c From the same viewpoint, each of and is preferably a methyl group or an ethyl group, respectively. In general formula (c4), R 29c , R 30c From the viewpoint of enhancing the antifouling performance of the component (c) and of the ease of the quaternization reaction, is preferably a methyl group or an ethyl group, and more preferably a methyl group. In the general formula (c4), X 6c is an anion, a halogen ion or C 2 H 5 SO 4 - is preferred, and C 2 H 5 SO 4 - is more preferred.

[0074] When component (c) contains the structural unit E, the content of structural unit E in component (c) is, from the viewpoint of enhancing antifouling performance, preferably at least 1 mol %, more preferably at least 2 mol %, and even more preferably at least 5 mol %, and from the same viewpoint, is preferably at most 70 mol %, more preferably at most 50 mol %, even more preferably at most 30 mol %, even more preferably at most 20 mol %, and even more preferably at most 10 mol %.

[0075] Furthermore, when the component (c) contains the structural unit E, the content of the structural unit E in the component (c) is, from the viewpoint of enhancing the antifouling performance, preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 5 mass% or more, and from the viewpoint of enhancing the antifouling performance of the component (c), preferably 70 mass% or less, more preferably 50 mass% or less, even more preferably 30 mass% or less, still more preferably 20 mass% or less, and even more preferably 10 mass% or less.

[0076] [Molar ratio of structural unit D to structural unit E] When component (c) contains structural units D and E, the molar ratio of structural units D to E in component (c), structural unit D / structural unit E, is, from the viewpoint of antifouling performance, preferably 30 / 70 or more, more preferably 50 / 50 or more, even more preferably 55 / 45 or more, even more preferably 60 / 40 or more, still more preferably 75 / 25 or more, and even more preferably 90 / 10 or more; and, from the viewpoint of enhancing the antifouling performance of component (c), it is preferably 99.9 / 0.1 or less, more preferably 98 / 2 or less, and even more preferably 96 / 4 or less.

[0077] [Constituent units other than constituent units D and E] The component (c) may contain a structural unit other than the structural unit D and the structural unit E, provided that the effects of the present invention are not impaired. As the structural unit other than the structural unit D and the structural unit E, a structural unit derived from an unsaturated monomer other than an unsaturated monomer having a sulfobetaine group is preferred, and a structural unit derived from a hydrophobic unsaturated monomer such as styrene is more preferred.

[0078] From the viewpoint of antifouling properties, the content of structural units other than the structural units D and E in the component (c) is preferably 10 mol% or less, more preferably 5 mol% or less, more preferably 1 mol% or less, even more preferably 0.5 mol% or less, and even more preferably 0.1 mol% or less. The content of structural units other than the structural units D and E in the component (c) may be 0 mol%. From the viewpoint of antifouling properties, the content of structural units other than the structural units D and E in the component (c) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. The content of structural units other than the structural units D and E in the component (c) may be 0% by mass.

[0079] When the component (c) contains the structural unit D and the structural unit E, the total content of the structural unit D and the structural unit E in the component (c) is preferably 90 mol% or more, more preferably 95 mol% or more, even more preferably 99 mol% or more, still more preferably 99.5 mol% or more, and even more preferably 99.9 mol% or more, from the viewpoint of antifouling properties. The total content of the structural unit D and the structural unit E in the component (a) may be 100 mol%. From the viewpoint of antifouling properties, the total content of the structural units D and E in the component (c) is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, still more preferably 99.5% by mass or more, and even more preferably 99.9% by mass or more. The total content of the structural units D and E in the component (c) may be 100% by mass.

[0080] The component (c) having a betaine group may be produced by any method, specifically, the following methods (i) and (ii) are mentioned. From the viewpoint of availability of raw materials and ease of production, method (ii) is preferred. (i) A method of copolymerizing an unsaturated monomer having a betaine group and a cationic group (ii) A method in which an unsaturated monomer having an amino group and a cationic group is copolymerized, followed by quaternization with a betaining agent.

[0081] In component (c), from the viewpoint of an antifouling effect due to sufficient adhesion to hard surfaces even when the polymer concentration is low, the total amount of structural units derived from monomers having a group selected from an amino group, a quaternary ammonium group, and a betaine group, relative to all structural units, is preferably 10 mol % or more, more preferably 30 mol % or more, even more preferably 50 mol % or more, and preferably 100 mol % or less, more preferably 95 mol % or less, even more preferably 90 mol % or less.

[0082] From the viewpoint of soil resistance, the weight average molecular weight of component (c) is preferably 1,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and even more preferably 30,000 or more, and from the viewpoint of soil resistance and blending suitability, it is preferably 200,000 or less, more preferably 150,000 or less, even more preferably 100,000 or less, and even more preferably 80,000 or less. The weight average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions.

[0083] *GPC conditions Equipment: GPC (gel permeation chromatography) manufactured by Tosoh Corporation Column: TSKgel α-M (two columns connected in series) (Tosoh Corporation) Eluent: 0.15molNa 2 SO 4 / 1%CH 3 COOH / water Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2mg / mL Standard material: Pullulan standard product

[0084] <Composition, other ingredients, etc.> The hard surface cleaning composition of the present invention contains component (a) in an amount of preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.4% by mass or more from the viewpoint of both cleaning properties and finish, and preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less from the viewpoint of finish. By containing component (a) in the above range, the hard surface cleaning composition of the present invention can not only maintain a sustained antifouling effect and a glossy surface on the hard surface, but also suppress the occurrence of wiping streaks, thereby further improving the finish of the hard surface.

[0085] The hard surface cleaning composition of the present invention contains the component (b) in an amount of preferably 0.005% by mass or more, more preferably 0.007% by mass or more, and even more preferably 0.01% by mass or more from the viewpoint of disinfecting property, and in an amount of preferably 2% by mass or less, more preferably 1% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less from the viewpoint of soil resistance and finish.

[0086] The cleaning composition for hard surfaces of the present invention contains the component (c) in an amount of preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more from the viewpoint of the efficiency of the hard surface modifying effect, and in an amount of preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less from the viewpoint of the finish quality.

[0087] In the cleaning composition for hard surfaces of the present invention, the total content of the components (b) and (c) is, from the viewpoint of the hard surface modification effect and finish quality, preferably 0.01 mass % or more, more preferably 0.02 mass % or more, even more preferably 0.05 mass % or more, and preferably 5 mass % or less, more preferably 4 mass % or less, even more preferably 3 mass % or less.

[0088] In the cleaning agent composition for hard surfaces of the present invention, the mass ratio (c) / (b) of the content of component (c) to the content of component (b) is more than 1, preferably 2 or more, more preferably 3 or more, and preferably 25 or less, more preferably 20 or less, still more preferably 10 or less, from the viewpoint of achieving both the surface modification effect and the bactericidal property of the hard surface.

[0089] The cleaning agent composition for hard surfaces of the present invention contains water. Water can be used as the balance other than component (a), component (b), component (c), and the following optional components. From the viewpoints of the stability and cost of the cleaning agent composition for hard surfaces, the water content in the cleaning agent composition for hard surfaces of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and preferably 97% by mass or less, more preferably 95% by mass or less. It is preferable to use ion-exchanged water, sterilized ion-exchanged water, or the like as the water. The cleaning agent composition for hard surfaces of the present invention may be a liquid cleaning agent composition for hard surfaces.

[0090] The cleaning agent composition for hard surfaces of the present invention preferably has a pH at 25°C of 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 10 or less, more preferably 9 or less, still more preferably 8 or less. As the pH adjuster, acid agents such as inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as lactic acid, citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, etc., and alkali agents such as sodium hydroxide, potassium hydroxide, ammonia and its derivatives, amine salts such as monoethanolamine, diethanolamine, triethanolamine, etc., and sodium carbonate, potassium carbonate, etc. may be used alone or in combination. Further, these acid agents and alkali agents may be combined and used as a buffer system. The pH at 25°C of the cleaning agent composition for hard surfaces is measured by the following method.

[0091] <Method for Measuring pH> A composite electrode for pH measurement (GST-5841C, manufactured by DKK TOA) is connected to a pH meter (pH / ion meter HM-42X, manufactured by DKK TOA) and the power is turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) is used as the internal solution of the pH electrode. Next, a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution) are filled in 100 mL beakers, and immersed in a thermostatic bath at 25°C for 30 minutes. The pH measurement electrode is immersed in the thermostatically adjusted standard solution for 3 minutes, and a calibration operation is performed in the order of pH 6.86 → pH 4.01 → pH 9.18. The hard surface cleaning composition of the present invention to be measured is adjusted to 25°C, and the electrode of the pH meter is immersed in the hard surface cleaning composition of the present invention, and the pH is measured after 1 minute.

[0092] <Surfactant> The cleaning composition for hard surfaces of the present invention may contain a surfactant other than the components (a) and (b) from the viewpoint of improving cleaning properties and foaming properties. The surfactant other than the components (a) and (b) may be one or more surfactants selected from the group consisting of (d) a nonionic surfactant (hereinafter referred to as the component (d)) and (e) anionic surfactant (hereinafter referred to as the component (e)). From the viewpoint of blend stability, the cleaning composition for hard surfaces of the present invention preferably contains component (d).

[0093] <(d) component> The component (d) is a nonionic surfactant. From the viewpoint of cleaning power and foaming power, the component (d) is preferably at least one selected from the group consisting of (d1) monoalkyl glyceryl ether (hereinafter referred to as the component (d1)), (d2) polyoxyalkylene monoalkyl or alkenyl ether (hereinafter referred to as the component (d2)), (d3) alkyl polyglycoside (glycoside-type nonionic surfactant) (hereinafter referred to as the component (d3)), (d4) sorbitan-based nonionic surfactant (hereinafter referred to as the component (d4)), (d5) aliphatic alkanolamide (hereinafter referred to as the component (d5)), (d6) fatty acid monoglyceride (hereinafter referred to as the component (d6)), and (d7) sucrose fatty acid ester (hereinafter referred to as the component (d7)). Two or more of these may be used. From the viewpoints of cleaning properties and blending stability, the component (d) is preferably a nonionic surfactant in which the hydrophilic group has a sugar skeleton or a glycerin skeleton, and examples thereof include one or more types selected from the group consisting of components (d1), (d3), (d6), and (d7).

[0094] The component (d1) is a monoalkyl glyceryl ether. Specifically, the component (d1) is preferably a compound represented by the following general formula (d1). R 1d -O-(Gly) r -H (d1) [In the formula, R 1d represents an alkyl group having 6 to 18 carbon atoms, Gly represents a structural unit derived from glycerin, preferably a residue obtained by removing one hydroxyl group and one hydrogen atom from glycerin, and r represents a number of 1 to 4.

[0095] In general formula (d1), R 1d From the viewpoint of detergency, R is an alkyl group having 6 or more carbon atoms, preferably 7 or more carbon atoms, more preferably 8 or more carbon atoms, and 18 or less carbon atoms, preferably 12 or less carbon atoms, more preferably 10 or less carbon atoms. Although linear alkyl groups such as hexyl, heptyl, octyl, nonyl, and decyl groups can be used, from the viewpoint of detergency in the present invention, branched alkyl groups are preferred. 1dSpecific examples of the branched alkyl group include groups selected from the group consisting of 2-ethylhexyl, sec-octyl, isononyl and isodecyl, more preferably 2-ethylhexyl or isodecyl, and particularly preferably 2-ethylhexyl.

[0096] In the general formula (d1), r is preferably 1 or more and preferably 2 or less. Compounds in which r is 1 are more preferred. Particularly preferred compounds are those in which R 1d is a 2-ethylhexyl group and r is 1. The structure represented by Gly is a -CH 2 CH(OH)CH 2 - or -CH(CH 2 OH)CH 2 -, which varies depending on the catalyst and reaction conditions.

[0097] To obtain the compound of the general formula (d1), for example, R 1d Using an alkyl alcohol represented by -OH, an epoxy compound such as epihalohydrin or glycidol is reacted with BF 3 For example, when 2-ethylhexanol is used, the resulting 2-ethylhexyl monoglyceryl ether is a mixture that may contain a plurality of products, as described in JP-A-2001-49291.

[0098] The component (d2) is a polyoxyalkylene monoalkyl or alkenyl ether. In the nonionic surfactant of component (d2), the number of carbon atoms in the alkyl or alkenyl group is, from the viewpoint of detergency, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and still more preferably 12 or more, and from the same viewpoint, preferably 22 or less, more preferably 18 or less, even more preferably 16 or less, and still more preferably 14 or less.

[0099] In the nonionic surfactant of component (d2), the average number of moles of oxyalkylene groups added is preferably more than 0, more preferably 1 or more, and even more preferably 3 or more, from the viewpoint of detergency, and from the same viewpoint, is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less. From the viewpoint of detergency, the oxyalkylene group is preferably one or more selected from an oxyethylene group, an oxypropylene group, and an oxybutylene group, and more preferably one or more selected from an oxyethylene group and an oxypropylene group.

[0100] The component (d2) can be one or more compounds selected from the compounds represented by the following general formula (d2). R 2d O[(C 2 H 4 O) l / (C 3 H 6 O) j ]H (d2) [In the formula, R 2d represents a hydrocarbon group having 6 to 22 carbon atoms. l and j represent the average number of moles added, l represents a number from 0 to 30, j represents a number from 0 to 30, and l and j cannot be 0 at the same time. " / " represents that the oxyethylene groups and oxypropylene groups may be added randomly or in blocks, regardless of the order.

[0101] R in the above general formula (d2) 2d From the viewpoint of detergency, the number of carbon atoms is preferably 8 or more, more preferably 10 or more, and even more preferably 12 or more, and from the same viewpoint, it is preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less. R 2d From the viewpoint of detergency, R is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and further preferably a secondary alkyl group. Here, the secondary alkyl group is R 2d R that binds to O in O 2dThis refers to an alkyl group in which the carbon atom is a secondary carbon atom. Specific examples of the alkyl group include various octyl groups (including 2-ethylhexyl groups), various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups (lauryl groups), various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, and various octadecyl groups. Examples of alkenyl groups include various octanyl groups, various nonanyl groups, various decanyl groups, various undecanyl groups, various dodecanyl groups, various tridecanyl groups, various tetradecanyl groups, various pentadecanyl groups, various hexadecanyl groups, various heptadecanyl groups, and various octadecanyl groups (e.g., oleyl and linoleyl groups). Note that "various" refers to various isomers including n-, sec-, tert-, and iso-.

[0102] In the above general formula (d2), l and j are each independently preferably 1 or more, more preferably 2 or more, from the viewpoint of storage stability, and from the same viewpoint, are each preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less.

[0103] The component (d3) is an alkyl polyglycoside (glycoside-type nonionic surfactant). The nonionic surfactant of the component (d3) is preferably a nonionic surfactant represented by the following general formula (d3). R 3d (OR 4d ) s G t (d3) [In the formula, R 3d represents a linear or branched alkyl group, alkenyl group, or alkylphenyl group having 8 to 18 carbon atoms, preferably 12 to 14 carbon atoms, and more preferably an alkyl group; R 4d represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms, s represents the average number of moles added and is a number of 0 to 5, and t represents a number whose average value is 1 to 5.

[0104] In general formula (d3), R3d From the viewpoint of detergency, preferably represents a linear or branched alkyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 14 or less, carbon atoms. In general formula (d3), from the viewpoint of storage stability, s is preferably 0 or more and preferably 2 or less, more preferably 0. From the viewpoint of storage stability, t is preferably 1.1 or more and preferably 1.5 or less, more preferably 1.4 or less. Here, t is a value measured by proton NMR method. In the general formula (d3), G may be a residue derived from one or more monosaccharides selected from glucose and fructose in terms of availability and cost. G may also be a residue derived from one or more polysaccharides selected from maltose and sucrose. G is preferably a residue derived from a monosaccharide of glucose.

[0105] (d4) Sorbitan-based nonionic surfactants, (d5) aliphatic alkanolamides, (d6) fatty acid monoglycerides, and (d7) sucrose fatty acid esters preferably have a linear or branched alkyl group having 8 to 18 carbon atoms, more preferably 12 to 14 carbon atoms.

[0106] From the viewpoint of improving detergency, the hard surface cleaning composition of the present invention may contain component (d) in an amount of preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less.

[0107] <(e) component> The component (e) is an anionic surfactant. Examples of the component (e) include an anionic surfactant having a sulfate ester group, a phosphate ester group, a phosphonic acid group, a sulfonic acid group, or a carboxy group. From the viewpoint of detergency, the hydrocarbon group of the anionic surfactant is preferably a straight-chain or branched alkyl group, alkylene group, or aryl group having a carbon number of preferably 5 or more, more preferably 6 or more, even more preferably 7 or more, still more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, and preferably 21 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less.

[0108] The component (e) is preferably one or more anionic surfactants selected from the group consisting of: (e1) a sulfosuccinate ester or a salt thereof having a hydrocarbon group having from 5 to 18 carbon atoms (hereinafter referred to as component (e1)); (e2) anionic surfactants having a hydrocarbon group having from 8 to 21 carbon atoms and a sulfate ester group or a sulfonic acid group (excluding component (e1)) (hereinafter referred to as component (e2)); (e3) anionic surfactants having a hydrocarbon group having from 8 to 21 carbon atoms and a carboxy group (hereinafter referred to as component (e3)); and (e4) anionic surfactants having a hydrocarbon group having from 8 to 21 carbon atoms and a phosphate ester group (hereinafter referred to as component (e4)).

[0109] The hard surface cleaning composition of the present invention may contain, as component (e), one or more selected from the group consisting of components (e1) to (e4) from the viewpoints of cleaning power and foaming power. However, it is preferable that the composition does not substantially contain component (e) since there is a risk of impairing blend stability and antifouling properties.

[0110] From the viewpoints of blend stability and antifouling properties, the hard surface cleaning composition of the present invention preferably contains 1 mass % or less of component (e), more preferably 0.2 mass % or less, even more preferably 0.1 mass % or less, and may contain, for example, more than 0 mass %, but it is desirable for the composition to contain substantially no component (e). From the viewpoints of blend stability and antifouling properties, the content of component (e) in the hard surface cleaning composition of the present invention is preferably as low as possible, and may be 0 mass %.

[0111] When the cleaning composition for hard surfaces of the present invention contains the component (e), the mass ratio (e) / (c) of the content of the component (e) to the content of the component (c) in the cleaning composition for hard surfaces of the present invention is, from the viewpoint of the hard surface modification effect, preferably 1 or less, more preferably 0.1 or less, even more preferably 0.01, and may be, for example, more than 0 and may be substantially 0. In terms of the hard surface modifying effect of the cleaning composition for hard surfaces of the present invention, the smaller the mass ratio (e) / (c) is, the more preferable, and it may be zero.

[0112] The hard surface cleaning composition used in the present invention may optionally contain added ingredients such as chelating agents; lower alcohols such as ethyl alcohol and isopropyl alcohol, solvents such as diethylene glycol monobutyl ether, solubilizers such as toluenesulfonate, xylenesulfonate, urea, etc.; clay minerals, viscosity modifiers; water-insoluble abrasives such as calcite, silica, calcium phosphate, zeolite, calcium carbonate, polyethylene, nylon, polystyrene, etc.; moisturizers such as glycerin, sorbitol, etc.; feel improvers; alkali builders such as sodium carbonate and sodium silicate, etc.; corrosion inhibitors such as sodium sulfite, etc.; enzymes, colorants, fragrances, preservatives and antifungal agents, etc., within the scope of not impairing the object of the present invention.

[0113] In the present invention, as a method for contacting the hard surface cleaning composition of the present invention with a hard surface, a trigger-type spray container capable of applying the contents in a foam form can be used, and a trigger-type spray container equipped with a mechanism for forming foam (foam-forming mechanism) is preferred. The present invention provides an article for cleaning hard surfaces in a trigger-type spray container, which is obtained by filling the hard surface cleaning agent composition of the present invention in a trigger-type spray container equipped with a foam-forming mechanism.

[0114] In addition, in the present invention, when a trigger-type sprayer equipped with a foaming mechanism is used, a foaming discharge container is suitable, which is equipped with a foaming cylinder attached to a discharge nozzle, and the liquid content discharged from the nozzle hole by the discharge operation of the dispenser is collided with the inner wall surface of the foaming cylinder and discharged in a foamed state. For the detailed structure, the one described in JP-A-2007-167719 can be referred to. Here, by adjusting the amount of air entering from the air introduction hole constituting the foaming cylinder, the amount of air mixed with the surfactant can be adjusted, and the specific foam volume at the time of foam application can be adjusted. That is, by increasing the amount of air introduced into the liquid hard surface cleaning composition, a foam with a large specific foam volume can be obtained.

[0115] When using a trigger-type spray equipped with a foam-forming mechanism, the spray container of the present invention sprays, in one operation, preferably 0.4 mL or more, more preferably 0.6 mL or more, and preferably 10 mL or less, more preferably 5 mL or less, even more preferably 3 mL or less, and even more preferably 1.5 mL or less of the composition. That is, the spray-contained hard surface cleaning article of the present invention sprays, in one operation, preferably 0.4 g or more, more preferably 0.6 g or more, and preferably 10 g or less, more preferably 5 g or less, even more preferably 3 g or less, and even more preferably 1.5 g or less of the composition.

[0116] The trigger-type spray container may be a commonly used container. For example, it may be obtained from polyethylene, polypropylene, or polyethylene terephthalate as a raw material, and may be manufactured by blow molding or the like. The thickness of the container may differ between the bottom and side surfaces, and is preferably 0.01 to 2 mm, and the container capacity is preferably 100 to 1000 mL. The amount of the hard surface cleaner composition filled in the container is preferably 200 to 500 mL for ease of handling. The liquid is filled while leaving a reasonable space.

[0117] <How to clean hard surfaces> The present invention provides a method for cleaning a hard surface, which comprises contacting the hard surface with the cleaning composition for hard surfaces of the present invention. The method for cleaning a hard surface of the present invention may be a method for cleaning a hard surface in which the detergent composition for hard surfaces of the present invention is brought into contact with the hard surface to impart a long-lasting shine to the hard surface. The method for cleaning a hard surface of the present invention may be a method for cleaning a hard surface in which the detergent composition for hard surfaces of the present invention is brought into contact with the hard surface in a foam state. Furthermore, the method for cleaning a hard surface of the present invention may be a method for cleaning a hard surface, which comprises contacting the hard surface with the cleaning agent composition for hard surfaces of the present invention and wiping off the contacted composition.

[0118] In the method for cleaning a hard surface of the present invention, after contacting the hard surface with the cleaning composition for hard surfaces of the present invention, one or more steps selected from scrubbing the hard surface with a cleaning tool such as a sponge or a scrubbing brush, rinsing the hard surface that has been brought into contact with the hard surface with water, and wiping off the cleaning composition for hard surfaces that has been brought into contact with the hard surface may be carried out. Examples of wiping products for wiping hard surfaces include cloth, paper, sponges, etc. The cloth may be woven or nonwoven. The wiping product may be impregnated with the hard surface cleaning composition of the present invention in advance, and the wiping product impregnated with the composition may be brought into contact with the hard surface, thereby allowing the hard surface to come into contact with the hard surface.

[0119] The hard surface is not particularly limited, and examples thereof include glass, pottery, porcelain, enamel, tile, ceramics; metals such as aluminum, stainless steel, brass, etc.; and synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP, etc. The hard surface to which the cleaning composition for hard surfaces and the cleaning method for hard surfaces of the present invention can be applied is preferably a hydrophilic hard surface. Here, the term "hydrophilic" as used herein refers to a surface having a static contact angle with water of less than 70°. The hard surface suitable for the present invention may be one or more hard surfaces selected from glass, pottery, porcelain, plastic, stainless steel, and silicon wafers. The subject of the present invention is hard surfaces, and in particular articles having hard surfaces, such as toilets, bathtubs, kitchen sinks, window panes, mirrors, faucets, and the like. The hard surface cleaning composition of the present invention may be for use on the hard surfaces of articles installed in one or more selected from a kitchen, a toilet, a bathroom, and a living room, and is preferably for use on the hard surfaces of articles installed in one or more selected from a kitchen, a toilet, and a bathroom. The hard surface cleaning composition of the present invention is preferably used for cleaning stainless steel articles, such as kitchen sinks, from the viewpoint of being able to impart gloss.

[0120] The method for cleaning a hard surface of the present invention can be carried out by contacting the hard surface with the foam of the cleaning composition for hard surfaces of the present invention discharged by the above-mentioned article. In the present invention, from the viewpoint of antifouling efficiency, the foam specific volume is preferably 5 mL / g or more, more preferably 10 mL / g or more, and from the viewpoints of economy and usability (ease of defoaming), it is preferable to bring foam of preferably 50 mL / g or less, more preferably 40 mL / g or less, even more preferably 30 mL / g or less, and even more preferably 20 mL / g or less into contact with a hard surface. A method of discharging the foam onto the hard surface by spraying or the like and then drying is preferred. If necessary, after discharging, the foam may be rinsed with water. After discharging, the hard surface cleaning composition may be wiped off using a wiping item such as cloth, paper, or sponge. The amount of foam that is brought into contact with the hard surface is, for example, 10 cm 2 The amount is preferably 0.001 mL or more and 1 mL or less, and more preferably 0.001 mL or more and 0.1 mL or less.

[0121] The temperature when cleaning a hard surface is preferably 5°C or higher, more preferably 10°C or higher, and even more preferably 15°C or higher, from the viewpoint of enhancing antifouling performance and ease of the treatment method, and is preferably 50°C or lower, more preferably 40°C or lower, and even more preferably 30°C or lower. Moreover, it is preferable that the hard surface cleaned by the method for cleaning a hard surface of the present invention is treated uniformly from the viewpoint of enhancing antifouling performance, etc. The uniformity of the surface treatment can be judged by visually observing the hard surface after the treatment. EXAMPLES

[0122] Polymer A and polymer B of the component (c) were synthesized by the method described in Production Example 1 or 2 below. <Production Example 1> Polymer A was produced by combining and synthesizing components in a prescribed molar ratio with reference to JP-A-6-212597 and JP-B-53-10539.

[0123] <Production Example 2> Polymer B was synthesized by the methods described in steps 1 and 2 below. (Process 1) 126.30 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 1000 mL four-neck flask, and the temperature was raised to 78° C. and refluxed. A solution containing 181.12 g of 2-(dimethylamino)ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 23.60 g of 2-(dimethylamino)ethyl methacrylate diethyl sulfate (manufactured by Kao Corporation / 90% aqueous solution), and 53.20 g of ethanol, and a solution containing 5.83 g of 2,2'-azobis(2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) and 10.00 g of ethanol were each added dropwise over 2 hours. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.

[0124] (Process 2) In a 1000 mL four-neck flask, 94.70 g of the obtained polymer solution, 3.15 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and 150.00 g of water were added and heated to 50° C. 38.70 g of 1,3-propane sultone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour to carry out a reaction. After aging for 3 hours, the mixture was heated under reduced pressure at 90° C. / 20 kPa for 2 hours to distill off ethanol, and an aqueous solution containing polymer B was obtained.

[0125] In polymer B, structural unit D had the following structure in formula (c3), structural unit E had the following structure in formula (c4), and the molar ratio of structural unit D / structural unit E was 95 / 5. Structural unit D:R 14c =R 15c =H, R 16c =CH 3 , R 17c =C 2 H 4 , R 18c =R 19c =CH 3 , X 2c =O, X 3c =R 21c SO 3 - , R 21c =C 3 H 6 Unit E:R 22c =R 23c =H, R 24c =CH 3 , X 4c =O, R 25c =C 2 H 4 , X 5c =N + R 26c R 27c R 28c X 6c , R 26c =R 27c =CH 3 , R 28c =C 2 H 5 , X 6c =C 2 H 5 SO 4 - Polymer B had a weight average molecular weight of 63,000.

[0126] The weight average molecular weight of Polymer B was measured by gel permeation chromatography (GPC) under the following conditions. Column: Two TSKgel α-M columns (manufactured by Tosoh Corporation) were used, connected in series. Column temperature: 40℃ Eluent: 0.15molNa 2 SO4 / 1%CH 3 COOH / water Flow rate: 1.0ml / min Detector: Differential refractometer Standard material: Pullulan standard product

[0127] The weight average molecular weight of polymer B was measured by SLS (static light scattering). That is, the weight average molecular weight was calculated by measuring static light scattering under the following conditions using a light scattering photometer "DLS-7000" (manufactured by Otsuka Electronics Co., Ltd.) and preparing a Zimm-plot. The refractive index increment required for calculating the molecular weight was measured using a differential refractometer "DRM3000" (manufactured by Otsuka Electronics Co., Ltd.). Wavelength: 632.8 nm (helium-neon laser) Scattering angle: Measured from 30° to 150° at 10° intervals. Temperature: 25℃ Solvent: Trifluoroethanol

[0128] <Example 1> Using each component in Table 1, a cleaning composition for hard surfaces shown in Table 1 was prepared and evaluated for the following items. The results are shown in Table 1. Note that the mass % of the blended components in Table 1 are all values ​​based on the active component.

[0129] <Component (a)> Lauryl dimethylamine oxide Lauryl amidopropyl dimethylamine oxide <(b) Component> Benzalkonium chloride (mixture of alkyl groups with 8 to 16 carbon atoms) <(c) component> Polymer A: Diallyldimethylammonium chloride / maleic acid / SO 2 =70:25:5 (molar ratio), copolymer with weight average molecular weight of 30,000 Polymer B: the copolymer obtained in Production Example 2 <(d) component> Alkyl polyglycoside: Alkyl (12-16 carbon atoms) polyglucose (average sugar condensation degree 1-2), product name "AG124", manufactured by Kao Corporation 2-Ethylhexyl glyceryl ether <Other ingredients> Sodium sulfite: manufactured by Shinshu Chemical Co., Ltd. ·Fragrance ·Pigment

[0130] <Method for evaluating sterilization performance> E. coli (NBRC3972) was cultured on SCDLP agar medium (Difco) for one day, and then cultured in SCDLP liquid medium for one day with shaking. After that, it was suspended in physiological saline and incubated for 10 8 ~10 9 The bacterial concentration was adjusted to CFU / mL, and the test bacterial solution was prepared by mixing an equal amount of this with a 3% BSA aqueous solution. 100 μL of the hard surface cleaning composition of Examples 1 to 7 in Table 1 was inoculated with 10 μL of the test bacteria solution and allowed to come into contact with the composition at 25° C. for 5 minutes, after which 10 mL of SCDLP liquid medium was added to inactivate the bacteria. An appropriate amount of SCDLP agar medium was poured into 1 mL of this inactivation solution and allowed to solidify, after which the number of bacteria was counted after 24 hours of incubation at 37° C. This number of bacteria was taken as the “viable bacteria count in the test solution.” In addition, the same procedure was carried out using ion-exchanged water instead of the hard surface cleaner compositions of Examples 1-7 in Table 1 (10 μL of test bacteria solution was inoculated into 100 μL of water, and after contact for 5 minutes, 10 mL of SCDLP liquid medium was added to inactivate), and the result was counted as the "viable bacteria count in blank (water)" and the disinfecting activity value was calculated from the following formula (1). A higher disinfecting activity value means better disinfecting performance. Sterilization activity value = Log (number of viable bacteria in blank (water)) - Log (number of viable bacteria in test liquid) (1) The disinfecting activity values ​​of Examples 1-7 were greater than 2, and thus the compositions had sufficient disinfecting performance. Moreover, the hard surface cleaner compositions of Examples 1-1 to 1-6 contain the same or more components (b) as the hard surface cleaner of Example 1-7, and have the same or more sterilizing performance as that of Example 1-7.

[0131] <Cleanability of oil stains> 10 mg of cooking oil was applied to one side of a stainless steel substrate (manufactured by Engineering Test Services, 10 cm x 10 cm x 1 mm, alkaline-cleaned). The mass of the stainless steel substrate was measured before and after the oil was applied, and the "initial oil mass" was calculated based on the increase in mass of the stainless steel substrate before and after the oil was applied. Using a commercially available trigger-type sprayer (Kao Corporation's Bus Magiclean Air Jet Trigger (Lot. W0262011)), 2 The hard surface cleaning composition in Table 1 was sprayed onto the oil on the SUS substrate with a single discharge amount (about 1 mL) per spray, and immediately afterwards, a kitchen paper was pressed lightly against the SUS substrate and moved back and forth across the SUS substrate 15 times to wipe off the hard surface cleaning composition on the SUS substrate. The "mass of oil remaining on the substrate" was calculated based on the difference between the mass of the SUS substrate before the oil was applied and the mass of the SUS substrate after the hard surface cleaning composition was wiped off. The oil stain removal rate was calculated from the following formula (2) to evaluate the cleaning ability of the hard surface cleaning composition against oil stains. The higher the oil stain removal rate, the better the cleaning ability of the hard surface cleaning composition against oil stains. Oil stain removal rate (%) = [1-(mass of oil remaining on the board) / (initial mass of oil)] x 100 (2)

[0132] <Hard surface gloss (water film retention)> 2 mL of the above hard surface cleaning composition was applied to a SUS substrate (manufactured by Engineering Test Services, 10 cm x 10 cm x 1 mm, alkaline-cleaned), lightly spread with a sponge and left for 1 minute, thereby coating the entire surface of one side of the SUS substrate with the composition. Next, the SUS substrate was held with the surface coated with the hard surface cleaning composition vertical, and the SUS substrate surface was rinsed with 25°C ion-exchanged water (flow rate: 2 mL / sec) for 5 seconds, and the time until the water film formed on the SUS substrate completely disappeared after rinsing was measured. The water film completely disappeared when the water was visually observed to be completely gone. When no water film was formed on the SUS substrate and water droplets were formed, the water film retention time was set to 0 seconds. It can be seen that the formation of a water film on the SUS substrate improves the antifouling properties of the SUS substrate surface. In addition, the formation of a water film on the SUS substrate suppresses the formation of water spots, improving the gloss and finish of the hard surface. Furthermore, it can be said that the longer the water film retention time on the hard surface, the better the gloss, antifouling properties, and finish of the hard surface.

[0133] [Table 1]

Claims

1. A cleaning agent composition for hard surfaces, which contains (a) an amphoteric surfactant [hereinafter referred to as component (a)], (b) a bactericide [hereinafter referred to as component (b)], (c) a polymer having one or more groups selected from an amino group, a quaternary ammonium group, and a betaine group [hereinafter referred to as component (c)], and water, and the mass ratio (c) / (b) of the content of component (c) to the content of component (b) exceeds 1.

2. The cleaning agent composition for hard surfaces according to Claim 1, wherein component (a) is an amine oxide.

3. The cleaning agent composition for hard surfaces according to Claim 1, which contains component (a) in an amount of 0.1% by mass or more and 3% by mass or less.

4. The cleaning agent composition for hard surfaces according to Claim 1, wherein component (b) is one or more compounds selected from a cationic surfactant and a biguanide compound.

5. The cleaning agent composition for hard surfaces according to Claim 1, wherein component (c) is a polymer containing a structural unit A derived from one or more monomers A selected from a monomer (c1) represented by the following general formula (c1) and a monomer (c2) represented by the following general formula (c2). 【Chemical Formula 1】 [In the formula, R １ｃ , R ２ｃ , R ３ｃ , R ７ｃ , R ８ｃ , R ９ｃ are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. X １ｃ , Y １ｃ are each independently an alkylene group having 1 to 12 carbon atoms, -COOR １２ｃ -, -CONHR １２ｃ -, -O COR １２ｃ -, -R １３ｃ -OCO-R １２ｃ - selected groups. Here, R １２ｃ , R １３ｃ are each independently an alkylene group having 1 to 5 carbon atoms. R ４ｃis an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms or R １ｃ R ２ｃ C═C(R ３ｃ )−X １ｃ −. R ５ｃ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ６ｃ is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfuric acid ester group, or a benzyl group, and when R ６ｃ is an alkyl group, a hydroxyalkyl group, or a benzyl group, Z － represents an anion. When R ６ｃ contains a carboxy group, a sulfonic acid group, or a sulfuric acid ester group, Z － does not exist, and these groups in R ６ｃ become anions. R １０ｃ is a hydrogen atom, an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms or R ７ｃ R ８ｃ C═C(R ９ｃ )−Y １ｃ −. R １１ｃ is a hydrogen atom, an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. ]

6. The cleaning composition for hard surfaces according to claim 1, wherein the component (c) is at least one selected from cation-modified polyvinyl alcohol and cation-modified hydroxyethyl cellulose.

7. The cleaning composition for hard surfaces according to claim 1, wherein the component (c) has a structural unit represented by the following general formula (c3). 【Chemical formula 2】 [In the formula, R １４ｃ ~R １６ｃ : The same or different, a hydrogen atom or an alkyl group R having 1 or 2 carbon atoms １７ｃ : An alkylene group having 1 to 4 carbon atoms, or -Y ２ｃ -OPO ３ － -Y ３ｃ - Y ２ｃ , Y ３ｃ : Independently the same or different, an alkylene group having 1 to 4 carbon atoms R １８ｃ , R １９ｃ : Independently the same or different, a hydrocarbon group having 1 to 4 carbon atoms X ２ｃ : O or NR ２０ｃ , where R ２０ｃ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X ３ｃ : A hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R ２１ｃ SO ３ － , or R ２１ｃ COO － is shown. However, when R １７ｃ is an alkylene group having 1 to 4 carbon atoms, X ３ｃ is R ２１ｃ SO ３ － , or R ２１ｃ COO － , R ２１ｃ is an alkylene group having 1 to 4 carbon atoms, and when R １７ｃ is -Y ２ｃ -OPO ３ － -Y ３ｃ -, X ３ｃ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

8. In the general formula (c3), X ３ｃ is R ２１ｃ SO ３ － , the hard surface cleaning agent composition according to claim 7.

9. Component (c) has a structural unit derived from an N,N-di(ω-alkenyl (2 to 10 carbon atoms))-N,N-dialkyl (1 to 3 carbon atoms) quaternary ammonium salt, the hard surface cleaning agent composition according to claim 1.

10. In component (c), the structural unit derived from a monomer having a group selected from an amino group, a quaternary ammonium group, and a betaine group is 10 mol% or more and 100 mol% or less based on all the structural units, the hard surface cleaning agent composition according to claim 1. Claim 11 The hard surface cleaning agent composition according to claim 1, wherein the weight average molecular weight of component (c) is 1,000 or more and 200,000 or less. Claim 12 Further, the hard surface cleaning agent composition according to claim 1, which contains a nonionic surfactant [hereinafter referred to as component (d)]. Claim 13 The hard surface cleaning agent composition according to claim 12, wherein component (d) has a sugar skeleton or a glycerin skeleton as a hydrophilic group. Claim 14 Further, the hard surface cleaning agent composition according to claim 1, which contains an anionic surfactant [hereinafter referred to as component (e)], and the mass ratio (e) / (c) of the content of component (e) to the content of component (c) is 1 or less. Claim 15 The hard surface cleaning agent composition according to claim 1, which is for a hard surface of an article provided in one or more selected from a kitchen, a toilet, a bathroom, and a living room. Claim 16 The hard surface cleaning agent composition according to claim 1, wherein the hard surface is stainless steel. Claim 17 The hard surface cleaning agent composition according to claim 1, which is for wiping a hard surface. Claim 18 A method for cleaning a hard surface, which comprises bringing the hard surface cleaning agent composition according to any one of claims 1 to 17 into contact with a hard surface. Claim 19 The method for cleaning a hard surface according to claim 18, wherein the hard surface cleaning agent composition is brought into contact with the hard surface in a foamed state. Claim 20 The method for cleaning a hard surface according to claim 18, which comprises bringing the hard surface cleaning agent composition into contact with the hard surface and wiping off the contacted composition.

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