Liquid antibacterial cleaning composition for hard surfaces and method for imparting antibacterial properties

Abstract

To provide an antibacterial cleaning agent composition and an antibacterial property imparting method, which are capable of imparting an antibacterial property to a processing target over a whole hard surface irrespective of a hydrophilic surface or a hydrophobic surface.SOLUTION: A liquid antibacterial cleaning detergent composition comprises a) a water-soluble polymer having a carboxylic acid and / or its salt: 0.05 to 5 wt.%, b) an antibacterial agent and / or bactericidal agent having a cationic group: 0.1 to 10 wt.%, and c) an electrolyte: 0.1 to 15 wt.%, and has a pH of 3 to 12. An antibacterial property imparting method treats a hard surface made of a hydrophilic material or a hydrophobic material with a liquid composition comprising a) a water-soluble polymer having carboxylic acid and / or its salt: 0.05 to 5 wt.%, b) an antibacterial agent and / or a sterilization agent having a cationic base: 0.1 to 10 wt.%, and c) an electrolyte: 0.1 to 15 wt.%, and having the pH of 3 to 12.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antibacterial detergent composition and a method for imparting antibacterial properties to hard surfaces by treating the hard surfaces. [Background technology]

[0002] Dirt caused by the growth 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 have been proposed that remove slimy and pink stains caused by bacterial or fungal growth. These cleaners are basically intended to remove existing bacteria and fungi, as well as their metabolites, and are unable to impart antibacterial or antifungal properties that would prevent new bacterial or fungal growth on the cleaned hard surface. In particular, in cleaning operations that involve rinsing with water, it has been difficult to leave a certain amount of antibacterial agent on the target hard surface at a concentration that would allow antibacterial properties to be exerted.

[0005] Residential spaces that require rinsing with water include kitchen sinks, bathroom bathtubs, floors, walls, mirrors, handrails, washbasins, chairs, sinks, and toilet bowls. However, these wet areas are prone to bacterial and fungal contamination due to the proliferation of bacteria and fungi. Furthermore, the hard surfaces in these areas are made of a variety of materials with hydrophobic or hydrophilic properties, such as plastic, stainless steel, enamel, tile, and ceramics.

[0006] For these reasons, there is a demand for cleaning agents that can impart antibacterial and antifungal properties to hard surfaces made of various materials in wet residential spaces where rinsing with water is required.

[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. 2 The 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. [Prior art documents] [Patent documents]

[0016] [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 Summary of the Invention [Problem to be solved by the invention]

[0017] An object of the present invention is to provide a detergent composition and a method for imparting antibacterial properties, which can impart antibacterial properties to surfaces to be treated, regardless of whether they are hydrophilic or hydrophobic hard surfaces, even in cleaning operations involving rinsing with water. [Means for solving the problem]

[0018] The present invention can be expressed, for example, as follows. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.05 to 5% by weight b) Antibacterial agents and / or bactericides having cationic groups: 0.1 to 10% by weight c) Electrolyte: 0.1~15% by weight A liquid antibacterial cleaning composition for hard surfaces, comprising the above compound and having a pH of 3 to 12.

[0019] The present invention can also be expressed as follows. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.05 to 5% by weight b) Antibacterial agents and / or bactericides having cationic groups: 0.1 to 10% by weight c) Electrolyte: 0.1~15% by weight A method for imparting antibacterial properties, which comprises treating a hard surface made of a hydrophilic or hydrophobic material with a liquid composition containing the above compound and having a pH of 3 to 12. [Effects of the Invention]

[0020] According to the present invention, the surface to be treated can be made antibacterial even in a cleaning operation that involves rinsing with water, regardless of whether it is a hydrophilic or hydrophobic hard surface. The antibacterial property here refers to the ability to inhibit the proliferation of bacteria when they adhere to the surface and are present in the presence of moisture and a nutrient source. DETAILED DESCRIPTION OF THE INVENTION

[0021] (1) The liquid antibacterial detergent composition for hard surfaces of the present invention and the liquid composition used in the antibacterial method for treating hard surfaces made of a hydrophilic or hydrophobic material of the present invention (hereinafter, both the "liquid antibacterial detergent composition" and the "liquid 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: 0.05 to 5% by weight b) Antibacterial agents and / or bactericides having cationic groups: 0.1 to 10% by weight c) Electrolyte: 0.1~15% by weight and its pH is 3 to 12.

[0022] (2) Antibacterial and / or disinfectant agents having cationic groups

[0023] (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."

[0024] 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.

[0025] 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.

[0026] (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.

[0027] 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.

[0028] 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 electrolyte to form a cleaning agent, the antibacterial agent and / or bactericide having a cationic group can be left 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.

[0029] 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.

[0030] 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.

[0031] (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.

[0032] 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.

[0033] (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.

[0034] 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; the same applies hereinafter).

[0035] (ii) As the quaternary ammonium salt type, tetraalkyl (or tetraalkenyl) ammonium salts or benzyltrialkyl (or trialkenyl) ammonium salts are preferred.

[0036] 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 specific 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, beef 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, N,N-Didecyl-N-methylpoly(oxyethyl)ammonium propionate Examples include:

[0037] (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.

[0038] 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.

[0039] 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.

[0040] 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; the same applies below]). Other examples include polyaminopropyl biguanide or a salt thereof (e.g., hydrochloride). Among these, polyhexamethylene guanidine or polyhexamethylene biguanide is particularly preferred.

[0041] The guanidine or biguanide skeleton compounds in 3) above are non-polymeric guanidine or biguanide skeleton compounds, i.e., excluding the cationic polymers having a guanidine or biguanide skeleton described above. Specific examples include chlorhexidine or its salts, such as the gluconate salt chlorhexidine gluconate (trade name: Spectradyne ["Spectradyne" is a trademark], manufactured by LONZA, Inc.; the same applies hereinafter), hydrochloride, acetate, etc. Further examples include alexidine hydrochloride.

[0042] 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.

[0043] (3) Water-soluble polymers containing carboxylic acids and / or their salts

[0044] It is presumed that when the liquid composition of the present invention is rinsed with water, the dilution effect causes the complex of the antibacterial agent and / or bactericide 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.

[0045] Materials in residential spaces that are subject to cleaning operations involving rinsing with water include hydrophilic hard surfaces such as ceramic tiles, porcelain, glass, and ceramics including enamel, as well as hydrophobic hard surfaces such as plastics (synthetic resins) such as acrylic resins (acrylic ester resins, methacrylic ester resins, etc.), polyester resins (polyethylene terephthalate resins, etc.), and polyvinyl chloride resins, and stainless steel.

[0046] Even if the liquid composition of the present invention is applied and then rinsed with water, it remains on hydrophilic and hydrophobic hard surfaces, including all of the materials exemplified above, not limited to those in residential spaces, and can thereby exert antibacterial and / or antifungal properties.

[0047] 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.

[0048] 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.

[0049] Among these, xanthan gum, gellan gum, diutan gum, succinoglycan, and carboxymethylcellulose are preferred, with xanthan gum being most preferred.

[0050] These water-soluble polymers containing carboxylic acids and / or their salts have a negative charge and can form complexes with antibacterial agents and / or bactericides containing cationic groups, which are presumably responsible for phase separation and insolubilization upon rinsing with water, resulting in the complexes remaining on the hard surface.

[0051] 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.

[0052] Furthermore, because water-soluble polymers containing carboxylic acids and / or their salts are negatively charged, they are presumed to hydrophilize hard surfaces, and can be used to modify hydrophilic hard surfaces such as ceramic tiles and hydrophobic hard surfaces such as plastics and stainless steel, providing excellent antifouling properties that prevent oily stains such as sebum from adhering to surfaces exposed to water.

[0053] 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.

[0054] 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 0.05 to 5% by weight.

[0055] If the content is less than 0.05% by weight, sufficient antibacterial properties are not exhibited. If the content exceeds 5.0% by weight, the viscosity becomes too high, impairing the handleability of the liquid composition. The content is preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, and even more preferably 0.25 to 0.6% by weight.

[0056] (4) Electrolyte

[0057] However, when a cationic surfactant and a water-soluble polymer having a carboxylic acid and / or its salt are used in a considerable amount in a cleaning agent or antibacterial agent, a water-insoluble complex is immediately formed, making the cleaning agent or antibacterial agent unusable. Therefore, in order to suppress the formation of a strong gel due to the complex formation and to enable uniform mixing, it is necessary to further contain the above-mentioned "c) electrolyte."

[0058] The concentration of "c) electrolyte" in the liquid composition of the present invention is 0.1 to 15% by weight, and depends on the concentration of the water-soluble polymer having a carboxylic acid and / or its salt and the antibacterial agent and / or disinfectant having a cationic group. It is preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight, and even more preferably 2 to 9% by weight.

[0059] The pH of the liquid composition of the present invention is 3 to 12, more preferably 4 to 12. By adjusting the pH to a level that allows use with bare hands, the liquid composition can be used easily and safely without particular concern about irritation to the skin, eyes, etc. Furthermore, when cleaning with bare hands, it is possible to check the degree to which dirt is removed by touching with the fingers.

[0060] (4-1) Examples of the “c) electrolyte” in the present invention include inorganic acids and / or salts thereof, monovalent organic acids and / or salts thereof, polycarboxylic acids having metal chelating ability and / or salts thereof, polyphosphonic acids and / or salts thereof, and polyphosphoric acids and / or salts thereof.

[0061] (4-2) Preferred examples of inorganic acids and / or salts thereof include hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid, and silicic acid, as well as their alkali metal salts, alkaline earth metal salts, and zinc salts. Considering that the pH of the final liquid composition is 3 to 12, it is preferable to mainly use inorganic salts.

[0062] (4-3) Preferred examples of monovalent organic acids and / or salts thereof include formic acid, acetic acid, lactic acid, propionic acid, fatty acids having a carbon number greater than these, and benzoic acid, as well as their respective alkali metal salts, alkaline earth metal salts, and zinc salts.

[0063] (4-4) Preferred examples of polycarboxylic acids and / or salts thereof having metal chelating ability include malonic acid, succinic acid, glutaric acid, gluconic acid, malic acid, citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenetriacetic acid, and hydroxyethyliminodiacetic acid, as well as their salts (e.g., sodium salts). Particularly preferred examples include trisodium citrate and sodium ethylenediaminetetraacetate.

[0064] (4-5) Preferred examples of polyphosphonic acids and / or salts thereof having metal chelating ability include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminopoly(methylenephosphonic acid), polyethylenepolyaminepoly(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and their salts. Examples of the salts include alkali metal salts such as sodium and potassium salts, ammonium salts, and alkanolamine salts such as monoethanolamine and triethanolamine salts.

[0065] (4-6) Preferred examples of polyphosphoric acids and / or salts thereof having metal chelating ability include metaphosphoric acid, orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid, and their respective salts.

[0066] The "electrolyte" may be any one of the above, or may be a combination of two or more of the above.

[0067] (5) Examples of components other than a), b) and c) that may be contained in the liquid composition of the present invention

[0068] (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 foaming properties and rinsing properties after cleaning. Foaming properties clearly indicate the state of supply of the detergent to the surface to be cleaned and also contribute to smooth movement of the sponge or brush.

[0069] (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.

[0070] Among these, alkyl glucosides are particularly preferred from the viewpoints of foaming ability, foam retention, and detergent adhesion to vertical hard surfaces. Specific examples include those represented by the following formula (I): R 1 -(OR 2 )nGm ....(I) [In formula (I), R 1 is an alkyl group having 8 to 18 carbon atoms, R 2 represents an alkylene group having 2 to 4 carbon atoms, G represents a group derived from a reducing sugar, n represents the average number of moles added (0 to 5), and m represents the average degree of condensation (1 to 3). The reducing sugar may be either an aldose or a ketose, but is preferably glucose.]

[0071] Examples of alkyl glucosides include octyl polyglucoside, 2-ethylhexyl polyglucoside, decyl polyglucoside, lauryl polyglucoside, myristyl polyglucoside, palmityl polyglucoside, stearyl polyglucoside, and oleyl polyglucoside, with alkyl glucosides having an alkyl group with 14 or less carbon atoms being particularly preferred.

[0072] Alkyl glucosides are less likely to generate aggregates during cleaning procedures involving rinsing with water, and provide a better finish in terms of feel when touching the target surface with your hands. The alkyl glucoside is preferably contained in the liquid composition of the present invention at 0.5 to 10% by weight. If the content is less than 0.5% by weight, the foaming properties, foam retention, and adhesion to hard surfaces are insufficient. If the content exceeds 10% by weight, the foam properties do not change.

[0073] (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 neutral to 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).

[0074] 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.

[0075] (iii) The liquid composition of the present invention may also contain an anionic surfactant, if necessary. Specific examples of the anionic surfactant that may be contained include alkyl ether sulfates, polyoxyalkylene alkyl ether sulfates, and fatty acid salts (soaps).

[0076] In addition, since anionic surfactants may form insoluble complexes with the "b) antibacterial agent and / or bactericide having a cationic group," it is necessary to suppress the formation of insoluble complexes by blending "c) electrolytes" to obtain a uniform liquid composition.

[0077] (5-2) The liquid composition of the present invention preferably contains a water-soluble solvent for one or more of the following reasons: maintaining uniform dissolution stability or uniform dispersion stability of the components; improving foamability and foam retention when sprayed; and further improving cleansing properties. The inclusion of a water-soluble solvent in the liquid composition of the present invention has the effect of enhancing uniform dissolution stability or uniform dispersion stability even when the electrolyte content is reduced.

[0078] 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).

[0079] 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.

[0080] 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 cleaning power for oily stains is not fully exhibited, and if it exceeds 30% by weight, the foaming ability and foam retention tend to be reduced, and there may be situations where the odor is unpleasant. More preferably, it is 3 to 20% by weight, and even more preferably, 5 to 15% by weight.

[0081] The viscosity of the liquid composition of the present invention is preferably in the range of 20 to 500 mPa·s. If the viscosity is less than 20 mPa·s, the components are easily washed away by rinsing with water, and if the viscosity is more than 500 mPa·s, it becomes difficult to apply the composition evenly over a wide area. A range of 50 to 400 mPa·s is more preferable, and a range of 70 to 350 mPa·s is particularly preferable. The viscosity of the liquid composition is measured using a B-type viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.) with a TM2 rotor at a speed of 60 rpm.

[0082] (5-3) The liquid composition of the present invention may contain 0.5 to 5 wt % of an alkaline agent such as alkanolamine to improve the cleansing properties of soap scum and sebum stains, 0.5 to 10 wt % of ethanol or isopropyl alcohol to improve the refreshing feeling and adjust the viscosity of the detergent, and other additives such as bactericides, preservatives, deodorants, fragrances, colorants, pigments, thickeners other than water-soluble polymers having carboxylic acids and / or salts thereof, and water. Deodorants may be contained in amounts of about 0.1 to 5 wt %, and preferred examples include green tea extract and cyclodextrin.

[0083] (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, examples of means for supplying the liquid composition to the hard surface include means for supplying the liquid composition by directly spraying it onto the target hard surface using a sprayer such as a trigger sprayer or an aerosol sprayer, means for supplying the liquid composition by squeezing it using a squeeze bottle and discharging it directly onto the target hard surface, and means for supplying the liquid composition to the target hard surface, i.e., a toilet bowl, together with water when flushing water is discharged, as in an automatic flush cleaner, etc. Preferred means include means that utilize the foaming properties of the liquid composition to generate foam and utilize the adhesiveness of the foam for application or cleaning, i.e., means for directly supplying the foamed liquid composition to the target hard surface using a trigger-type or squeeze-type foam dispenser.

[0084] The liquid composition of the present invention supplied to a hard surface can be applied to the target hard surface using, for example, a cloth-like, sponge-like, brush-like, or other form of tool for cleaning or application, or with bare hands or using rubber gloves, etc., to perform cleaning or application, etc. 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 perform cleaning or application, etc. [Example]

[0085] Example 1

[0086] Examples of water-soluble polymers having a carboxylic acid and / or a salt thereof include xanthan gum (trade name: KELZAN AR ["KELZAN" is a trademark], manufactured by CP KELCO; the same applies hereinafter), As an antibacterial agent and / or bactericide having a cationic group, cationic surfactant coconut alkylbenzyldimethylammonium chloride [ Benzalkonium chloride ] (Product name: Hyamine 3500J ["Hyamine" is a trademark], manufactured by LONZA. The same applies below.) As an electrolyte, trisodium citrate (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), which is a polycarboxylic acid and / or its salt having metal chelating ability, and As a water-soluble solvent, diethylene glycol monobutyl ether (product name: Butyl Diglycol NO ["Butyl Diglycol NO" is a trademark], manufactured by Nippon Nyukazai Co., Ltd.; the same applies hereinafter) A cleaning agent (liquid composition; the same applies to the following Examples and Comparative Examples) having the composition shown in Example 1 of Table 1 was prepared using the above.

[0087] 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 at a speed of 60 rpm (the same applies to viscosity measurements in the following Examples and Comparative Examples). Antibacterial tests and evaluations were then conducted on acrylic boards and ceramic tile boards using each cleaner. The results are shown in Table 1.

[0088] Comparative Example 1

[0089] Using the same components as in Example 1, a cleaning agent having the composition shown in Comparative Example 1 in Table 1 was prepared.

[0090] The appearance of the cleaners was then observed, and their pH and viscosity were measured. Antibacterial tests and evaluations were then conducted on acrylic boards and ceramic tile boards using each cleaner. The results are shown in Table 1.

[0091] <Antibacterial testing and evaluation>

[0092] The antibacterial test and evaluation were carried out in accordance with JIS Z2801 antibacterial test for plastic products.

[0093] 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).

[0094] Two milliliters of the prepared cleaner was dripped onto the horizontally positioned top surface of each test plate (ceramic tile: 45 mm × 45 mm, acrylic plate: 50 mm × 50 mm) to treat the hard surface. After leaving the test plate for 3 minutes (180 seconds), the entire top surface of the test plate was immediately rinsed with tap water at a flow rate of 25 ml / sec for 8 seconds (200 ml total). The back surface was also rinsed with tap water for 3 seconds. The test plate was then immediately placed with the treated side facing up in a sterile dish and dried in a constant temperature dryer maintained at 50°C for 12 hours to obtain treated test specimens.

[0095] For untreated (blank) test pieces, which were not treated with a cleaning agent, the entire top surface of the test piece was rinsed with tap water at a flow rate of 25 ml / sec for 8 seconds (200 ml in total). The acrylic and ceramic tile test pieces were prepared in the same manner.

[0096] <Antibacterial test>

[0097] Equal amounts of Staphylococcus aureus (NBRC13276) and Escherichia coli (NBRC3972) cultured in suspension in 3% nutrient bouillon were mixed and then diluted 400 times with saline to obtain a 2.5 × 10 5 ~1.0×10 6 A bacterial solution of cfu / ml was prepared.

[0098] 0.4 ml of bacterial solution was inoculated onto the detergent-treated surface of the treated test specimen (a 50 x 50 mm acrylic plate or a 45 x 45 mm ceramic tile plate) 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.

[0099] These test samples sealed in petri dishes were cultured for 24 hours in a thermostatic chamber set at 35±1°C and 90% humidity.

[0100] 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.

[0101] 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).

[0102] 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.

[0103] 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.

[0104] 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]

[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 are shown in Table 1.

[0107] [Table 1]

[0108] The test specimens treated with the detergent of Example 1 exhibited excellent antibacterial effects with antibacterial activity values ​​of 4 or more on both the hydrophobic acrylic board and the hydrophilic ceramic tile board, whereas the test specimens of Comparative Examples 1-1 and 1-2, which were treated with detergents that did not contain a water-soluble polymer having a carboxylic acid and / or its salt (xanthan gum), and the test specimens of Comparative Examples 1-3 and 1-4, which were treated with detergents that did not contain a cationic surfactant, which is an antibacterial agent and / or bactericide having a cationic group, only exhibited antibacterial effects with antibacterial activity values ​​of less than 0.4 on both the acrylic board and the ceramic tile board.

[0109] Example 2

[0110] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As an antibacterial agent and / or bactericide having a cationic group, a cationic surfactant is Coconut alkylbenzyldimethylammonium chloride (trade name: Hyamine 3500J), N,N-didecyl-N-methylpoly(oxyethyl)ammonium propionate / polyethylene glycol ethylene glycol (trade name: Bardap26 ["Bardap" 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), Dodecyltrimethylammonium chloride (trade name: Nissan Cation BB ["Nissan Cation" is a trademark], manufactured by NOF Corporation; the same applies hereinafter) The electrolyte is a polycarboxylic acid and / or its salt having metal chelating ability. Trisodium citrate (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), Sodium ethylenediaminetetraacetate (EDTA-4Na) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) A cleaning agent having the composition shown in Example 2 of Table 2 was prepared using the above.

[0111] The appearance of the cleaners was then observed, and their pH and viscosity were measured. Antibacterial tests and evaluations were then conducted on acrylic boards and ceramic tile boards using each cleaner in the same manner as in Example 1. The results are shown in Table 2.

[0112] [Table 2]

[0113] The test pieces treated with the cleaning agent containing the cationic surfactant shown in Example 2 showed excellent antibacterial activity on the hydrophobic acrylic plate, with an antibacterial activity value of 4 or 2 or more.

[0114] Example 3

[0115] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, Xanthan gum (product name: KELZAN AR) Diutan gum (product name: KELCO-CRETE DG ["KELCO" is a trademark], manufactured by CP KELCO), Carboxymethylcellulose (trade name: FINNFIX ["FINNFIX" is a trademark], manufactured by CP KELCO) of, As an antibacterial agent and / or bactericide having a cationic group, a cationic surfactant is used. Coconut alkylbenzyldimethylammonium chloride (trade name: Hyamine 3500J), Dodecyltrimethylammonium chloride (product name: Nissan Cation BB) of, As an electrolyte, trisodium citrate (anhydrous), a polycarboxylic acid and / or its salt with metal chelating ability (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) A cleaning agent having the composition shown in Example 3 of Table 3 was prepared using the above.

[0116] Next, the appearance of the cleaners was observed, and the pH and viscosity were measured. Antibacterial tests and evaluations were then carried out on acrylic boards and ceramic tile boards using each cleaner in the same manner as in Example 1. The results are shown in Table 3.

[0117] Comparative Example 2

[0118] 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 having the composition shown in Comparative Example 2 in Table 3 was prepared using the same ingredients as in Example 3, except that the above was used (thus, polycarboxylic acid and / or its salt having metal chelating ability, which is an electrolyte, was not used).

[0119] Next, the appearance of the cleaners was observed, and the pH and viscosity were measured. Antibacterial tests and evaluations were then carried out on acrylic boards and ceramic tile boards using each cleaner in the same manner as in Example 1. The results are shown in Table 3.

[0120] [Table 3]

[0121] The test specimens treated with the cleaner of Example 3 exhibited an antibacterial activity value of 1.7 or 4 or more on the hydrophobic acrylic board and an antibacterial activity value of 1.6 or 2 or more on the hydrophilic ceramic tile board. On the other hand, the test specimens treated with the cleaner of Comparative Example 2, which used a water-soluble polymer that did not contain a carboxylic acid, exhibited only an antibacterial activity value of less than 0.5 on the acrylic board and less than 1.5 on the ceramic tile board.

[0122] Example 4

[0123] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As an antibacterial agent and / or disinfectant having a cationic group, cationic surfactant coconut alkyl benzyl dimethyl ammonium chloride (trade name: Hyamine 3500J) was used. As an electrolyte, trisodium citrate (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), which is a polycarboxylic acid and / or its salt having metal chelating ability, Diethylene glycol monobutyl ether (product name: Butyldiglycol NO) as a water-soluble solvent The cleaning agent shown in Example 4 of Table 4 was prepared using the above.

[0124] Next, the appearance of the cleaners was observed, and the pH and viscosity were measured. Antibacterial tests and evaluations were then carried out on acrylic boards and ceramic tile boards using each cleaner in the same manner as in Example 1. The results are shown in Table 4.

[0125] [Table 4]

[0126] As shown in Example 4, test pieces treated with a cleaning agent containing a cationic surfactant in a concentration range of 0.1 to 0.9 wt% showed excellent antibacterial activity on hydrophobic acrylic plates, with an antibacterial activity value of 1 or more at a concentration of 0.1 wt%, and an antibacterial activity value of 4 or more at concentrations of 0.2 wt% or more.

[0127] Example 5

[0128] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As an antibacterial agent and / or disinfectant having a cationic group, cationic surfactant coconut alkyl benzyl dimethyl ammonium chloride (trade name: Hyamine 3500J) was used. As an electrolyte, trisodium citrate (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), which is a polycarboxylic acid and / or its salt having metal chelating ability, The cleaning agent shown in Example 5 of Table 5 was prepared using diethylene glycol monobutyl ether (trade name: Butyl Diglycol NO) as the water-soluble solvent.

[0129] The appearance of the cleaners was then observed, and their pH and viscosity were measured. Antibacterial tests and evaluations were then conducted on acrylic boards and ceramic tile boards using each cleaner in the same manner as in Example 1. The results are shown in Table 5.

[0130] [Table 5]

[0131] As shown in Example 5, test pieces treated with a cleaning agent containing xanthan gum in a concentration range of 0.1 to 0.4 wt% showed excellent antibacterial activity, with an antibacterial activity value of 1 or more at concentrations of 0.1 and 0.2 wt%, and an antibacterial activity value of 4 or more at concentrations of 0.3 and 0.4 wt%, on both hydrophobic acrylic boards and hydrophilic ceramic tile boards.

[0132] Example 6

[0133] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As an antibacterial agent and / or bactericide having a cationic group, a cationic surfactant is Coco-alkylbenzyldimethylammonium chloride (trade name: Hyamine 3500J) and Dodecyltrimethylammonium chloride (trade name: Nissan Cation BB) The electrolyte is a polycarboxylic acid and / or its salt having metal chelating ability. Trisodium citrate (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), Sodium ethylenediaminetetraacetate (EDTA-4Na) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) of, Other surfactants include lauryl glucoside (trade name: Mydol 12, manufactured by Kao Corporation; the same applies below), Lauryl dimethylamine oxide (trade name: Unisafe A-LM ["Unisafe" is a trademark], manufactured by NOF Corporation) of, As a water-soluble solvent Diethylene glycol monobutyl ether (trade name: Butyl diglycol NO) The bathroom cleaner shown in Example 6 in Table 6 was prepared using the above ingredients. The values ​​for each component in Table 6 are in weight percent.

[0134] The appearance of the detergent was then observed, and the pH and viscosity were measured. Each detergent was tested and evaluated as follows. The results are shown in Table 6.

[0135] Each detergent was placed in a commercially available trigger spray container (Condor C Spray Container 500 ["Condor" is a trademark], manufactured by Yamazaki Sangyo Co., Ltd.) and used to evaluate the foaming properties when sprayed and the adhesion of the foam to vertical surfaces. The cleaning power for the bathtub and the effectiveness in inhibiting the adhesion of soil to a bathtub model were also evaluated. Furthermore, antibacterial testing and evaluation were carried out in the same manner as in Example 1, except that the treatment of hard surfaces was carried out by spraying each detergent onto an acrylic plate and a ceramic tile plate using the container (and leaving it for 3 minutes).

[0136] <Evaluation of foaming when spraying>

[0137] 100 g of each cleaner was placed in the commercially available trigger spray container, and the tip of the trigger nozzle was set 20 cm away from a vertically placed black acrylic plate (32 cm wide x 55 cm long x 0.2 cm thick, acrylic surface-hardened plate "801, MR00", manufactured by Acri Sunday Co., Ltd.). The cleaner was sprayed, and the foaming and adhesion of the foam were observed according to the following criteria.

[0138] [Evaluation criteria for foaming] 〇: Foam is formed well △: There is little foam and it is mixed with the liquid. ×: The amount of foam is very small and it is almost liquid.

[0139] [Evaluation criteria for foam adhesion]

[0140] The state of foam adhesion is observed and evaluated 30 seconds after spraying. A: Immediately after spraying, the foam remains in the area where it was applied. B: Immediately after spraying, the foam slowly drips and spreads downward from the spot where it first adhered. C: Immediately after spraying, the foam slowly drips downwards from the spot where it was applied. D: Immediately after spraying, the foam quickly drips downwards from the spot where it was applied. E: Immediately after spraying, the foam is dripping downward and moving away from the spot where it was attached, and the foam is beginning to disappear.

[0141] <Bathtub cleaning power test>

[0142] A polyester plate (20 cm wide x 20 cm long x 0.3 cm thick) and an acrylic plate (16 cm wide x 18 cm long x 0.3 cm thick) were fixed to the inside wall of a typical household bathtub as test plates.

[0143] Two adult men, two adult women, and one junior high school boy took a bath once a day for three months (during which time the bath water was changed every two days, and the polyester and acrylic plates were used without being washed), and sebum stains were left on the surface of the test plates.

[0144] After the soiled test plate was allowed to dry naturally at room temperature, 1.0 ml of each cleaning agent from Example 6 was applied in a circular pattern to the test plate, and the test plate was gently scrubbed five times with a sponge cut to a size of 1 cm wide x 2 cm long x 2 cm thick.

[0145] Immediately afterwards, the test plate was rinsed with tap water at a flow rate of 35 ml / sec, dried, and the degree of removal of the stain was visually observed according to the following criteria.

[0146] [Criteria for evaluating cleaning power] 〇: Dirt is removed cleanly △: Slight dirt remains ×: noticeable dirt remains

[0147] <Bathtub model dirt adhesion test>

[0148] As a model sebum stain for a bathtub, stains having the following composition were prepared. Model sebum soil: oleic acid / linoleic acid / palmitic acid / cholesterol / liquid paraffin = 20 / 40 / 20 / 10 / 10 (wt%)

[0149] (Test Method)

[0150] As hard surface test plates, a 50 mm × 50 mm × 3 mm black acrylic plate (manufactured by Hyoshin, an acrylic specialty store) and a 45 mm × 45 mm × 7 mm white ceramic tile (white mosaic tile) were prepared.

[0151] Using the spray bottle described above, each cleaning agent was sprayed once (1.4 ml) onto the hard surface of the test plate, covering the top surface. After leaving it for 3 minutes (180 seconds), the test plate was immediately rinsed by spraying tap water over the entire top surface at a flow rate of 25 ml / sec for 8 seconds (200 ml total). The back surface was also rinsed with tap water for 3 seconds. The test plate was then dried at 50°C for 30 minutes to obtain a treated test specimen.

[0152] For untreated (blank) test plates that were not treated with a cleaning agent, tap water was sprayed onto the entire top surface of the test plate at a flow rate of 25 ml / sec for 8 seconds (total of 200 ml), and then the same procedure was repeated to obtain untreated (blank) test pieces.

[0153] The model sebum soil was heated to about 60°C and dissolved (into a liquid state) by stirring. 80 ml of hot water (70 ml for ceramic tile boards) was placed in a 100 ml beaker, and when the temperature of the hot water reached 43°C, 0.104 g of the model sebum soil that had been heated and dissolved was added. After addition, the oily model sebum soil was finely dispersed by vigorously stirring.

[0154] Immediately afterwards, the stirring with the stirrer was switched to medium stirring, and the treated test piece that had been treated with the detergent was immersed vertically with its treated surface facing the stirring bar, and this was maintained for 3 minutes, allowing the model sebum stains to adhere to the treated test piece.

[0155] After 3 minutes, the stirring was stopped, the treated test piece was slowly pulled out, the back side of the treated test piece was wiped with tissue paper, and the treated test piece was dried at 50°C for 30 minutes.

[0156] After drying, the test plate was conditioned for 30 minutes and then weighed. The weight was then measured and the amount of dirt attached was calculated from the difference between the weight of the test plate before and after treatment with the detergent.

[0157] Furthermore, an untreated (blank) test piece was tested in the same manner, and the amount of adhesion was calculated in the same manner.

[0158] The adhesion rate of model sebum soil on each of the test plates treated with the detergent and the untreated (blank) test piece was calculated using the following formula. Sebum stain adhesion rate = [amount of stain (g) / amount of stain placed in beaker (0.104g)] x 100 (%)

[0159] <Antifungal test>

[0160] The cleaning agent of Example 6-3 was subjected to an antifungal test.

[0161] 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.

[0162] A 50 mm × 50 mm × 2 mm white acrylic plate (manufactured by Hyoshin, an acrylic specialty store) was prepared as a hard surface test plate.

[0163] Treated test pieces (five pieces) of acrylic plates were prepared in the same manner as in Example 1, except that the hard surfaces of the test plates were treated by spraying the cleaning agent of Example 6-3 onto the test plates from the container (and leaving it for 3 minutes).

[0164] For untreated (blank) test pieces, which were not treated with a cleaning agent, the entire top surface of the test piece was rinsed with tap water at a flow rate of 25 ml / sec for 8 seconds (200 ml in total). Five acrylic test pieces were prepared using the same procedure.

[0165] <Antifungal test>

[0166] 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.

[0167] 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 (50 mm x 50 mm x 2 mm acrylic 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 cleaning solution of Example 6-3 and untreated.

[0168] These test samples sealed in petri dishes were cultured in a thermostatic chamber set at 24±1°C and 95% humidity for 4 weeks.

[0169] The samples cultured in this antifungal test were then first observed with the naked eye, and then, if necessary, observed under a stereomicroscope.

[0170] The growth status of black mold was evaluated according to the following criteria in accordance with Appendix A of JIS Z2911:2018.

[0171] 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.

[0172] [Table 6]

[0173] The cleaning agents suitable for use in bathrooms shown in Examples 6-1, 6-2 and 6-3 exhibited excellent performance in terms of foaming, foam adhesion and cleaning power when sprayed onto hard surfaces using a spray container.

[0174] In addition, in the treatment by spray application, when treated with the cleaning agent of Example 6-1, the antibacterial activity value was 3 or more for the acrylic board and 2 or more for the ceramic tile board, and when treated with the cleaning agents of Examples 6-2 and 6-3, the antibacterial activity value was 4 or more for the acrylic board and 3 or more for the ceramic tile board, showing excellent antibacterial effects.

[0175] When treated by spray application with the cleaning agent of Example 6-3, the mold growth state was 0,0,2,2,2 (N=5), while the mold growth state of the blank (untreated) was 4,4,4,4,4 (N=5). This treatment significantly suppressed mold growth and demonstrated excellent antifungal effects.

[0176] Furthermore, the rate of sebum adhesion to the acrylic panel treated with the cleaner was reduced to about 30% compared to the untreated acrylic panel, and the rate of sebum adhesion to the ceramic tile panel treated in the same way was reduced to about 30-50% compared to the untreated ceramic tile panel, demonstrating an excellent effect in inhibiting the adhesion of sebum stains.In other words, the anti-fouling properties that inhibit the adhesion of oily stains to the treated hard surface were confirmed, regardless of whether it was a hydrophilic or hydrophobic surface.

[0177] Reference example

[0178] Next, six commercially available bathroom cleaners were used to test and evaluate the antibacterial properties of the acrylic boards and ceramic tile boards in the same manner as in Example 1, except that each was sprayed once using a spray bottle from each manufacturer to cover the top surface of the acrylic boards and ceramic tile boards, thereby treating their hard surfaces.

[0179] The results are shown in Table 7. The product names were not disclosed and were indicated by symbols.

[0180] The following commercially available bathroom cleaners were used: Magiclean (trademark) foaming spray (Kao Corporation) Magiclean Bath Foaming Spray Super Clean Aroma Rose Scent (Kao Corporation) Bath Magiclean (trademark) Air Jet Herbal Citrus Scent (Kao Corporation) Look Plus™ Bathtub Cleansing, Floral Soap Scent (Lion Corporation) Look Plus™ Bathtub Cleansing Silver Ion Plus (Lion Corporation) Bath Look (trademark) (manufactured by Lion Corporation)

[0181] [Table 7]

[0182] Treatment with commercial bathroom cleaners did not provide antibacterial activity of 0.4 or more on hydrophobic acrylic boards or hydrophilic ceramic tile boards.

[0183] Example 7

[0184] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As antibacterial and / or bactericidal agents having a cationic group, Polyhexamethylene biguanide (trade name: ProxelIB), a cationic polymer with a biguanide structure, and chlorhexidine curconate (trade name: Spectradyne), a non-polymer biguanide compound, are used as antibacterial agents with a biguanide structure. The electrolyte is a polycarboxylic acid and / or its salt having metal chelating ability. Trisodium citrate (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) Other surfactants include lauryl glucoside (trade name: Mydol 12), As a water-soluble solvent, diethylene glycol monobutyl ether (trade name: Butyl Diglycol NO) The bathroom cleaner shown in Example 7 of Table 8 was prepared using the above ingredients.

[0185] Comparative Example 3

[0186] Using the components in Example 7, a cleaning agent having the composition shown in Comparative Example 3 in Table 8 was prepared.

[0187] Next, the appearance of each of the cleaners in Example 7 and Comparative Example 3 was observed, and the pH and viscosity were measured. Then, each cleaner was used to conduct an antibacterial test and evaluation on an acrylic plate in the same manner as in Example 1. The results are shown in Table 8.

[0188] [Table 8]

[0189] All of the acrylic sheets treated with the cleaner of Example 7 exhibited excellent antibacterial effects with antibacterial activity values ​​of 4 or more, whereas the acrylic sheets of Comparative Examples 3-1 and 3-2, which were treated with a cleaner that did not contain a water-soluble polymer having a carboxylic acid and / or its salt (xanthan gum), and the acrylic sheet of Comparative Example 3-3, which was treated with a cleaner that did not contain an antibacterial agent and / or a disinfectant with a cationic group, only exhibited antibacterial effects with antibacterial activity values ​​of less than 0.7.

[0190] Example 8

[0191] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As an antibacterial agent and / or bactericide having a cationic group, a cationic surfactant is used. Coconut alkylbenzyldimethylammonium chloride (trade name: Hyamine 3500J), Dodecyltrimethylammonium chloride (product name: Nissan Cation BB) of, As an electrolyte, It is a phosphoric acid-based chelating agent having metal chelating ability. Sodium tripolyphosphate (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), 1-hydroxyethane-1,1-diphosphonic acid 60% aqueous solution (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), Inorganic salts such as potassium chloride (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), sodium chloride (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), sodium bicarbonate (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), sodium sulfate (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), magnesium chloride (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), calcium chloride (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), and zinc sulfate heptahydrate (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) were used. Other surfactants include lauryl glucoside (trade name: Mydol 12), As a water-soluble solvent, diethylene glycol monobutyl ether (trade name: Butyl Diglycol NO), As a pH adjuster, a 10% by weight aqueous solution of sodium hydroxide (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) A cleaning agent having the composition shown in Example 8 of Table 9 was prepared using the above.

[0192] Next, the appearance of each of the cleaners in Example 8 was observed, and the pH and viscosity were measured. Then, an antibacterial test and evaluation were carried out on an acrylic plate using each cleaner in the same manner as in Example 1. The results are shown in Table 9.

[0193] [Table 9]

[0194] The test pieces treated with the cleaning agent containing a phosphate chelating agent and a monovalent or divalent water-soluble inorganic salt shown in Example 8 exhibited excellent antibacterial activity on hydrophobic acrylic panels, with antibacterial activity values ​​of 4 or more, 2 or more, or 1.7 or more.

[0195] Example 9

[0196] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As an antibacterial agent and / or bactericide having a cationic group, a cationic surfactant is Coco-alkylbenzyldimethylammonium chloride (trade name: Hyamine 3500J) and Dodecyltrimethylammonium chloride (trade name: Nissan Cation BB) and polyhexamethylene biguanide (trade name: Proxel IB), which is a cationic polymer antibacterial agent with a biguanide skeleton, The electrolyte is a polycarboxylic acid and / or its salt having metal chelating ability. Trisodium citrate (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), Sodium ethylenediaminetetraacetate (EDTA-4Na) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) of, Other surfactants include lauryl glucoside (trade name: Mydol 12), Diethylene glycol monobutyl ether (product name: Butyldiglycol NO) as a water-soluble solvent The bathroom cleaner shown in Example 9 of Table 10 was prepared using the above ingredients. The values ​​for each component in Table 10 are in weight percent.

[0197] Next, the appearance of the cleaner was observed, and the pH and viscosity were measured. The foaming ability when sprayed and the adhesion of the foam to a vertical surface were then evaluated using the same test methods as in Example 6. The cleaning power for the bathtub and the effect of inhibiting the adhesion of soil to a bathtub model were also evaluated. Furthermore, antibacterial and antifungal tests and evaluations were conducted using the same methods as in Example 6. The results are shown in Table 10.

[0198] <Antibacterial testing and evaluation against Rhodotorula>

[0199] In humid places such as bathrooms, a type of yeast called Rhodotorula can grow, using soap scum and sebum as a nutrient source. When this fungus grows, it turns pink and is recognized as an unpleasant and disgusting stain.

[0200] The antibacterial test and evaluation of Rhodotorula bacteria were carried out in accordance with the antibacterial test for plastic products of JIS Z2801, as in Example 1.

[0201] A 50 mm × 50 mm × 2 mm white acrylic plate (manufactured by Hyoshin, an acrylic specialty store) was prepared as a hard surface test plate.

[0202] The treatment for the hard surface was carried out in the same manner as in Example 6, by spraying the solution onto an acrylic plate and leaving it for 3 minutes. The entire top surface of the test plate was then immediately rinsed with tap water at a flow rate of 25 ml / sec for 8 seconds (200 ml in total). The back surface was also rinsed with tap water for 3 seconds. The test plate was then immediately placed with the treated surface facing up in a sterile dish and dried in a constant temperature dryer maintained at 50°C for 12 hours to obtain a treated test specimen.

[0203] For untreated (blank) test pieces, which were not treated with a cleaning agent, the entire top surface of the test piece was rinsed with tap water at a flow rate of 25 ml / sec for 8 seconds (200 ml in total). Untreated (blank) test pieces of acrylic plate were prepared using the same procedure.

[0204] <Antibacterial test>

[0205] Rhodotorula mucilaginosa (NBRC0909) cultured in NB (nutrient broth) medium was diluted 500 times with purified water to obtain 3.5 × 10 5 A bacterial solution containing cfu / ml of bacteria was prepared, and the antibacterial test and evaluation were carried out in the same manner as in Example 1.

[0206] The results are shown in Table 10.

[0207] [Table 10]

[0208] The cleaning agent suitable for use in bathrooms shown in Example 9 exhibited excellent performance in terms of foaming, foam adhesion, and cleaning power when sprayed onto hard surfaces using a spray container.

[0209] Furthermore, when treated by spray application, the cleaner of Example 9 showed excellent antibacterial activity with an antibacterial activity value of 4 or higher on both acrylic and tile panels. On the other hand, the cleaner also showed excellent antibacterial activity with an antibacterial activity value of 4 or higher on acrylic panels. Furthermore, in the treatment by spray application, the mold growth state was 0,0,0,0,0 (N=5), while the mold growth state in the blank (untreated) was 4,4,4,4,4 (N=5). This treatment significantly suppressed mold growth, demonstrating excellent antifungal activity. Example 9 has a neutral cleaner composition similar to that of Example 6-3, but the inclusion of polyhexamethylene biguanide resulted in even better antibacterial and antifungal activity.

[0210] Furthermore, the rate of sebum adhesion on the acrylic panel treated with the cleaning agent was reduced by about 25% compared to the untreated acrylic panel, demonstrating an excellent effect in inhibiting the adhesion of sebum stains.

[0211] Example 10

[0212] The detergent of Example 6-3 was prepared as Example 10-1, the detergent of Example 9 as Example 10-2, a detergent in which chlorhexidine gluconate (trade name: Spectradyne) was added instead of the polyhexamethylene biguanide in the detergent of Example 9 as Example 10-3, and a detergent with the same composition as Example 10-2 except that it did not contain xanthan gum as Comparative Example 4 were prepared. The compositions of each detergent are shown in Table 11. The values ​​of each component in Table 11 are in weight percent.

[0213] The appearance of the detergent was then observed, and the pH and viscosity were measured. The results are shown in Table 11.

[0214] <Antibacterial testing and evaluation>

[0215] As in Example 6, the cleaner was sprayed onto the top surface of an acrylic plate (50 mm x 50 mm x 2 mm) using a trigger spray container (Condor C spray container 500) to cover the surface (and left for 3 minutes).

[0216] Immediately afterwards, the acrylic plates were rinsed with tap water pre-adjusted to 9°C (antibacterial test 1), 18°C ​​(antibacterial test 2), 28°C (antibacterial test 3), or 40°C (antibacterial test 4) by pouring 100 ml of water onto the top surface of the plates using a wash bottle (product name: J Washing Bottle 500 ml, manufactured by Nikko Hansen). The back surface was also rinsed with 20 ml of tap water adjusted to the same temperature. The test plates were then immediately placed with the treated side facing up in a sterile dish and dried for 12 hours in a constant temperature dryer maintained at 50°C to obtain treated test specimens.

[0217] In antibacterial test 4-1, a treated test piece was obtained in the same manner as in antibacterial test 4, except that the amount of tap water at 40° C. poured onto the top surface of the acrylic plate was 200 ml.

[0218] In Antibacterial Test 4-2, similar to Antibacterial Test 4-1, the top surface of the acrylic plate was rinsed with 200 ml of tap water adjusted to 40 ° C using the wash bottle, and the back surface was rinsed with 20 ml of tap water also adjusted to 40 ° C. The test plate was then dried in a thermostatic bath at 50 ° C for 30 minutes. Then, the top surface was rinsed again with 200 ml of tap water adjusted to 40 ° C, and the back surface was rinsed with 20 ml of tap water. Then, similar to Antibacterial Tests 1 to 4, the test plate was immediately placed with the treated side facing up in a sterile dish and dried for 12 hours in a thermostatic dryer maintained at 50 ° C to obtain a treated test piece.

[0219] Thereafter, each treated test piece was subjected to an antibacterial test and evaluation in the same manner as in Example 1. The results are shown in Table 11.

[0220] <Bathtub model dirt adhesion test>

[0221] As in Example 6, the cleaner was sprayed onto the top surface of a black acrylic plate and left for 3 minutes (180 seconds). Immediately afterwards, the top surface of the acrylic plate was rinsed with 200 ml of tap water adjusted to 40°C using a wash bottle (product name: J wash bottle 500 ml). The back surface was also rinsed with 20 ml of tap water adjusted to 40°C. The treated test piece was then dried at 50°C for 30 minutes to obtain a treated test piece.

[0222] In addition, without treatment with a detergent, an untreated (blank) test piece was obtained by rinsing with tap water adjusted to a water temperature of 40°C and drying at 50°C for 30 minutes in the same manner.

[0223] Using the obtained treated test piece and untreated (blank) test piece, a bathtub model soil adhesion test was carried out in the same manner as in Example 6, and the effect of inhibiting the adhesion of soil to the bathtub model was evaluated.

[0224] [Table 11]

[0225] The evaluations of Antibacterial Tests 1, 2, 3, 4, and 4-1 showed that the detergents of Examples 10-2 (Test No. 2) and 10-3 (Test No. 3), which contained polyhexamethylene biguanide or chlorhexidine gluconate, exhibited excellent antibacterial effects even when rinsing the top surface (where the detergent was sprayed) with 200 ml of water at 40°C. Furthermore, in a test (Antibacterial Test 4-2) in which the top surface was rinsed with 200 ml of water at 40°C, dried once, and then rinsed again with 200 ml of water at 40°C, the detergent of Example 10-2 (Test No. 2) exhibited the best antibacterial effects.

[0226] The cleaning agent of Comparative Example 4, which had the same composition as Test No. 2 except that it did not contain xanthan gum, only achieved an antibacterial activity value of less than 0.4 under all treatment conditions.

[0227] The sebum stain adhesion rate on the acrylic plate treated with each detergent was 4% for Test No. 2 detergent containing polyhexamethylene biguanide, and 1% for Test No. 3 detergent containing chlorhexidine gluconate, demonstrating superior sebum stain inhibition effects. The sebum stain adhesion rate on the untreated (blank) test piece in this test was 25%. The sebum stain adhesion rate on the acrylic plate treated with the detergent of Comparative Example 4 was close to that of the untreated (blank) test piece.

[0228] Example 11

[0229] The antibacterial performance of acrylic sheets treated with the cleaning agent of Example 9 in the following manner was evaluated. The results are shown in Table 12. The values ​​for each component in Table 12 are in weight percent.

[0230] <Antibacterial testing and evaluation>

[0231] As in Example 6, a trigger spray container (Condor C spray container 500) was used to apply the coating to test plates (a 50 mm x 50 mm x 2 mm white acrylic plate and a 45 mm x 45 mm x 7 mm white ceramic tile) using the following procedure.

[0232] In Test No. 1, as in Example 10, the detergent was sprayed once to cover the top surface (horizontal top surface) of the test plate, and after leaving it for 3 minutes, tap water whose temperature had been adjusted to 40°C was immediately poured onto the top surface of the acrylic plate using a wash bottle (product name: J wash bottle 500ml) to rinse, with 200ml of water aimed at the top surface. The back surface was also rinsed with 20ml of water, and the plate was then dried in a constant temperature bath at 50°C for 30 minutes. Next, the antibacterial properties 1 to 4 tests were performed as follows.

[0233] For the antibacterial 1 (acrylic plate) and antibacterial 2 (tile plate) tests, the top surface of the test plate was rinsed with room temperature (31°C) tap water at a flow rate of 25 ml / sec for 120 seconds (3000 ml). Immediately afterwards, the test plate was placed in a sterilized petri dish with the detergent-treated surface facing up and dried for 12 hours in a constant temperature dryer maintained at 50°C to obtain a treated test specimen.

[0234] Meanwhile, for the antibacterial properties 3 (acrylic plate) and 4 (tile plate) tests, the test plate was immersed for 30 minutes in hot water (tap water) maintained at 40°C. Immediately after that, the test plate was placed in a sterilized petri dish with the detergent-treated surface facing up and dried for 12 hours in a thermostatic dryer maintained at 50°C to obtain a treated test specimen.

[0235] In Test No. 2, the test panel was placed upright and the vertical top surface was sprayed with the detergent to cover the entire surface. The entire vertical top surface was then immediately scrubbed three times with a sponge cut to 1 cm wide x 2 cm long x 2 cm thick and soaked in a small amount of water. The test panel was then left for three minutes. The top and back surfaces were then immediately rinsed and dried, and the test pieces for Antibacterial Properties 1 to 4 were then performed in the same manner as in Test No. 1, to obtain treated test specimens.

[0236] Thereafter, each treated test piece was subjected to an antibacterial test and evaluation in the same manner as in Example 1. The results are shown in Table 12.

[0237] [Table 12]

[0238] In Test No. 1, the evaluations of Antibacterial Tests 1 and 2 showed that both the acrylic board and the tile board treated with a detergent containing polyhexamethylene biguanide maintained their excellent antibacterial effect even when the treated surface was rinsed with a large amount of water (3000 ml).

[0239] Furthermore, the evaluations in antibacterial tests 3 and 4 showed that the excellent antibacterial effect was maintained even after immersion in hot water maintained at 40°C for 30 minutes.

[0240] On the other hand, in Test No. 2, the test board was stood upright and the entire vertical top surface to which the cleaner had been applied was scrubbed three times with a sponge, which is thought to have reduced the amount of cleaner applied to the test board compared to Test No. 1. However, even under these application conditions, the same excellent antibacterial effect was maintained as in Test No. 1. It is common for bathroom cleaners to be used to scrub the target surface with a tool such as a sponge, and this suggests that excellent antibacterial effects can be provided even in such a cleaning operation.

[0241] Example 12

[0242] To impart antibacterial properties to the inside of a toilet bowl, toilet cleaners with the compositions shown in Table 13 were prepared as Test Nos. 1 and 2 of Example 12. The values ​​for each component in Table 13 are in weight percent. Test No. 1 cleaner has the same composition as the cleaner of Example 9, while Test No. 2 cleaner contains 0.1 weight percent more xanthan gum than No. 1 cleaner.

[0243] The appearance of the detergent was then observed, and the pH and viscosity were measured. The results are shown in Table 13.

[0244] <Antibacterial testing and evaluation>

[0245] As in Example 6, the detergent was sprayed once onto the top surface of a test plate (a 45 mm x 45 mm x 7 mm white ceramic tile) using a trigger spray container (Condor C spray container 500). After leaving the mixture for 3 minutes, the top surface of the test plate was immediately rinsed with tap water at room temperature (28°C) at a flow rate of 100 ml / sec for 50 seconds (5 L: antibacterial 1), 150 seconds (15 L: antibacterial 2), 300 seconds (30 L: antibacterial 3), or 450 seconds (45 L: antibacterial 4). The back surface of each test plate was then rinsed for 5 seconds with tap water at the same flow rate and temperature. The test plate was then immediately placed with the detergent-treated surface facing up in a sterile dish and dried in a constant temperature dryer maintained at 50°C for 12 hours to obtain treated test specimens. Each treated test specimen was then subjected to antibacterial testing and evaluation using the same method as in Example 1. The results are shown in Table 13.

[0246] [Table 13]

[0247] Since ceramic is a common material for toilet bowls, tests were conducted on ceramic tiles. Furthermore, according to the Tokyo Metropolitan Government Bureau of Waterworks' "Survey on Living Water Use," the average amount of water used per person per day in the home is 214 liters (2019), of which 21% is used in the toilet (2015 survey). Therefore, tests were conducted on a rinse volume of up to 45 liters.

[0248] The detergent in Test No. 1 maintained its antibacterial effect exceeding an antibacterial activity value of 4 up to a rinse water volume of 30 L, as evaluated in Antibacterial Tests 1, 2, 3, and 4.

[0249] On the other hand, the detergent test No. 2, in which the amount of xanthan gum was increased by 0.1% by weight, maintained an antibacterial effect exceeding an antibacterial activity value of 4 up to a rinse water volume of 45 L.

[0250] This suggests that good antibacterial effects can be provided even in environments where a large amount of water flows, such as in a toilet.

Claims

1. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.05 to 5% by weight b) Antibacterial and / or bactericidal agents having cationic groups: 0.1 to 10% by weight c) Electrolyte: 0.1-15% by weight a pH of 3 to 12, a weight ratio a) / b) of the water-soluble polymer a) to the antibacterial agent and / or disinfectant having a cationic group b) of 0.167 to 5.00, and a viscosity of 20 to 500 mPa s as measured with a Brookfield viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.) using a TM2 rotor at a speed of 60 revolutions (rpm), A liquid cleaning composition for imparting and maintaining antibacterial properties to hard surfaces, which, when applied to a hard surface and rinsed with water, insolubilizes the complex of the water-soluble polymer (a) and the antibacterial agent and / or bactericide having a cationic group (b) and remains on the hard surface, thereby imparting and maintaining antibacterial properties to the hard surface and making it hydrophilic, regardless of whether the hard surface is made of a hydrophilic or hydrophobic material.

2. The above a) and b) are, respectively, a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.2 to 5% by weight b) Antibacterial and / or bactericidal agents having cationic groups: 0.3 to 10% by weight The composition according to claim 1, wherein

3. 3. The composition of claim 1 or 2, which imparts and maintains antibacterial and antifungal properties to a hard surface after application to the hard surface and rinsing with water.

4. 3. The composition according to claim 1 or 2, which, after being applied to a hard surface and then rinsed with water, is capable of inhibiting adhesion of oily stains to the hard surface when water containing oily stains splashes on the hard surface or when water splashes on the hard surface after contact with oily stains.

5. 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 3. The composition according to claim 1, which is one or more antibacterial agents and / or bactericides selected from the group consisting of:

6. The antibacterial agent and / or bactericide having a cationic group of the above b) is 3. 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.

7. The antibacterial agent and / or bactericide having a cationic group of the above b) is 3. The composition according to claim 1, 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.

8. The antibacterial agent and / or bactericide having a cationic group of the above b) is The composition according to claim 7, further comprising a quaternary ammonium salt type cationic surfactant.

9. The composition according to claim 1 or 2, wherein the water-soluble polymer having a carboxylic acid and / or a salt thereof (a) is xanthan gum, pectin and / or a salt thereof, gellan gum and / or a salt thereof, diutan gum, welan gum, gum arabic and / or a salt thereof, alginic acid and / or a salt thereof, hyaluronic acid and / or a salt thereof, tragacanth gum and / or a salt thereof, succinoglycan and / or a salt thereof, carboxymethylcellulose and / or a salt thereof, carboxyethylcellulose and / or a salt thereof, carboxyvinyl polymer and / or a salt thereof, or polyacrylic acid and / or a salt thereof.

10. 3. The composition according to claim 1 or 2, wherein the electrolyte c) is one or more electrolytes selected from the group consisting of inorganic acids and / or salts thereof, monovalent organic acids and / or salts thereof, polycarboxylic acids and / or salts thereof having metal chelating ability, polyphosphonic acids and / or salts thereof having metal chelating ability, and polyphosphoric acids and / or salts thereof having metal chelating ability.

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

12. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.05 to 5% by weight b) Antibacterial agents and / or disinfectants having a cationic group, containing 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: 0.1 to 10% by weight c) Electrolyte: 0.1-15% by weight A method for imparting antibacterial properties, comprising treating a hard surface made of a hydrophilic or hydrophobic material with a liquid composition containing the above compound and having a pH of 3 to 12.

13. 13. The method of claim 12, which can impart antifungal properties to hard surfaces.

14. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.05 to 5% by weight b) Antibacterial agents and / or disinfectants having a cationic group, containing 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: 0.1 to 10% by weight c) Electrolyte: 0.1-15% by weight A liquid antibacterial cleaning composition for hard surfaces, comprising:

15. The antibacterial agent and / or bactericide having a cationic group of the above b) is The composition according to claim 14, further comprising a quaternary ammonium salt type cationic surfactant.

16. The composition according to claim 14 or 15, wherein the water-soluble polymer having a carboxylic acid and / or a salt thereof (a) is xanthan gum, pectin and / or a salt thereof, gellan gum and / or a salt thereof, diutan gum, welan gum, gum arabic and / or a salt thereof, alginic acid and / or a salt thereof, hyaluronic acid and / or a salt thereof, tragacanth gum and / or a salt thereof, succinoglycan and / or a salt thereof, carboxymethylcellulose and / or a salt thereof, carboxyethylcellulose and / or a salt thereof, carboxyvinyl polymer and / or a salt thereof, or polyacrylic acid and / or a salt thereof.

17. 16. The composition according to claim 14 or 15, wherein the electrolyte c) is one or more electrolytes selected from the group consisting of inorganic acids and / or salts thereof, monovalent organic acids and / or salts thereof, polycarboxylic acids and / or salts thereof having metal chelating ability, polyphosphonic acids and / or salts thereof having metal chelating ability, and polyphosphoric acids and / or salts thereof having metal chelating ability.

18. 16. The composition according to claim 14 or 15, which contains 2 to 30% by weight of glycol and / or glycol ether.

Images