Liquid acidic cleaning composition for imparting antibacterial property to hard surface, and method for imparting antibacterial property

Abstract

To provide a liquid acidic cleaning composition for imparting an antibacterial property to a hard surface, and a method for imparting an antibacterial property, whereby it is possible to impart an antibacterial property to any hard surface to be treated, whether hydrophilic or hydrophobic.SOLUTION: A liquid acidic cleaning composition for imparting an antibacterial property to a hard surface, comprising: a) 0.1 to 5 wt.% of a water-soluble polymer having a carboxylic acid and / or a salt thereof; b) 0.1 to 10 wt.% of an antibacterial agent and / or a bactericidal agent having a cationic group; and c) 0.1 to 15 wt.% of an inorganic acid and / or an organic acid having a sulfonic acid group, wherein the pH is 3 or less. A method for imparting an antibacterial property, configured to treat a hard surface using a liquid composition comprising: a) 0.1 to 5 wt.% of a water-soluble polymer having a carboxylic acid and / or a salt thereof; b) 0.1 to 10 wt.% of an antibacterial agent and / or a bactericidal agent having a cationic group; and c) 0.1 to 15 wt.% of an inorganic acid and / or an organic acid having a sulfonic acid group, wherein the pH is 3 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a detergent composition and a method for imparting antibacterial properties, which can treat hard surfaces to remove accumulated inorganic soiling and also impart antibacterial properties to the hard surfaces. [Background technology]

[0002] Dirt caused by the proliferation of bacteria occurs in various places in a home. Various cleaning agents are available to remove such dirt, such as bacteria, mold, and slime.

[0003] In particular, areas around water such as kitchens, bathrooms, sinks, and toilets are prone to bacterial and fungal growth, making them the areas in a home where bacterial contamination is a major concern. As a result, these areas require frequent cleaning and are a time-consuming task to maintain.

[0004] Against this backdrop, disinfectant cleaners and hypochlorous acid-based cleaners have been proposed to remove slimy and pink stains caused by bacterial or fungal growth, as well as dark stains around the waterline in the toilet bowl puddle. These cleaners are primarily designed to remove existing bacteria and fungi, as well as their metabolites, and are unable to provide antibacterial or antifungal properties to prevent new bacterial or fungal growth on cleaned hard surfaces. For example, to prevent dark stains on toilet bowls, on-tank disinfectant cleaners that deliver a fixed amount of disinfectant to the bowl during flushing and gel-type disinfectant (antibacterial) cleaners that are stamped onto the surface of the bowl and deliver a fixed amount of disinfectant to the bowl during flushing have been proposed. However, with spray-type and squeeze-bottle cleaners, it has been difficult to retain a consistent amount of antibacterial agent on the target hard surface during cleaning procedures that involve rinsing with water.

[0005] Residential spaces that require rinsing with water include wet areas such as toilet bowls, kitchen sinks, bathroom bathtubs, floors, walls, mirrors, handrails, washbasins, chairs, and sinks. These wet areas are prone to the formation of inorganic compound stains such as urinary stones, soap scum, and limescale, as well as bacterial and fungal growth, resulting in slimy, pink, dark, and moldy stains. Furthermore, the hard surfaces in these areas are made of a variety of materials with hydrophobic or hydrophilic properties, including plastic, stainless steel, enamel, tile, and ceramics.

[0006] For these reasons, there is a demand for cleaning agents that can remove inorganic complex soils that have accumulated in wet areas of homes where rinsing with water is required, while at the same time imparting antibacterial, antifungal, and even stain-resistant properties to hard surfaces of various materials in order to suppress the generation of bacterial stains as mentioned above.

[0007] Meanwhile, a spray has been proposed that imparts antibacterial properties to a target surface when sprayed on it. This product claims to eliminate viruses and bacteria when sprayed on the target surface, while at the same time fixing antibacterial ingredients to the surface, allowing the antibacterial effect to last for one week. The product's label mentions Patent Nos. 4848484 and 4830075.

[0008] Patent No. 4848484 describes a silicon-containing compound containing a molecule with bactericidal properties, such as octadecylammonium chloride. It shows that the silicon-containing compound reacts with oxygen-containing functional groups, such as -OH groups and -O- groups, on the surface of a substrate to form a covalent bond, thereby imparting antibacterial properties.

[0009] Patent No. 4830075 describes a silicon-containing compound containing a molecule with bactericidal properties, such as octadecylammonium chloride. It shows that the silicon-containing compound reacts with oxygen-containing functional groups, such as -OH groups and -O- groups, on the surface of a substrate to form covalent bonds, thereby imparting antiviral properties.

[0010] Japanese Patent No. 5830359 describes a liquid laundry detergent containing an amine surfactant that imparts antibacterial properties to laundry. In the examples of this patent, antibacterial performance was evaluated using cotton knitted fabric, which has a negative charge in water, rather than synthetic fabric, which does not have a negative charge. Furthermore, the cotton fibers that make up cotton knitted fabric are known to have a high negative charge density, and the patent describes how cationic amine surfactants are adsorbed onto the cotton fibers in the wash water, thereby exerting antibacterial properties. However, no adsorption of cationic surfactants capable of exerting antibacterial properties was observed during the washing and rinsing processes on various hard surfaces, such as those used in residential facilities.

[0011] Japanese Patent No. 7002176 describes an antibacterial cleaning composition consisting of a specific quaternary ammonium chloride and a specific amine surfactant. This cleaning agent is characterized by leaving less visible residue or streaks on surfaces. The antibacterial properties described in this patent are different from those defined in the present invention, and are described as the effect of killing bacteria in a short period of time upon contact with the cleaning agent. The specification also lists xanthan gum as an example of a suitable thickening agent. It states that the aim is to improve cleaning and antibacterial properties by imparting appropriate viscosity to the cleaning agent, thereby extending the contact time with dirt and bacteria on inclined surfaces. However, this patent does not disclose antibacterial properties such as antibacterial ingredients remaining on hard surfaces after cleaning and rinsing, thereby inhibiting the growth and proliferation of bacteria.

[0012] Japanese Patent Publication No. 2020-83855 describes an antibacterial and antifungal agent containing a monoterpene compound and a quaternary ammonium salt. This antibacterial and antifungal agent is effective against a wide range of bacteria even at low concentrations, and is also gentle on the human body and the environment. Considering the antibacterial evaluation method in the examples, this antibacterial and antifungal agent is assumed to be applied to a surface without being rinsed with water.

[0013] Patent No. 2963065 describes a kitchen detergent containing benzalkonium chloride, a metal chelating agent, a water-soluble solvent, and a thickening polysaccharide (such as xanthan gum) and having a pH of 6 to 8. The "Effects of the Invention" section of the specification states that the detergent has high detergency, particularly against inorganic complex stains primarily composed of silica and calcium, as well as limescale, and also has excellent rinsing and wiping properties, and a good finish. The examples also evaluate the detergent's ability to clean actual stains attached to a stainless steel piece attached to a typical household sink. However, there is no mention of imparting antibacterial and antifungal properties or stain resistance to hard surfaces.

[0014] Japanese Patent No. 5,779,390 discloses a toilet cleaner having a pH of 3 or less, which contains an organic or inorganic acid, an anionic surfactant, a nonionic surfactant, and a thickening polysaccharide (such as xanthan gum). Paragraph 0035 of the patent describes the use of a thickening polysaccharide to improve detergent residue, limescale inhibition, and spreadability on the toilet bowl, but does not mention imparting antibacterial or antifouling properties to the target surface. Paragraph 0044 also describes that the use of a cationic surfactant, such as benzalkonium chloride, reduces the functionality of the anionic surfactant, significantly reducing detergent residue, limescale inhibition, and spreadability, and therefore it is preferable to substantially avoid the use of a cationic surfactant.

[0015] JP 2017-78134 discloses a composition containing a nonionic surfactant, a glycol solvent, an aminocarboxylic acid type chelating agent, and a water-soluble polymer (such as xanthan gum), and having a kinematic viscosity of 1.5 to 20 mm as measured with a capillary viscometer. 2The document discloses a bathroom cleaner containing 100% hydroxybenzoates (100%). Paragraph 0006 of the document states that the cleaner has both good adhesion retention and good spreadability, thereby achieving excellent cleaning power even on vertical surfaces. Paragraph 0037 also states that the water-soluble polymer is used to impart good adhesion retention and good spreadability to the vertical surface of a bathtub. The examples also describe an evaluation of cleaning power using glass fiber reinforced plastic test pieces. However, there is no mention of imparting antibacterial, antifungal, or antifouling properties to the hard surfaces of bathtubs and bathroom spaces.

[0016] Examples 32, 69, and 106 of Japanese Patent Laid-Open Publication No. 2003-183697 disclose toilet cleaners containing alkyl quaternary ammonium salts, hydrochloric acid, xanthan gum, and diethylene glycol monobutyl ether. The authors state that the incorporation of an acidic agent provides excellent removal of inorganic soils derived from tap water. However, there is no mention of imparting antibacterial or antifouling properties to hard surfaces.

[0017] Examples 16, 51, and 86 of JP 2003-183698 A disclose bathroom cleaners containing alkyl quaternary ammonium salts, acetic acid, xanthan gum, and diethylene glycol monobutyl ether. The description states that the blending of surfactants, chelating agents, polymeric compounds, solvents, and fragrances provides a product that simultaneously exhibits cleaning power, foam quality, rinsability, and stain resistance. However, there is no description of imparting antibacterial properties to hard surfaces.

[0018] JP 2022-89322 A is a patent filed by the present applicant, which discloses a liquid antifouling detergent composition for hard surfaces, which contains xanthan gum, a cationic surfactant, and an inorganic or organic acid, and has a pH of 5.5 or less, and an antifouling method. This specification does not mention imparting antibacterial properties to hard surfaces.

[0019] JP 2023-143721 A is a patent filed by the present applicant, which discloses a liquid antibacterial detergent composition for hard surfaces with a pH of 3 to 12, which contains a water-soluble polymer having a carboxylic acid and / or its salt, an antibacterial agent and / or germicide having a cationic group, and an electrolyte, and a method for imparting antibacterial properties. The specification describes that the detergent composition remains on the surface after cleaning and rinsing in situations where water is used, such as in bathrooms, toilets, and kitchen sinks, and provides sustained antibacterial properties. [Prior art documents] [Patent documents]

[0020] [Patent Document 1] Patent No. 4848484 [Patent Document 2] Patent No. 4830075 [Patent Document 3] Patent No. 5830359 [Patent Document 4] Patent No. 7002176 [Patent Document 5] Japanese Patent Publication No. 2020-83855 [Patent Document 6] Patent No. 2963065 [Patent Document 7] Patent No. 5779390 [Patent Document 8] Japanese Patent Application Laid-Open No. 2017-78134 [Patent Document 9] Japanese Patent Application Laid-Open No. 2003-183697 [Patent Document 10] Japanese Patent Application Laid-Open No. 2003-183698 [Patent Document 11] Japanese Patent Publication No. 2022-89322 [Patent Document 12] Japanese Patent Application Publication No. 2023-143721 Summary of the Invention [Problem to be solved by the invention]

[0021] The object of the present invention is to provide a detergent composition and antibacterial method that can remove complex inorganic stains such as urinary scale stains, soap scum stains (metal soap), and limescale stains (calcium carbonate and silicon dioxide) that occur in wet areas such as toilets, bathrooms, and kitchen sinks, and that can impart antibacterial properties to the treated surface across all hard surfaces, regardless of whether they are hydrophilic or hydrophobic, after rinsing.Furthermore, the object of the present invention is to provide antifouling properties that suppress the adhesion of oily stains to the treated surface. [Means for solving the problem]

[0022] The present invention can be expressed, for example, as follows. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.1 to 5% by weight b) Antibacterial agents and / or bactericides having cationic groups: 0.1 to 10% by weight c) Inorganic acid and / or organic acid having a sulfonic acid group: 0.1 to 15% by weight and a pH of 3 or less.

[0023] The present invention can also be expressed as follows. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.1 to 5% by weight b) Antibacterial agents and / or bactericides having cationic groups: 0.1 to 10% by weight c) Inorganic acid and / or organic acid having a sulfonic acid group: 0.1 to 15% by weight A method for imparting antibacterial properties to a hard surface by treating the surface with a liquid acidic cleaning composition containing the above and having a pH of 3 or less. [Effects of the Invention]

[0024] According to the present invention, it is possible to effectively remove stains that have been left unattended for a certain period of time, such as urinary scale stains (calcium carbonate, calcium phosphate, etc.), soap scum stains (metallic soap), and limescale stains (calcium carbonate and silicon dioxide), which are frequently found in places around water such as toilets, bathrooms, and kitchen sinks, and after cleaning and rinsing, it is possible to impart antibacterial properties to the treated surface, regardless of whether it is a hydrophilic or hydrophobic hard surface. Here, antibacterial properties refer to the ability to inhibit the proliferation of bacteria when they adhere to a surface and are present in the presence of moisture and a nutrient source. DETAILED DESCRIPTION OF THE INVENTION

[0025] (1) The antibacterial liquid acidic detergent composition for hard surfaces of the present invention and the composition used in the antibacterial method for treating hard surfaces made of a hydrophilic or hydrophobic material of the present invention (hereinafter, both the "antibacterial liquid acidic detergent composition" and the "composition used in the antibacterial method" are also referred to as the "liquid composition of the present invention") are: a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.1 to 5% by weight b) Antibacterial agents and / or bactericides having cationic groups: 0.1 to 10% by weight c) Inorganic acid and / or organic acid having a sulfonic acid group: 0.1 to 15% by weight and its pH is 3 or less.

[0026] (2) Antibacterial and / or disinfectant agents having cationic groups

[0027] (2-1) In the present invention, the antibacterial agent exhibits antibacterial properties is the above-mentioned "b) antibacterial agent and / or bactericide having a cationic group."

[0028] Antibacterial and / or disinfectant agents having a cationic group are bases that become positive ions in water, but do not include amphoteric bases that have both cationic and anionic properties in the same molecule.

[0029] The concentration of "b) antibacterial agent and / or bactericide having a cationic group" in the liquid composition of the present invention is 0.1 to 10% by weight. If it is less than 0.1% by weight, the antibacterial properties are not fully exhibited. If it exceeds 10.0% by weight, it becomes an excessive amount. It is preferably 0.2 to 7% by weight, more preferably 0.3 to 3% by weight, and even more preferably 0.4 to 2% by weight.

[0030] (2-2) Antibacterial agents and / or germicides with cationic groups are already used in various cleaning agents to kill bacteria or fungi present on target surfaces, providing sterilization, disinfection, sterilization, and antifungal effects. This is said to occur because antibacterial agents and / or germicides with cationic groups adsorb and penetrate the cell membranes of bacteria or fungi, destroying the cell membrane or inactivating cell membrane proteins, thereby killing the bacteria or fungi. These effects are achieved by contacting the cleaning agent with bacteria or fungi for a certain period of time. They also act on viruses, inactivating them.

[0031] However, when a cleaning agent containing an antibacterial agent and / or bactericide having a cationic group with bactericidal activity as described above is used on a hard surface and a cleaning operation involving rinsing with water is performed, most of the antibacterial agent and / or bactericide having a cationic group contained in the cleaning agent is rinsed away, making it extremely difficult for the antibacterial agent and / or bactericide having a cationic group to remain on the hard surface and exert its bactericidal activity.In particular, when a cleaning operation involving rinsing with water is performed using such a cleaning agent on hard surfaces such as kitchen sinks, bathrooms, washbasins, and toilet bowls, and the surfaces are then in an environment where they are repeatedly splashed with water or rinsed with water, it is almost impossible for the antibacterial agent and / or bactericide having a cationic group contained in the cleaning agent to remain on the hard surface and exert and maintain its bactericidal effect.

[0032] The present inventors have discovered that by combining an antibacterial agent and / or bactericide having a cationic group with a water-soluble polymer having a carboxylic acid and / or its salt, and further mixing them uniformly with an inorganic acid and / or an organic acid having a sulfonic acid group, the antibacterial agent and / or bactericide having a cationic group can remain on the target hard surface even after the cleaning agent is applied to the target hard surface and then rinsed with water. This makes it possible to impart antibacterial properties to the target hard surface. Furthermore, it may also be possible to impart antifungal properties in addition to antibacterial properties to the target hard surface.

[0033] The present invention can provide antifungal properties in addition to antibacterial properties to the treated surface, even in a cleaning operation involving rinsing with water, for all hard surfaces, regardless of whether they are hydrophilic or hydrophobic. The term "antifungal properties" used here refers to the ability to inhibit fungal growth when fungi adhere to a surface and are present in the presence of moisture and a nutrient source.

[0034] In addition, antibacterial agents and / or disinfectants having a cationic group are thought to have the effect of easily breaking down the dirt by undergoing a substitution reaction with the metal ions of fatty acid metal salts, which are known as soap scum, a typical dirt in bathrooms, making them excellent cleaning bases in this respect as well.Furthermore, they also have the effect of weakening the adhesive strength of sebum dirt that adheres to bathtubs and other surfaces in bathrooms, making them easier to remove from the bathtub surface.

[0035] (2-3) The "b) antibacterial agent and / or bactericide having a cationic group" in the present invention is preferably, but not limited to, 1) a cationic surfactant, 2) a cationic polymer, or 3) a guanidine skeleton or biguanide skeleton compound.

[0036] The cationic surfactant 1) above is preferably an alkylamine salt type or alkenylamine salt type, a quaternary ammonium salt type, or a pyridine ring salt-containing type cationic surfactant, but is not limited thereto. Any one of the cationic surfactants can be used alone, or a plurality of cationic surfactants can be used in combination.

[0037] (i) As the alkylamine salt type and alkenylamine salt type, monoalkyl (or alkenyl) amine, dialkyl (or dialkenyl) amine, and trialkyl (or trialkenyl) amine are preferred.

[0038] The number of carbon atoms in the alkyl group in the alkylamine salt type (or the alkenyl group in the alkenylamine salt type) is preferably 6 to 20, and more preferably 10 to 18. The alkyl group (or alkenyl group) can be linear or branched, but is preferably linear. A preferred example is N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (trade name: LONZABAC12 ["LONZABAC" is a trademark], manufactured by LONZA).

[0039] (ii) As the quaternary ammonium salt type, tetraalkyl (or tetraalkenyl) ammonium salts or benzyltrialkyl (or trialkenyl) ammonium salts are preferred.

[0040] The number of carbon atoms in the alkyl group or alkenyl group in the quaternary ammonium salt type is preferably 6 to 20, and more preferably 8 to 18. The alkyl group (or alkenyl group) can be linear or branched, but is preferably linear. Preferred examples include dodecyltrimethyl quaternary ammonium chloride, tetradecyltrimethyl quaternary ammonium chloride, hexadecyltrimethyl quaternary ammonium chloride, coconut alkyltrimethyl quaternary ammonium salt, palm oil or palm kernel oil alkyltrimethyl quaternary ammonium salt, tallow alkyltrimethyl quaternary ammonium salt, benzalkonium chloride having an alkyl group having 8 to 18 carbon atoms, benzethonium chloride, dialkyldimethylammonium salt having 8 to 10 carbon atoms, dioctyldimethylammonium salt, didecyldimethylammonium salt, and N,N-didecyl-N-methylpoly(oxyethyl)ammonium propionate. In particular, from the viewpoint of maintaining antibacterial activity under conditions where a large amount of running water is used for rinsing, such as in a toilet or kitchen sink, alkyltrimethyl quaternary ammonium chlorides having alkyl groups mainly containing 16 to 18 carbon atoms, dialkyldimethylammonium chlorides having 8 to 10 carbon atoms, benzalkonium chloride and benzethonium chloride having 8 to 18 carbon atoms are more preferred.

[0041] (iii) As the pyridine ring salt-containing type, alkyl (or alkenyl) pyridinium salts are preferred. The number of carbon atoms in the alkyl (or alkenyl) group is preferably 6 to 20, and more preferably 10 to 18. A preferred example is cetylpyridinium chloride.

[0042] As for the cationic polymer of 2) above, a cationic polymer having a quaternary ammonium salt in the main chain or side chain, a cationic polymer having a guanidine skeleton or a biguanide skeleton in the main chain or side chain, a cationic polymer having an amine in the main chain, or a cationic polymer having an amino group in the side chain is preferred.

[0043] A specific example of a cationic polymer having a quaternary ammonium salt in the main chain is N,N-dimethyl-2-propylammonium chloride polymer (trade name: Barquat PQ ["Barquat" is a trademark], manufactured by LONZA). Specific examples of cationic polymers having a quaternary ammonium salt in the side chain include diallyldimethylammonium chloride polymer (trade name: Merquat 100 ["Merquat" is a trademark], manufactured by Lubrizol), and a copolymer of diallyldimethylammonium chloride and acrylamide (trade name: Merquat 550 ["Merquat" is a trademark], manufactured by Lubrizol). An example of a cationic polymer having an amine in the main chain is polyethyleneimine. An example of a cationic polymer having an amino group in the side chain is ε-poly-L-lysine, in which the amino acid lysine is linked by an amide bond. Products produced by fermentation are commercially available. Chitosan is also an example of a cationic polymer consisting of β1→4 bonds of glucosamine. Industrially, chitosan is produced by deacetylating chitin (poly-β1→4-N-acetylglucosamine) obtained from crustaceans such as crabs and shrimp by boiling in concentrated alkali. The conversion of chitin to chitosan (deacetylation) is not complete, and in some cases about 30% of the chitin remains in the chitosan.

[0044] Specific examples of cationic polymers having a guanidine skeleton or a biguanide skeleton include polyhexamethylene guanidine or a salt thereof (e.g., phosphate), polyhexamethylene biguanide or a salt thereof, such as hydrochloride (an example of a hydrochloride product: Proxel IB [trade name, "Proxel" is a trademark, manufactured by LONZA]). Other examples include polyaminopropyl biguanide or a salt thereof (e.g., hydrochloride). Among these, polyhexamethylene guanidine or polyhexamethylene biguanide is particularly preferred.

[0045] The guanidine or biguanide skeleton compounds in 3) above are non-polymeric guanidine or biguanide skeleton compounds, i.e., excluding the above-mentioned cationic polymers having a guanidine or biguanide skeleton, and specific examples thereof include chlorhexidine or a salt thereof, such as the gluconate salt chlorhexidine gluconate (trade name: Spectradyne ["Spectradyne" is a trademark], manufactured by LONZA), hydrochloride, acetate, etc. Further examples include alexidine hydrochloride.

[0046] In particular, in residential spaces such as kitchen sinks, bathrooms, washstands, and toilets, warm water is commonly used not only for rinsing during cleaning operations but also for washing dishes and bathing, and in toilets, large amounts of running water are used to flush urine and feces.Even in such environments, cationic polymers or compounds having a guanidine skeleton or a biguanide skeleton can impart excellent antibacterial properties to the target hard surface.Furthermore, they can also impart antifungal properties in addition to antibacterial properties to the target hard surface.

[0047] (3) Water-soluble polymers containing carboxylic acids and / or their salts

[0048] It is presumed that when the liquid composition of the present invention is rinsed with water, the dilution effect and the increase in pH cause the complex of the antibacterial agent and / or disinfectant having a cationic group and the water-soluble polymer having a carboxylic acid and / or its salt to undergo layer separation and become insolubilized, remaining on the target surface.

[0049] Residential spaces that are subject to cleaning operations involving rinsing with water include hard surfaces made of hydrophilic and hydrophobic materials, such as toilet bowls and / or their drains, kitchen sinks and / or their drains, bathroom floors, walls, bathtubs and / or their drains, and washbasins and / or their drains.

[0050] Even if the liquid composition of the present invention is rinsed with water after application, it can remain on the hydrophilic hard surfaces and hydrophobic hard surfaces in residential spaces as exemplified above or other surfaces not limited to residential spaces, thereby exerting antibacterial properties, and may also exert antifungal properties.

[0051] In the present invention, the water-soluble polymer having a carboxylic acid and / or its salt plays a role in allowing the antibacterial agent and / or bactericide having a cationic group that imparts antibacterial properties (and may also impart antifungal properties) to remain on the hard surface.

[0052] a) Various water-soluble polymers having a carboxylic acid and / or its salt can be used. Examples of natural polymers include xanthan gum, pectin, gellan gum, diutan gum, welan gum, gum arabic, sodium (potassium) alginate, hyaluronic acid, tragacanth gum, and succinoglycan. Examples of semi-synthetic polymers include sodium (potassium) carboxymethylcellulose and sodium (potassium) carboxyethylcellulose. Examples of synthetic polymers include sodium (potassium) salts of carboxyvinyl polymers, sodium (potassium) polyacrylate, and modified polyvinyl alcohols having carboxylate salts.

[0053] Among these, xanthan gum, gellan gum, diutan gum, succinoglycan, and carboxymethyl cellulose are preferred, with xanthan gum and carboxymethyl cellulose being more preferred, and xanthan gum being most preferred.

[0054] These water-soluble polymers containing carboxylic acids and / or their salts have a negative charge above a certain pH range, and therefore can form complexes with antibacterial agents and / or disinfectants containing cationic groups. This is thought to result in phase separation upon rinsing with water, resulting in insolubilization and remaining on hard surfaces.

[0055] Furthermore, the water-soluble polymer having a carboxylic acid and / or a salt thereof plays a role in allowing the antibacterial agent and / or bactericide having a cationic group that exhibits antibacterial activity to remain on the hard surface. Even after a cleaning operation involving rinsing with water, in areas around water such as kitchen sinks, bathrooms, and toilets, where water is expected to constantly splash on the hard surface during use, the water-soluble polymer continues to act to allow the antibacterial agent and / or bactericide having a cationic group to remain on the surface.

[0056] Furthermore, because water-soluble polymers containing carboxylic acids and / or their salts are negatively charged, they are presumed to hydrophilize hard surfaces. They can be used to modify hydrophilic hard surfaces, such as ceramic tiles and hydrophobic hard surfaces, such as plastics and stainless steel, to provide excellent antifouling properties that prevent the adhesion of oily stains, such as fecal stains, sebum stains, and oily grease, even in wet environments. The hydrophilic nature of these polymers also contributes to the resistance of limescale stains, such as calcium carbonate and silicic acid stains.

[0057] Such antifouling function means that the organic soiling that serves as nutrients for bacteria and fungi to grow on hard surfaces is reduced, thereby improving the function of imparting antibacterial and even antifungal properties to hard surfaces, which is the objective of the present invention.

[0058] The concentration of "a) a water-soluble polymer having a carboxylic acid and / or a salt thereof" in the liquid composition of the present invention is 0.1 to 5% by weight.

[0059] If the content is less than 0.1% by weight, sufficient antibacterial properties will not be exhibited. If the content exceeds 5.0% by weight, the viscosity will be too high, impairing the handleability of the liquid composition. The content is preferably 0.2 to 3% by weight, more preferably 0.3 to 1.5% by weight, even more preferably 0.4 to 0.9% by weight, and particularly preferably 0.5 to 0.8% by weight.

[0060] (4) Inorganic acids and / or organic acids having sulfonic acid groups

[0061] Acidic cleaning agents are known to be suitable for effectively removing stains that have been left unattended for a certain period of time, such as urinary scale stains (calcium carbonate, calcium phosphate, etc.), soap scum stains (metal soap), and limescale stains (calcium carbonate and silicon dioxide), which frequently occur in wet areas such as toilets, bathrooms, and kitchen sinks. In the present invention, an acidic agent is also used to remove such stains. Furthermore, in the present invention, a cationic base and a water-soluble polymer having a carboxylic acid and / or its salt are contained in order to impart antibacterial properties to the hard surface to be treated after cleaning and rinsing. However, when both bases are cationic and anionic, a water-insoluble complex is formed, making the cleaning agent unusable as a cleaning agent or antibacterial agent. An acidic agent is also used to suppress the formation of a strong gel due to the formation of such a complex, thereby enabling uniform mixing. From the perspective of cleaning and removing these unattended stains and uniform mixing, it is necessary to include the above-mentioned "c) inorganic acid and / or organic acid having a sulfonic acid group." Organic acids having a carboxylic acid group are not included in the acidic agent of the present invention because they are difficult to mix uniformly.

[0062] The concentration of "c) inorganic acid and / or organic acid having a sulfonic acid group" in the liquid composition of the present invention is 0.1 to 15% by weight. From the viewpoints of the detergency for the target stain and the uniform mixing of the liquid composition, it is preferably 0.5 to 9.95% by weight, more preferably 0.75 to 5.5% by weight, even more preferably 1.0 to 3% by weight, and particularly preferably 1.5 to 2.5% by weight.

[0063] The pH of the liquid composition of the present invention is 3 or less. This is adjusted from the viewpoint of cleaning and removing tough urinary stone stains and limescale stains that have been left for a long period of time, and from the viewpoint of uniform mixing of the liquid composition. The pH is preferably 2 or less, more preferably 1.5 or less.

[0064] Examples of "c) inorganic acid and / or organic acid having a sulfonic acid group" in the present invention include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, toluenesulfonic acid, styrenesulfonic acid, etc. From the viewpoints of stain removal ability and uniform mixing with various cationic bases, hydrochloric acid and sulfamic acid are particularly preferred. The "c) inorganic acid and / or organic acid having a sulfonic acid group" may be used singly or in combination of two or more.

[0065] (5) Examples of components other than a), b) and c) that may be contained in the liquid composition of the present invention

[0066] (5-1) In the present invention, in addition to the antibacterial agent and / or bactericide having a cationic group, it is preferable to use a nonionic surfactant or an amphoteric surfactant from the viewpoint of improving detergency.

[0067] (i) The nonionic surfactant is preferably at least one selected from polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene branched alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxypropylene alkyl ethers, polyoxypropylene alkenyl ethers, polyoxyethylene polypropylene alkyl ethers, polyoxybutylene alkyl ethers, polyoxybutylene alkenyl ethers, sucrose fatty acid esters, aliphatic alkanolamides, fatty acid glycerin monoesters, and alkyl glycosides. The alkyl or alkenyl group in these nonionic surfactants preferably has 8 to 18 carbon atoms.

[0068] (ii) Preferred amphoteric surfactants include alkylamine oxides, alkenylamine oxides, alkylamidopropyl-N,N-dimethylacetate betaine, alkylamidopropyl-N,N-dimethyl-2-hydroxypropylsulfobetaine, and alkylamidopropyl-N,N-dimethyl-propylsulfobetaine. Among these, alkylamine oxides are cationic in the acidic range and therefore, like cationic surfactants, have the property of adhering to hard surfaces even during cleaning procedures involving rinsing with water. However, since the acidic state is not maintained thereafter, they are unable to exhibit sufficient antibacterial properties (or even antifungal properties).

[0069] More specific examples of preferred amphoteric surfactants include laurylamine oxide, myristylamine oxide, lauric acid amidopropyl-N,N-dimethylacetic acid betaine, myristate amidopropyl-N,N-dimethylacetic acid betaine, cocamidopropyl-N,N-dimethylacetic acid betaine, and laurylhydroxysulfobetaine.

[0070] (iii) Furthermore, it is desirable that the liquid composition of the present invention does not contain an anionic surfactant. An anionic surfactant may form an insoluble complex with the "b) antibacterial agent and / or bactericide having a cationic group" when blending the liquid composition of the present invention or when rinsing with water after washing. As a result, the anionic surfactant may inhibit the formation of a complex between the water-soluble polymer having a carboxylic acid and / or its salt and the antibacterial agent and / or bactericide having a cationic group, which may lead to a loss of the antibacterial effect.

[0071] (5-2) The liquid composition of the present invention preferably contains a water-soluble solvent in order to maintain the uniform dissolution stability or uniform dispersion stability of the components and to further enhance the cleaning properties. The inclusion of a water-soluble solvent in the liquid composition of the present invention has the effect of enhancing the uniform dissolution stability or uniform dispersion stability even when the content of the acid agent is reduced.

[0072] The liquid composition of the present invention may contain glycol and / or glycol ether (i.e., one or both of glycol and glycol ether) as a water-soluble solvent. For example, the liquid composition may contain 2 to 30% by weight of glycol and / or glycol ether (when both glycol and glycol ether are contained, the total of both is 2 to 30% by weight).

[0073] Specific examples of glycol ethers used as the water-soluble solvent include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, polyoxyethylene-polyoxypropylene glycol dimethyl ether, polyoxyethylene glycol phenyl ether, phenyl carbitol, phenyl cellosolve, benzyl carbitol, and hexylene glycol. Among these, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and hexylene glycol are preferred in terms of detergency, odor, and feel. Among these, diethylene glycol monobutyl ether is particularly preferred.

[0074] The water-soluble solvent is preferably contained in the liquid composition of the present invention in an amount of 2 to 30% by weight. If it is less than 2%, the effect of uniformly stabilizing the liquid composition and the cleaning power for oily stains are not sufficiently exhibited, and if it exceeds 30% by weight, the amount becomes excessive and there may be situations where the odor is unpleasant. More preferably, it is 3 to 15% by weight, and even more preferably, it is 4 to 10% by weight.

[0075] The viscosity of the liquid composition of the present invention is preferably in the range of 50 to 1000 mPa·s. To effectively clean and remove urinary stone stains, soap scum, and limescale stains, a longer contact time between the stains and the liquid composition is preferred. Facilities prone to such stains, such as toilet bowls, bathroom walls, bathtubs, and kitchen sinks, often have inverted, vertical, or inclined surfaces, which can easily cause the liquid composition to drip off the stains. Therefore, it is preferable for the liquid composition to have sufficient viscosity to ensure sufficient contact time between the stains and the liquid composition even in such locations. A viscosity of less than 50 mPa·s makes it difficult to ensure sufficient contact time with the stains. A viscosity of more than 1000 mPa·s tends to reduce the liquid composition's ability to spread properly, resulting in a smaller area of ​​antibacterial properties after rinsing with water. A viscosity of 80 to 800 mPa·s is preferred, more preferably 100 to 600 mPa·s, and particularly preferably 150 to 500 mPa·s. The viscosity of the liquid composition is within the range of values ​​measured using a Brookfield viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.) with a TM2 rotor or TM3 rotor at a rotation speed (rpm) of 60.

[0076] (5-3) The liquid composition of the present invention may also contain an appropriate amount of ethanol, isopropyl alcohol, aromatic alcohol, or the like to enhance the feeling of freshness and disinfection (sterilization during washing). Other ingredients may also be added: electrolytes, chelating agents, disinfectants, preservatives, deodorizers, fragrances, colorants, pigments, thickeners other than water-soluble polymers containing carboxylic acids and / or salts thereof, and water. Electrolytes and chelating agents have the effect of improving the uniform dissolution stability and uniform dispersion stability of the liquid composition. Examples of electrolytes and chelating agents that may be added include water-soluble inorganic salts, water-soluble organic salts, polycarboxylic acids and / or salts thereof with metal chelating ability, polyphosphonic acids and / or salts thereof, and polyphosphoric acids and / or salts thereof. Examples of deodorizing agents that may be added include green tea extract and cyclodextrin, which may be added in an amount of approximately 0.1 to 5 wt%.

[0077] (6) When the liquid antibacterial detergent composition of the present invention is used on a hard surface, and when a hard surface made of a hydrophilic or hydrophobic material is treated with the liquid composition by the method of the present invention, preferred examples of means for supplying the liquid composition to the hard surface include squeeze-type dispensing containers and trigger-type dispensing containers that can apply the liquid composition to the target surface in liquid, gel, or foam form.

[0078] The liquid composition of the present invention supplied to a hard surface can be used, for example, with a cloth-like, sponge-like, fibrous, brush-like, or other type of tool to clean or apply the target hard surface. Alternatively, for example, the liquid composition can be supplied to such a tool and then applied to the target hard surface using the tool to clean or apply the composition. [Example]

[0079] Example 1

[0080] i) Xanthan gum (trade name: KELZAN AR ["KELZAN" is a trademark], manufactured by CP KELCO) as a water-soluble polymer having a carboxylic acid and / or a salt thereof ii) as antibacterial and / or bactericidal agents having cationic groups, It is a cationic surfactant Coconut alkylbenzyldimethylammonium chloride [benzalkonium chloride] (trade name: Hyamine 3500J ["Hyamine" is a trademark], manufactured by LONZA), Dioctyldimethylammonium chloride (trade name: BardacLF80 ["Bardac" is a trademark], manufactured by LONZA), N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (trade name: Lonzabac 12 ["Lonzabac" is a trademark], manufactured by LONZA), Hexadecyltrimethylammonium chloride (trade name: Nissan Cation PB-300 ["Nissan Cation" is a trademark], manufactured by NOF Corporation), A mixture consisting of benzalkonium chloride / dioctyldimethylammonium chloride / didecyldimethylammonium chloride / octyldecyldimethylammonium chloride in a composition ratio of 40 / 30 / 15 / 15 (wt%) (product name: Bardac 205M, "Bardac" is a trademark manufactured by LONZA), or As an antibacterial and / or disinfectant having a cationic group, polyhexamethylene biguanide (trade name: Proxel IB, "Proxel" is a trademark, manufactured by LONZA), which is a cationic polymer having a biguanide structure.

[0081] iii) As an inorganic acid and / or an organic acid having a sulfonic acid group, sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), which is an inorganic acid Using the above, cleaning agents (Nos. 1-5) (liquid compositions; the same applies to the following Examples and Comparative Examples) having the compositions shown in Example 1 of Table 1 were prepared.

[0082] Next, the appearance of the cleaners was observed, and their pH and viscosity were measured. Viscosity measurements were performed using a B-type viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.) with a TM2 rotor or TM3 rotor at a speed of 60 rpm (the same applies to viscosity measurements in the following Examples and Comparative Examples). Each cleaner was then used to conduct an antibacterial test and evaluation on ceramic tile boards. The results are shown in Table 1.

[0083] Comparative Example 1

[0084] Using the same components as in Example 1, a cleaning agent (No. 1-2) having the composition shown in Comparative Example 1 in Table 2 was prepared.

[0085] The appearance of the cleaners was then observed, and their pH and viscosity were measured. Antibacterial tests and evaluations were then conducted on ceramic tile boards using each cleaner. The results are shown in Table 1.

[0086] <Antibacterial testing and evaluation based on the antibacterial function of toilet bowls>

[0087] The antibacterial test and evaluation were carried out in accordance with JIS Z2801 antibacterial test for plastic products.

[0088] A white ceramic tile (white mosaic tile) measuring 45 mm x 45 mm x 7 mm was prepared as a hard surface test plate.

[0089] For the test, a flush toilet was used that combined a toilet bowl (TOTO CS220BM), a flush tank (TOTO SH221BAS), and a warm water washing toilet seat (TOTO TCF4711 type).

[0090] A screen net cut to an appropriate size was fixed with double-sided tape from the top of the puddle area to the bowl of the toilet, and two test plates were fixed with double-sided tape on top of the screen net at the front of the toilet bowl. In other words, the test plates were fixed to the toilet bowl so that they would not fall off and would not impair the flushing water flow of the toilet.

[0091] After repeating the water flush (amount of water for flushing: 4.8 L / time) three times, water droplets adhering to the surface of the test plate were lightly wiped off with tissue paper.

[0092] Next, 2 ml of the prepared cleaner was dripped onto the front surface of a test board (ceramic tile: 45 mm x 45 mm) to cover the hard surface. After leaving it for 3 minutes (180 seconds), the test board was immediately rinsed with water to rinse off the cleaning solution. After that, the water flush was repeated four times, each time water accumulated in the tank. The cumulative amount of water used for washing was 24 L (4.8 L x 5 times).

[0093] After flushing the toilet a predetermined number of times, the test plate was peeled off from the toilet bowl and immediately placed in a sterile dish with the treated surface facing up, followed by drying for 12 to 15 hours in a constant temperature dryer maintained at 50°C to obtain a treated test piece.

[0094] For untreated (blank) test pieces, which were not treated with a cleaning agent, the test pieces were flushed with water in the same manner as above, except that the application of the cleaning solution was omitted. After that, the test pieces were peeled off from the toilet bowl and immediately placed in a sterile dish with the treated side facing up, and dried in a constant temperature dryer maintained at 50°C for 12 to 15 hours to obtain treated test pieces.

[0095] <Antibacterial test>

[0096] E. coli (NBRC3972) suspended in 3% nutrient bouillon was diluted 400 times with saline to obtain a 2.5 × 10 5 ~1.0×10 6 A bacterial solution of cfu / ml was prepared.

[0097] 0.4 ml of bacterial solution was inoculated onto the detergent-treated surface of the treated test piece placed in the petri dish, and then a sterilized polypropylene film cut to a size of 40 mm x 40 mm was immediately placed on top of it and tightly adhered, and the petri dish was then sealed with a lid.

[0098] These test samples sealed in petri dishes were cultured for 24 hours in a thermostatic chamber set at 35±1°C and 90% humidity.

[0099] After 24 hours of incubation, the entire top surface of the test piece, still covered with film, was washed with 9.6 ml of saline using a pipette, and the bacteria that had been cultivated between the film and the top surface of the test piece were washed out into the saline.

[0100] 1.0 ml of each of the washed-out bacterial solution, a solution obtained by further diluting the bacterial solution 100-fold with physiological saline, and a solution obtained by diluting the bacterial solution 10,000-fold with physiological saline were smeared onto a petri dish containing SCDLP medium (Soybean Casein Digest Agar with Lecitin, polysorbate 80).

[0101] Thereafter, the mixture was cultured in a constant temperature bath at 37°C for 24 hours, and the number of colonies (viable bacteria count) was measured.

[0102] On the other hand, for the blanks (untreated), the test pieces were taken immediately after inoculation with the bacterial solution and the test pieces were cultured for 24 hours in a thermostatic chamber set at 35±1°C and 90% humidity. The extraction procedure was carried out in the same manner as above, and the pieces were smeared onto a petri dish. After culturing for 24 hours in a thermostatic chamber at 37°C, the number of colonies (number of viable bacteria) was measured.

[0103] From this antibacterial evaluation test, the antibacterial activity value was calculated based on the following formula. Antibacterial activity value: log [number of viable bacteria on untreated (blank) test piece after 24 hours] - log [number of viable bacteria on treated test piece after 24 hours]

[0104] For each test, two test plates were used, and the average of the antibacterial activity values ​​was calculated as the result.

[0105] The antibacterial activity values ​​obtained were evaluated for their antibacterial effect according to the following criteria. AAA: Antibacterial activity value 4.0 or higher (Live bacteria count less than 0.01% of blank viable bacteria count) AA: Antibacterial activity value 3.0 or more to less than 4.0 (Viable bacteria count of 0.01% to less than 0.1% of the blank viable bacteria count) A: Antibacterial activity value 2.0 or more to less than 3.0 (Live bacteria count of 0.1% to less than 1% of the blank viable bacteria count) BB: Antibacterial activity value 1.0 or more to less than 2.0 (Live bacteria count between 1% and 10% of the blank viable bacteria count) B: Antibacterial activity value 0.7 or more to less than 1.0 (Live bacteria count between 10% and 20% of the blank viable bacteria count) C: Antibacterial activity value 0.4 or more to less than 0.7 (Viable cell count between 20% and 39.8% of blank viable cell count) D: Antibacterial activity value less than 0.4 (Viable bacteria count of 39.8% or more of the blank viable bacteria count)

[0106] The results of the Examples are shown in Table 1, and the results of the Comparative Examples are shown in Table 2.

[0107] [Table 1]

[0108] [Table 2]

[0109] The treated test piece (hydrophilic ceramic tile board) treated with the cleaning agent of Example 1 exhibited an antibacterial effect with an antibacterial activity value of 2 or more, whereas the test piece of Comparative Example 1-1 treated with a cleaning agent that did not contain a water-soluble polymer having a carboxylic acid and / or its salt (xanthan gum) and the test piece of Comparative Example 1-2 treated with a cleaning agent that did not contain an antibacterial agent and / or a bactericide having a cationic group only exhibited an antibacterial effect with an antibacterial activity value of less than 0.4.

[0110] Example 2

[0111] i) As a water-soluble polymer having a carboxylic acid and / or its salt, xanthan gum (trade name: KELZAN AR) and carboxymethyl cellulose (trade name: CMC Daicel 2260, degree of ether substitution 0.8 to 1.0, viscosity at 1% concentration 4000 to 6000) ii) As antibacterial and / or disinfectant agents having a cationic group, benzalkonium chloride (trade name: Hyamine 3500J), a cationic surfactant, and polyhexamethylene biguanide (trade name: Proxel IB), a cationic polymer having a guanide structure, are used.

[0112] iii) As an inorganic acid and / or an organic acid having a sulfonic acid group, sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), which is an inorganic acid A cleaning agent (No. 1-2) having the composition shown in Example 2 of Table 3 was prepared using the above.

[0113] Comparative Example 2

[0114] The water-soluble polymer does not contain carboxylic acid. Guar gum (trade name: SUPERGEL CSA200, manufactured by Pakistan Gum & Chemicals), Hydroxyethyl cellulose (product name: SANHEC ["SANHEC" is a trademark], product sold by Sansho Co., Ltd.) A cleaning agent (No. 3-4) having the composition shown in Comparative Example 2 in Table 3 was prepared using the same ingredients as in Example 2, except that the following was used.

[0115] Next, the appearance of the cleaners was observed, and the pH and viscosity were measured. Antibacterial tests and evaluations were then conducted on test boards (hydrophilic ceramic tile boards and hydrophobic acrylic boards) using each cleaner, simulating the antibacterial function of toilet bowls, in the same manner as in Example 1. The results are shown in Table 3.

[0116] As test plates, 50 mm x 50 mm x 2 mm white acrylic plates (manufactured by Hyoshin, an acrylic specialty store) were prepared together with the 45 mm x 45 mm x 7 mm white ceramic tiles (white mosaic tiles) used in Example 1. The treated test specimens were prepared in the same manner as in Example 1, except that the test plates were rinsed 21 times with water (cumulative amount of water used for rinsing: 101 L (4.8 L x 21 times)) after application of the cleaning solution.

[0117] For each cleaning agent, we conducted the following antifouling tests to simulate the antifouling function of a toilet bowl. The results are shown in Table 3.

[0118] <Stain-resistant testing and evaluation based on the anti-stain function of toilet bowls>

[0119] As hard surface test plates, we prepared a 45mm x 45mm x 7mm white ceramic tile (white mosaic tile) and a 50mm x 50mm x 2mm white acrylic plate (manufactured by Hyoshin, an acrylic specialty store).

[0120] As in Example 1, a screen net cut to an appropriate size was fixed with double-sided tape from the top of the puddle area to the bowl of the same toilet as in Example 1, and one test plate (a hydrophilic ceramic tile plate or a hydrophobic acrylic plate) was fixed with double-sided tape on the screen net at the front of the toilet bowl. In other words, the test plates were fixed to the toilet bowl so that they would not fall off and would not impair the flushing water flow of the toilet.

[0121] After repeating the water flushing three times in the same manner as in Example 1, water droplets adhering to the surface of the test plate were lightly wiped off with tissue paper.

[0122] Next, 2 ml of the prepared cleaner was dripped onto the front surface of a test board (ceramic tile: 45 mm x 45 mm, acrylic board: 50 mm x 50 mm) to cover the hard surface. After leaving it for 3 minutes (180 seconds), the test board was immediately rinsed with water to rinse off the cleaning solution. After that, the water flush was repeated 20 times, each time water accumulated in the tank. The cumulative amount of water used for the rinse was 101 L (4.8 L x 21 times).

[0123] After flushing the test plate a predetermined number of times, it was peeled off from the toilet bowl and immediately dried with the treated surface facing up in a thermostatic oven maintained at 50°C for 30 minutes to obtain a treated test piece.

[0124] For untreated (blank) test pieces, which were not treated with detergent, the test pieces were flushed with water (cumulative flushing volume: 101 L) in the same manner, except that the application of the cleaning solution was omitted. The test pieces were then peeled off from the toilet bowl and immediately placed with the treated side facing up and dried for 30 minutes in a constant temperature dryer maintained at 50°C to obtain treated test pieces.

[0125] For the acrylic plates obtained, the back side of each antifouling treated surface was attached to one side of a 50 mm x 50 mm x 5 mm glass plate using double-sided tape so that the outlines of the two matched. This was to prevent the treated test specimen from floating when it was placed at the bottom of a beaker and tap water was poured down the side of the beaker.

[0126] Each of the ceramic tile plates and acrylic plates bonded to a glass plate prepared as treated test pieces was placed in the center of the bottom of a 600 ml transparent glass beaker with the top surface, which was the anti-fouling treated surface, facing up, and 0.5 ml of model soil (a mixture of 50 g of oleic acid and 50 g of rapeseed oil to which 0.04 g of methyl red had been added and heated to dissolve) was dropped onto the center of the top surface of the treated test piece.

[0127] In this state, tap water was slowly filled into the beaker, allowing it to run down the walls.As the level of tap water in the beaker rose, the top surface of the treated test piece (the anti-fouling treated surface) became wet from all sides.As this process progressed, the rolling up of the model dirt was promoted, and eventually most of the model dirt separated from the top surface of the treated test piece and floated to the surface of the water.

[0128] Immediately after the model soil floating on the water surface was collected with a dropper, the state of the soil remaining on the top surface of the treated test piece was photographed from above.

[0129] The degree of stain removal was evaluated by approximately determining the remaining area ratio to the top surface of the treated test piece using a planar photograph taken from above.

[0130] The level of antifouling property was ranked based on the following index. AAA: No stains remain. AA:Residual area rate ≦1.0% A: Residual area rate ≦2.0% BBB:Residual area rate ≦3.0% BB:Residual area rate ≦4.0% B:Residual area rate ≦5.0% CCC:Residual area rate ≦7.5% CC:Residual area rate ≦10% C:Residual area ratio ≦20% D: Residual area rate ≦100%

[0131] [Table 3]

[0132] The cleaning agent of Example 2, which contains a water-soluble polymer having a carboxylic acid, exhibited superior antibacterial effects on both hydrophilic ceramic tile boards and hydrophobic acrylic boards compared to the cleaning agent of Comparative Example 2, which contains a water-soluble polymer without a carboxylic acid. The difference in antibacterial effects was particularly significant on hydrophobic acrylic boards. Meanwhile, in terms of stain resistance, while the cleaning agent of Comparative Example 2 performed well on hydrophilic ceramic tile boards compared to the blank (untreated), the cleaning agent of Example 2 performed one rank better. On hydrophobic acrylic boards, the cleaning agent of Example 2 exhibited significantly superior performance compared to the cleaning agent of Comparative Example 2 and the blank (untreated).

[0133] Example 3

[0134] i) Xanthan gum (trade name: KELZAN AR) was blended at 0.5% by weight as a water-soluble polymer having a carboxylic acid and / or its salt. ii) as antibacterial and / or bactericidal agents having cationic groups, Dodecyltrimethylammonium chloride (trade name: Nissan Cation BB) was added at 0.5% by weight. Contains 0.5% by weight of benzalkonium chloride (trade name: Hyamine 3500J), Polyhexamethylene biguanide (trade name: ProxelIB), a cationic polymer with a guanide structure, is blended at 0.2% by weight and benzalkonium chloride (trade name: Hyamine 3500J) at 0.5% by weight.

[0135] iii) As inorganic acids and / or organic acids having a sulfonic acid group, inorganic acids such as hydrochloric acid, sulfuric acid, sulfamic acid, nitric acid, and phosphoric acid (all reagents, manufactured by Wako Pure Chemical Industries, Ltd.), and as organic acids having a sulfonic acid group, methanesulfonic acid, benzenesulfonic acid, and meta-xylenesulfonic acid (all reagents, manufactured by Tokyo Chemical Industry Co., Ltd.) were each mixed in the amounts by weight shown in the column for "acid agent" in Table 4; The balance of the remainder was made up with ion-exchanged water to prepare a cleaning agent having the composition shown in Example 3 of Table 4.

[0136] Comparative Example 3

[0137] Similarly, a cleaning agent having the composition shown in Comparative Example 3 in Table 4 was prepared using formic acid, acetic acid, citric acid, and lactic acid (all reagents, manufactured by Wako Pure Chemical Industries, Ltd.) as organic acids having a carboxylic acid group.

[0138] Next, the uniformity of the liquid composition was evaluated based on the appearance of the detergent according to the following criteria. 〇: The appearance of the cleaning solution is uniformly transparent to uniformly translucent △: The appearance of the cleaning solution is uniform white ×: The appearance of the cleaning solution is cloudy or heterogeneous due to the precipitation of gel-like substances.

[0139] Table 4 shows the evaluation results of the uniformity of the cleaning solution.

[0140] [Table 4]

[0141] The liquid composition of Example 3, which used an inorganic acid and / or an organic acid having a sulfonic acid group as the acid agent, was in a homogeneous state, whereas the liquid composition of Comparative Example 3, which used an organic acid having a carboxylic acid group, was in a heterogeneous state.

[0142] Example 4

[0143] i) Xanthan gum (trade name: KELZAN AR) as a water-soluble polymer having a carboxylic acid and / or a salt thereof ii) As antibacterial and / or disinfectant agents having a cationic group, benzalkonium chloride (trade name: Hyamine 3500J), a cationic surfactant, and polyhexamethylene biguanide (trade name: Proxel IB), a cationic polymer having a guanide structure, are used.

[0144] iii) Inorganic acids and / or organic acids having a sulfonic acid group, such as inorganic sulfamic acid or hydrochloric acid (both reagents, manufactured by Wako Pure Chemical Industries, Ltd.) A cleaning agent (No. 1-2) having the composition shown in Example 4 of Table 5 was prepared using the above.

[0145] Next, the appearance of the cleaners was observed, and their pH and viscosity were measured. Antibacterial tests and evaluations were then conducted on test boards (hydrophilic ceramic tile boards and hydrophobic acrylic boards) using each cleaner, simulating the antibacterial function of toilet bowls, in the same manner as in Example 2. The cumulative volume of flushing water was 101 L (4.8 L / flush × 21 flushes), the same as in Example 2.

[0146] The results are shown in Table 5.

[0147] [Table 5]

[0148] When inorganic acids such as sulfamic acid and hydrochloric acid were used as inorganic acids and / or organic acids having sulfonic acid groups, excellent antibacterial effects were observed on both hydrophilic ceramic tile boards and hydrophobic acrylic boards.

[0149] Example 5

[0150] i) xanthan gum (trade name: KELZAN AR) as a water-soluble polymer having a carboxylic acid and / or a salt thereof, ii) Cationic surfactants as antibacterial and / or bactericidal agents having cationic groups Dodecyltrimethylammonium chloride (trade name: Nissan Cation BB), Benzalkonium chloride (trade name: Hyamine 3500J) and Polyhexamethylene biguanide (trade name: ProxelIB), a cationic polymer containing a guanide structure

[0151] iii) As an inorganic acid and / or an organic acid having a sulfonic acid group, sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), which is an inorganic acid,

[0152] iv) As another surfactant, polyoxyethylene alkyl ether (trade name: Emulgen 707, manufactured by Kao Corporation; "Emulgen" is a trademark),

[0153] v) Diethylene glycol monobutyl ether (trade name: Butyl Diglycol NO ["Butyl Diglycol NO" is a trademark], manufactured by Nippon Nyukazai Co., Ltd.) as a water-soluble solvent. Using these, cleaning agents (Nos. 1-4) having the compositions shown in Example 5 of Table 6 were prepared.

[0154] Next, the appearance of the cleaner was observed, and the pH and viscosity were measured. Each cleaner was then used to conduct antibacterial and antifouling tests on ceramic tile boards and acrylic boards. The same procedures as in Example 2 were used, except that the cumulative amount of water used for flushing was 202 L (4.8 L / flush × 42 flushes).

[0155] Furthermore, the cleaning agents of Examples 5-3 and 5-4 and the blank (untreated) were subjected to the following antifungal test and evaluation. The results are shown in Table 6.

[0156] <Antifungal testing and evaluation based on the antifungal function of toilet bowls>

[0157] Antifungal tests were conducted on black mold (Cladosporium sphaerospermum NBRC 6348), which is known to grow in bathrooms and other places, in accordance with Method B (glucose-added inorganic salts agar medium) of the testing methods for plastic products in Appendix A of JIS Z2911:2018.

[0158] A white ceramic tile (white mosaic tile) measuring 45 mm x 45 mm x 7 mm was prepared as a hard surface test plate.

[0159] The hard surface of the test plate was treated in the same manner as in the antibacterial test of Example 5 above (cumulative amount of water used for washing: 202 L [4.8 L / time x 42 times]), to prepare treated test pieces (5 pieces) of ceramic tile plate.

[0160] For untreated (blank) test pieces, in which the test plate was not treated with a detergent, the test plate was flushed with a cumulative total of 202 L (4.8 L / time x 42 times) of water in the same manner as in the antibacterial test of Example 5, except that the application of the detergent solution was omitted. After that, the test plate was peeled off from the toilet bowl and immediately placed with the treated side facing up in a sterile dish, where it was dried for 12 to 15 hours in a constant temperature dryer maintained at 50°C, to obtain a treated test piece.

[0161] <Antifungal test>

[0162] The spore suspension was prepared according to the method for preparing a single spore suspension in JIS Z2911:2018. Approximately 10 6 The concentration was adjusted to 100 cfu / ml.

[0163] The glucose-added inorganic salt agar medium was aseptically dispensed into another petri dish to a thickness of approximately 5 mm and allowed to solidify. The treated test specimens (45 mm x 45 mm x 7 mm ceramic tile plates) contained in the petri dish were removed and placed on the medium with the treated surface facing up. Then, 0.1 ml of the spore suspension was inoculated onto the treated surface and the agar medium using a sprayer, and the petri dish was sealed with a lid. The test was conducted on five test specimens each, treated with the cleaners of Examples 5-3 and 5-4 and untreated.

[0164] These test samples sealed in petri dishes were cultured in a thermostatic chamber set at 24±1°C and 95% humidity for 4 weeks.

[0165] The samples cultured in this antifungal test were then first observed with the naked eye, and then, if necessary, observed under a stereomicroscope.

[0166] The growth status of black mold was evaluated according to the following criteria in accordance with Appendix A of JIS Z2911:2018.

[0167] Mycelium growth rating: Mold growth status (0 to 5) No mold growth is visible to the naked eye or under a stereomicroscope. Mold growth is not visible to the naked eye, but is clearly visible under a stereomicroscope. Mold growth is visible to the naked eye and the area of ​​growth is less than 25% of the total area of ​​the sample: 2 Mold growth is visible to the naked eye and the area of ​​the growth is 25% or more but less than 50% of the total area of ​​the sample: 3 The mycelium is well developed and the area of ​​the developed part is more than 50% of the total area of ​​the sample: 4 The mycelium grows vigorously and covers the entire surface of the sample.

[0168] [Table 6]

[0169] As shown in Example 5, when the cumulative amount of flush water used for washing was 202 L, the antibacterial effect and antifouling performance tended to improve as the xanthan gum content increased.

[0170] Regarding antifungal properties, the mold growth state in Example 5-3 was 0, 2, 2, 2, 2 (N=5), the mold growth state in Example 5-4 was 0, 0, 0, 2, 2 (N=5), and the mold growth state in the blank (untreated) was 4, 4, 4, 4, 4 (N=5). These treatments significantly suppressed mold growth, demonstrating excellent antifungal properties.

[0171] Thus, it was confirmed that good antibacterial and antifungal effects and antifouling properties could be provided even in a usage environment where a large amount of water flows.

Claims

1. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.1 to 5% by weight b) Antibacterial and / or bactericidal agents having cationic groups: 0.1 to 10% by weight c) Inorganic acid and / or organic acid having a sulfonic acid group: 0.1 to 15% by weight and a pH of 3 or less.

2. 2. The composition of claim 1, which, after being applied to a hard surface and then rinsed with water, can render the hard surface antibacterial.

3. 10. The composition of claim 1, which is capable of imparting antifungal properties to hard surfaces.

4. 4. The composition of claim 3, which, after application to a hard surface and subsequent rinsing with water, can render the hard surface antibacterial and antifungal.

5. 5. The composition according to claim 1, which is capable of inhibiting adhesion of oily dirt to a hard surface when the hard surface is applied thereto and then rinsed with water, and when water containing oily dirt splashes on the hard surface or when water splashes on the hard surface after contact with oily dirt.

6. The antibacterial agent and / or bactericide having a cationic group of the above b) is Alkylamine salt type cationic surfactants, alkenylamine salt type cationic surfactants, quaternary ammonium salt type cationic surfactants, pyridine ring salt-containing cationic surfactants, cationic polymers having a quaternary ammonium salt in the main chain or side chain, cationic polymers having a guanidine skeleton or biguanide skeleton in the main chain or side chain, cationic polymers having an amino group in the side chain, and guanidine skeleton or biguanide skeleton compounds other than polymers 5. The composition according to claim 1, which is one or more antibacterial and / or bactericidal agents selected from the group consisting of:

7. The antibacterial agent and / or bactericide having a cationic group of the above b) is 5. The composition according to claim 1, comprising a cationic surfactant having at least one linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and one or both of a cationic polymer having a guanidine skeleton or a biguanide skeleton.

8. The antibacterial agent and / or bactericide having a cationic group of the above b) is The composition according to any one of claims 1 to 4, comprising one or more selected from polyhexamethylene guanidine or a salt thereof, polyaminopropyl biguanide or a salt thereof, polyhexamethylene biguanide or a salt thereof, and chlorhexidine or a salt thereof.

9. The antibacterial agent and / or bactericide having a cationic group of the above b) is The composition according to claim 8, further comprising a quaternary ammonium salt type cationic surfactant.

10. The composition according to any one of claims 1 to 4, wherein the water-soluble polymer having a carboxylic acid and / or its salt (a) is xanthan gum, pectin and / or its salt, gellan gum and / or its salt, diutan gum, welan gum, gum arabic and / or its salt, alginic acid and / or its salt, hyaluronic acid and / or its salt, tragacanth gum and / or its salt, succinoglycan and / or its salt, carboxymethylcellulose and / or its salt, carboxyethylcellulose and / or its salt, carboxyvinyl polymer and / or its salt, or polyacrylic acid and / or its salt.

11. 5. The composition according to claim 1, wherein the water-soluble polymer having a carboxylic acid and / or a salt thereof is xanthan gum.

12. 5. The composition according to claim 1, wherein the inorganic acid and / or the organic acid having a sulfonic acid group in c) is one or more acidic agents selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, toluenesulfonic acid, and styrenesulfonic acid.

13. 5. The composition according to claim 1, wherein the viscosity measured under the conditions described in the specification is in the range of 50 to 1000 mPa·s.

14. 5. The composition according to claim 1, which contains 2 to 30% by weight of glycol and / or glycol ether.

15. 15. The composition of claim 14, wherein said glycol is hexylene glycol and said glycol ether is diethylene glycol monobutyl ether and / or propylene glycol monomethyl ether.

16. The composition according to any one of claims 1 to 4, wherein the hard surface is a toilet bowl and / or its drain, a kitchen sink and / or its drain, a bathroom floor, wall, bathtub and / or its drain, or a washbasin and / or its drain.

17. 5. The composition according to claim 1, wherein the antibacterial liquid acidic cleaning composition for hard surfaces is used for cleaning and antibacterial purposes in toilet bowls.

18. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.1 to 5% by weight b) Antibacterial and / or bactericidal agents having cationic groups: 0.1 to 10% by weight c) Inorganic acid and / or organic acid having a sulfonic acid group: 0.1 to 15% by weight A method for imparting antibacterial properties to a hard surface by treating the surface with a liquid composition containing the compound and having a pH of 3 or less.

19. 20. The method of claim 18, which can impart antifungal properties to hard surfaces.

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