Liquid cleaning composition for preventing stain adhesion to hard surfaces and method for preventing stain adhesion

Abstract

To provide a liquid detergent composition for suppressing adhesion of dirt on a hard surface having an effect of making it difficult for skin dirt such as the skin dirt generated from a body when bathing and washing to adhere regarding a hard surface in general irrespective of a hydrophilic surface, a hydrophobic surface such as of a bathtub, bathtub lids, floors, walls, buckets, and chairs, and a dirt adhesion suppression method.SOLUTION: A dirt adhesion suppressing liquid detergent composition for a hard surface comprises a) a water-soluble polymer having carboxylic acid and / or its salt: 0.05 to 5 wt.%, b) a base in a state having a cationic property made one or more selected from surfactants, antibacterial agents, and polymers that have cationic properties: 0.02 to 10 wt.%, c) electrolyte: 0.1 to 15 wt.%, and has the pH of 3 to 12. A dirt adhesion suppressing method treats a hard surface made of a hydrophilic material or a hydrophobic material with a bath chamber antifouling detergent composition including a), b), and c) and exhibiting skin fat dirt adhesion suppressing capacity for a hard surface having pH of 3 to 12.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a detergent composition and a method for inhibiting the adhesion of dirt by treating a hard surface. [Background technology]

[0002] Dirt occurs in various places in a home, and various cleaning agents are available to remove such dirt.

[0003] Bathrooms and bathtubs are places that are used almost every day, and the bathtub in particular is the place that bare skin touches every day, so it is the place where dirt is the most of the concern. Therefore, it is a place that needs to be cleaned frequently and takes a lot of effort to keep clean.

[0004] A variety of anti-fouling products have been proposed for surfaces that are primarily hydrophilic hard surfaces (ceramic tiles), such as the inside of a toilet bowl, but there are very few products that can be adsorbed to surfaces that are primarily hydrophobic hard surfaces (artificial marble, plastic, stainless steel, etc.), such as the inside of a bathroom or bathtub, to make the surface hydrophilic and prevent the adhesion of sebum stains.

[0005] Hydrophobic surfaces have a high affinity for oily sebum stains, making them prone to adhesion, so many people scrub bathtubs with detergents every time they use them. This is particularly tough work for elderly people and pregnant women. Given this situation, a technology has been proposed to make hydrophobic surfaces hydrophilic.

[0006] For example, JP-A-2008-523184 describes a cleaning adjuvant containing a cationic acrylic polymer containing a hydrophobic group.

[0007] JP-A-2009-545642 describes a composition comprising an amphiphilic block copolymer.

[0008] Japanese Patent Application Laid-Open Nos. 2015-206020, 2015-206021, 2016-199679, and 2016-222773 describe cleaning agents containing copolymers of a monomer having a sulfobetaine structure and a monomer having an alkyl group (hydrophobic portion).

[0009] Patent No. 6,960,510 describes a cleaning composition for hard surfaces that contains a cationized polysaccharide, an alkaline agent, an anionic surfactant, and water and has a pH of 13.1 to 14.

[0010] However, in terms of antifouling of hydrophobic surfaces, there are issues with achieving sufficient antifouling effect and the durability of that effect in practical use, and few such products have been put to practical use. Furthermore, for example, bathrooms and bathtubs are made of a variety of materials, including mirrors, tiles, enamel, artificial marble (polyester, acrylic, etc.), vinyl chloride, and stainless steel, and it is desirable to achieve antifouling properties for all hard surfaces, from hydrophilic to hydrophobic, with a single detergent. Furthermore, bathroom cleaners for general household use used in bathrooms and bathtubs are preferably weakly acidic to weakly alkaline liquid detergents, from the viewpoints of irritation to the skin and safety to the eyes.

[0011] For example, Japanese 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 stains such 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 stain resistance on hard surfaces.

[0012] Japanese Patent No. 5,779,390 discloses a toilet cleaner with 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 its ability to resist oily stains or stains on plastic surfaces. 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 avoid the use of a cationic surfactant.

[0013] Patent 5637586 discloses a cleaning agent that essentially contains a thickener (such as xanthan gum) selected from sulfamic acid, alkylamine oxide, propylene glycol, and polysaccharides. Paragraph 0006 of the specification states that the cleaning agent has high detergency against accumulated inorganic dirt that is difficult to remove, such as calcium and silicate, but there is no mention of its ability to prevent oily dirt or plastic from being soiled.

[0014] 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% acrylic acid and 100% acrylic acid. Paragraph 0006 of the document states that the cleaner has both adhesion retention and spreadability, thereby achieving excellent cleaning power even on vertical surfaces. Paragraph 0037 also states that the water-soluble polymer is used to impart adhesion retention and spreadability to the vertical surface of a bathtub. In addition, the examples describe an evaluation of cleaning power using glass fiber reinforced plastic test pieces. However, there is no description of the anti-fouling properties of the cleaner on oily soils, sebum soils, or plastic surfaces.

[0015] Patent 6584004 discloses a foam-dispensing cleaner containing a non-soap anionic surfactant, a water-soluble solvent, an aminocarboxylic acid-type chelating agent, and a water-soluble polymer, adjusted to a pH of 10-12. The invention discloses a cleaning method in which foam from the cleaner is directly applied to the area around the waterline of a bathtub filled with water, and then the water is drained from the bathtub. This provides convenience by eliminating the need for conventional scrubbing. Paragraph 0030 states that the water-soluble polymer, when used in combination with a water-soluble solvent, prevents the foam dispensed from the container from diffusing into the water, thereby improving foam retention. However, no mention is made of the cleaner's ability to prevent oily or sebum-based stains or stains on plastic surfaces. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] Special Publication No. 2008-523184 [Patent Document 2] Special Publication No. 2009-545642 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-206020 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-206021 [Patent Document 5] Japanese Patent Application Laid-Open No. 2016-199679 [Patent Document 6] Japanese Patent Application Laid-Open No. 2016-222773 [Patent Document 7] Patent No. 2963065 [Patent Document 8] Patent No. 5779390 [Patent Document 9] Patent No. 5637586 [Patent Document 10] Japanese Patent Application Laid-Open No. 2017-78134 [Patent Document 11] Patent No. 6584004 [Patent Document 12] Patent No. 6960510 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 inhibiting stain adhesion that can maintain the antifouling properties of the treated object for a long time across all hard surfaces, whether hydrophilic or hydrophobic, in a bathroom including a shower stall or other areas, and that can effectively inhibit the adhesion of sebum stains and the like generated from the body during bathing or washing in a bathroom to hard surfaces in particular. [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) A base in a cationic state, which is composed of one or more selected from surfactants, antibacterial agents, and polymers in a cationic state: 0.02 to 10% by weight c) Electrolyte: 0.1~15% by weight A liquid cleaning composition for inhibiting adhesion of dirt to hard surfaces, which contains the above and has 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) A base in a cationic state, which is composed of one or more selected from surfactants, antibacterial agents, and polymers in a cationic state: 0.02 to 10% by weight c) Electrolyte: 0.1~15% by weight A method for inhibiting the adhesion of dirt, 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, adhesion of dirt to the treatment target can be suppressed across all hard surfaces, regardless of whether the surface is hydrophilic or hydrophobic. DETAILED DESCRIPTION OF THE INVENTION

[0021] (1) The liquid detergent composition for inhibiting the adhesion of dirt to hard surfaces of the present invention and the liquid composition used in the method for inhibiting the adhesion of dirt by treating a hard surface made of a hydrophilic or hydrophobic material of the present invention (hereinafter, both the "liquid detergent composition for inhibiting the adhesion of dirt to hard surfaces" and the "liquid composition used in the method for inhibiting the adhesion of dirt" are also referred to as the "liquid composition of the present invention"): a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.05 to 5% by weight b) A base in a cationic state, which is composed of one or more selected from surfactants, antibacterial agents, and polymers in a cationic state: 0.02 to 10% by weight c) Electrolyte: 0.1~15% by weight and its pH is 3 to 12.

[0022] (2) Water-soluble polymers containing carboxylic acids and / or their salts

[0023] (2-1) In the present invention, the function of inhibiting adhesion of dirt (especially sebum dirt) is exhibited by the "a) water-soluble polymer having a carboxylic acid and / or a salt thereof." When this water-soluble polymer is adsorbed onto a hard surface, it is presumed that the negative charge of the carboxylic acid and / or a salt thereof possessed by the water-soluble polymer causes hydrophilicity of the hard surface.

[0024] 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, hyaluronic acid, tragacanth gum, succinoglycan, and sodium (potassium) alginate. 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.

[0025] Among these, xanthan gum, gellan gum, diutan gum, succinoglycan, and carboxymethylcellulose are preferred, with xanthan gum being more preferred.

[0026] It was not previously known that water-soluble polymers containing these carboxylic acids and / or their salts can modify a wide range of surfaces, from hydrophilic hard surfaces such as ceramic tiles to hydrophobic hard surfaces such as plastics and stainless steel, and exhibit excellent antifouling properties.

[0027] (2-2) For hydrophilic hard surfaces such as ceramic tiles, porcelain, glass, and enamel, treatment with a water-soluble polymer containing a carboxylic acid and / or its salt alone can adsorb to the treated surface and inhibit the adhesion of dirt (especially sebum stains), but for hydrophobic hard surfaces such as plastics (synthetic resins) such as acrylic resins (acrylic acid ester resins, methacrylic acid ester resins, etc.), polyester resins (polyethylene terephthalate resins, etc.), and polyvinyl chloride resins, as well as stainless steel, the above-mentioned "b) cationic base consisting of one or more selected from surfactants, antibacterial agents, and polymers in a cationic state" must be used in combination. Even for hydrophilic hard surfaces, it is difficult to sustainably inhibit the adhesion of dirt by treatment with a water-soluble polymer containing a carboxylic acid and / or its salt alone if the surface is exposed to large amounts of water or multiple applications of water.

[0028] However, when a water-soluble polymer having a carboxylic acid and / or its salt is used in combination with a substantial amount of the cationic base (hereinafter also referred to as the "cationic base"), an insoluble complex is immediately formed, making it unusable as a cleaning agent or antifouling agent. Therefore, it is necessary to further contain the above-mentioned "c) electrolyte."

[0029] In the liquid composition of the present invention, the water-soluble polymer having a carboxylic acid and / or its salt and the cationic base do not form a complex but are uniformly dissolved or dispersed due to the action of the electrolyte. For example, this liquid composition is applied to a hard surface by direct coating or spraying, and the hard surface is scrubbed with a sponge or a scrubbing brush, or the liquid composition is applied to the hard surface and scrubbed with a sponge or a scrubbing brush, to remove dirt.

[0030] The detergent of the present invention, which has been applied to a hard surface as described above, is then rinsed with water, such as shower water. It is believed that the dilution effect during this process causes the complex of the cationic base, which is comprised of one or more selected from surfactants, antibacterial agents, and polymers, and the water-soluble polymer having a carboxylic acid and / or its salt, to undergo phase separation and become insolubilized, remaining on the target surface.

[0031] (2-3) Materials in bathrooms and other residential spaces that are subject to cleaning operations involving rinsing with water include hydrophilic hard surfaces such as ceramic tiles, porcelain, glass, and 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, as well as stainless steel.

[0032] As described above, the liquid detergent composition for inhibiting the adhesion of dirt to hard surfaces and the method for inhibiting the adhesion of dirt of the present invention can modify hydrophilic hard surfaces such as glass, ceramics, ceramic tiles, and enamel, as well as hydrophobic hard surfaces such as artificial marble, FRP, plastics such as polyvinyl chloride, and stainless steel, particularly in wet areas such as bathrooms, bathtubs, bath tubs, bath stools, and washbasins, to exhibit an anti-fouling effect that effectively inhibits the adhesion of sebum dirt that occurs during body washing.

[0033] In addition, the cationic base in the liquid composition of the present invention, which is one or more selected from cationic surfactants, antibacterial agents, and polymers, is thought to have the effect of causing a substitution reaction with the metal ions of fatty acid metal salts, known as soap scum, a typical stain on bathrooms and bathtubs, thereby facilitating the removal of the stains.Furthermore, it also has the effect of weakening the adhesive strength of sebum stains that adhere to bathtubs and the like, making them easier to remove from the bathtub surface.

[0034] Furthermore, by applying the detergent composition and method of the present invention to various hard surfaces often used in bathtubs, a water-soluble polymer having a carboxylic acid and / or its salt can be adsorbed onto the hard surface, thereby achieving a sustained antifouling effect. Even if the hard surface is a hydrophobic hard surface such as plastic or stainless steel, it maintains its hydrophilicity after repeated rinsing with water, and adhesion of oily stains such as sebum stains is suppressed.

[0035] (2-4) 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.

[0036] If the content is less than 0.05% by weight, the effect of inhibiting adhesion of dirt (especially sebum dirt) is not sufficient. 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.

[0037] (2-5) Among water-soluble polymers containing carboxylic acid and / or its salt, particularly preferred is xanthan gum, which exhibits high viscosity at low concentrations while rapidly decreasing in viscosity when subjected to shear forces such as stirring. Therefore, liquid compositions containing xanthan gum exhibit properties such as smooth discharge from foam dispensers, not impairing the foaming properties of surfactants, and being more likely to remain on vertical surfaces such as bathtubs and bathroom walls, thereby enhancing ease of use in terms of cleansing properties and antifouling properties, including the inhibition of sebum stain adhesion.

[0038] (3) A base in a cationic state

[0039] (3-1) The liquid composition of the present invention uses “b) a base in a cationic state, which is composed of one or more selected from surfactants, antibacterial agents, and polymers in a cationic state.”

[0040] The term "bases in a cationic state" includes bases having cationic groups as well as bases that exhibit cationic properties when, for example, the pH is within a certain range. However, it also includes amphoteric bases that exhibit only cationic properties when the pH is within a certain range, but does not include amphoteric bases that exhibit both cationic and anionic properties in the same molecule.

[0041] It is presumed that when the liquid composition of the present invention is applied to a hard surface and then rinsed with water, the dilution effect causes the complex of the base in a cationic state and the water-soluble polymer having a carboxylic acid and / or a salt thereof to undergo layer separation and become insolubilized, and the complex behaves in such a way that it remains on the target surface.

[0042] The concentration of "b) a base in a cationic state, which is one or more selected from surfactants, antibacterial agents, and polymers in a cationic state" in the liquid composition of the present invention is 0.02 to 10% by weight. If it is less than 0.02% by weight, the antifouling properties of xanthan gum on hydrophobic surfaces will be insufficient, and if it exceeds 10.0% by weight, it will be 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.

[0043] (3-2) As the "surfactant in a cationic state" (hereinafter also referred to as a cationic surfactant) in b) of the present invention, alkylamine oxides and alkenylamine oxides used at pH 8 or less, as well as alkylamine salt types or alkenylamine salt types, quaternary ammonium salt types, and pyridine ring salt-containing types are preferred, but are not limited thereto. The surfactant in a cationic state can be used alone or in combination of two or more types.

[0044] For example, when the cationic surfactant in b) is one or more surfactants selected from the group consisting of alkylamine oxides, alkenylamine oxides, alkylamine salt types, alkenylamine salt types, quaternary ammonium salt types, and pyridine ring salt-containing types, and the alkylamine oxide and / or alkenylamine oxide (i.e., one or both of alkylamine oxide and alkenylamine oxide) is contained in the surfactant in a cationic state in an amount of 50% by weight or more (when both alkylamine oxide and alkenylamine oxide are contained, the total of both is 50% by weight or more), the pH can be adjusted to 3 to 8 before use.

[0045] (i) Alkylamine oxides and alkenylamine oxides exhibit both cationic and nonionic properties depending on the pH, and exhibit cationic properties at neutral to acidic pH levels as shown below.

[0046] [ka]

[0047] In order for the alkyl (or alkenyl) amine oxide in the liquid composition of the present invention to have cationic properties, the pH of the liquid composition is preferably adjusted to 3 to 8, more preferably 3 to 6. An organic acid or an inorganic acid can be used as an agent for adjusting the pH to the neutral to acidic side. From the viewpoint of pH stability, organic acids are preferred, and citric acid is particularly preferred.

[0048] The number of carbon atoms in the alkyl group in the alkylamine oxide (or the alkenyl group in the alkenylamine oxide) is preferably 6 to 18, and more preferably 10 to 16. Specifically, an amine oxide having an alkyl group with 10 to 16 carbon atoms is more preferred. Furthermore, dodecyl(lauryl)amine oxide is particularly preferred.

[0049] (ii) As the alkylamine salt type and alkenylamine salt type, monoalkyl (or alkenyl) amines, dialkyl (or dialkenyl) amines, and trialkyl (or trialkenyl) amines are preferred.

[0050] 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 LONZABAC12 [N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine] ("LONZABAC" is a trademark) from LONZA.

[0051] (iii) As the quaternary ammonium salt type, tetraalkyl (or tetraalkenyl) ammonium salts or benzyltrialkyl (or trialkenyl) ammonium salts are preferred.

[0052] 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:

[0053] (iv) 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.

[0054] (3-3) Examples of antibacterial agents in a cationic state in b) of the present invention include guanidine or biguanide skeleton compounds other than polymers (i.e., compounds having a guanidine or biguanide skeleton, excluding the "cationic polymer having a guanidine or biguanide skeleton" described below). 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. Other examples include alexidine hydrochloride.

[0055] (3-4) As the polymer having cationic properties in b) of the present invention, 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.

[0056] 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).

[0057] 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).

[0058] An example of a cationic polymer having an amine in the main chain is polyethyleneimine.

[0059] An example of a cationic polymer with amino groups in the side chain is ε-poly-L-lysine, in which the amino acid lysine is linked by amide bonds. Products made by fermentation are commercially available. Another example of a cationic polymer consisting of β1→4 bonds of glucosamine is chitosan. Industrially, chitin (poly-β1→4-N-acetylglucosamine) obtained from crustaceans such as crabs and shrimp is deacetylated by boiling in concentrated alkali to produce chitosan. The conversion of chitin to chitosan (deacetylation) is not complete, and in some cases, about 30% of the chitin remains in the chitosan.

[0060] 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.

[0061] In particular, in residential spaces such as kitchen sinks, bathrooms, washstands, and toilets, warm water is generally used not only for rinsing during cleaning operations but also for washing dishes and bathing, and in toilets, large amounts of running water are involved in flushing urine, feces, and the like. Even in such usage environments, cationic polymers or compounds having a guanidine skeleton or a biguanide skeleton can impart excellent stain resistance to the target hard surface.

[0062] 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, and is not limited to those in residential spaces, and can exhibit antifouling properties.

[0063] Furthermore, in the present invention, the water-soluble polymer having a carboxylic acid and / or its salt plays a role in allowing the surfactant, antibacterial agent, and polymer having a cationic group, which can impart antibacterial properties (or may even impart antifungal properties) to the target surface, to remain on the hard surface.

[0064] (4) Electrolyte

[0065] (4-1) The liquid composition of the present invention contains "c) an electrolyte."

[0066] As described above, when a water-soluble polymer having a carboxylic acid and / or its salt is mixed with a cationic base, a complex is formed due to electrostatic interaction, forming a strong gel, resulting in a non-uniform composition that cannot function as a cleaning agent or antifouling agent. Therefore, in order to suppress the formation of a strong gel due to complex formation and to ensure a uniform mixture, the liquid composition needs to contain a required amount of electrolyte.

[0067] 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 cationic base, preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight, and even more preferably 2 to 9% by weight.

[0068] 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.

[0069] (4-2) Examples of the “c) electrolyte” in the present invention include inorganic acids and / or salts thereof, monovalent organic acids and / or salts thereof, and polycarboxylic acids, polyphosphonic acids, and polyphosphoric acids, each of which has a metal chelating ability (i.e., divalent or higher carboxylic acids, phosphonic acids, and phosphoric acids, each of which has a bidentate or higher ligand that binds to a metal ion to form a chelate compound) and / or their salts.

[0070] (4-3) 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.

[0071] (4-4) 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.

[0072] (4-5) Preferred examples of polycarboxylic acids and / or salts thereof having metal chelating ability (polycarboxylic acid-based metal chelating agents) 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.

[0073] (4-6) Preferred examples of polyphosphonic acids and / or salts thereof having metal chelating ability (polyphosphonic acid-based metal chelating agents) 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, aminopolymethylenephosphonic acid, polyethylenepolyaminepolymethylenephosphonic 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.

[0074] (4-7) Preferred examples of polyphosphoric acid and / or its salts having metal chelating ability (polyphosphate-based metal chelating agents) include metaphosphoric acid, orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid, and their respective salts.

[0075] The "electrolyte" may be any one of the above, or may be a combination of two or more of the above.

[0076] (5) Examples of components other than a), b) and c) that may be contained in the liquid composition of the present invention

[0077] (5-1) In the present invention, in addition to the cationic base, 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.

[0078] (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.

[0079] 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 2represents 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.]

[0080] 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.

[0081] 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.

[0082] (ii) Preferred examples of amphoteric surfactants include alkylamidopropyl-N,N-dimethylacetic acid betaine, alkylamidopropyl-N,N-dimethyl-2-hydroxypropyl sulfobetaine, alkylamidopropyl-N,N-dimethyl-propyl sulfobetaine, etc. More specific examples of preferred amphoteric surfactants include lauric acid amidopropyl-N,N-dimethylacetic acid betaine, myristate amidopropyl-N,N-dimethylacetic acid betaine, cocamidopropyl-N,N-dimethylacetic acid betaine, and lauryl hydroxysulfobetaine.

[0083] (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).

[0084] In addition, since anionic surfactants may form insoluble complexes with the "b) base in a cationic state," it is necessary to suppress the formation of insoluble complexes by blending "c) electrolytes" to obtain a uniform liquid composition.

[0085] (5-2) The liquid composition of the present invention has excellent uniform dissolution or uniform dispersion stability, and preferably contains a water-soluble solvent to further enhance the cleansing properties of soap scum and sebum stains. By containing a water-soluble solvent, the liquid composition of the present invention has the effect of enhancing the uniform dissolution or uniform dispersion stability even when the electrolyte content is reduced.

[0086] 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).

[0087] Specific examples 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. The water-soluble solvent is preferably contained in the liquid composition in an amount of 2 to 30% by weight. If the amount is less than 2%, the cleaning power for oily stains will not be fully exerted, and if it exceeds 30% by weight, the foaming ability and foam retention will tend to decrease, and there may be situations where the odor is unpleasant.The amount is more preferably 3 to 20% by weight, and even more preferably 5 to 15% by weight.

[0088] 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.

[0089] (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.

[0090] (6) When the liquid antifouling 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, the means for supplying the respective liquid compositions to the hard surface include, for example, a 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, a means for supplying the liquid composition by squeezing it using a squeeze bottle and discharging it directly onto the target hard surface, and a means for supplying the liquid composition together with water onto the target hard surface, i.e., a toilet bowl, which is the target hard surface, when flushing water is discharged, as in an automatic flush cleaner, etc. Preferred means include a means that utilizes the foaming properties of the liquid composition to generate foam and utilizes the adhesiveness of the foam for application or cleaning, i.e., a means for directly supplying the foamed liquid composition onto the target hard surface using a trigger-type or squeeze-type foam dispenser.

[0091] The liquid composition supplied to the 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 rubber gloves, etc., to perform cleaning or application. 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. [Example]

[0092] Example 1

[0093] 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 the cationic base, a cationic surfactant is used. Benzalkonium chloride (Product name: Hyamine 3500J ["Hyamine" is a trademark], manufactured by LONZA. The same applies below.) Dodecyltrimethyl quaternary ammonium chloride (trade name: Nissan Cation BB ["Nissan Cation" is a trademark], manufactured by NOF Corporation; 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.

[0094] Next, the pH of each was measured and the appearance was observed. After that, sebum stain adhesion tests were conducted on acrylic boards and ceramic tile boards using each detergent. The results are shown in Table 1.

[0095] Comparative Example 1

[0096] Example 1 Benzalkonium chloride Liquid antifouling detergents having the compositions shown in Comparative Example 1 were prepared using the compound alone and xanthan gum alone.

[0097] Next, the pH of each was measured and the appearance was observed. After that, sebum stain adhesion tests were conducted on acrylic boards and ceramic tile boards using each detergent. The results are shown in Table 1.

[0098] <Sebum stain adhesion test>

[0099] 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%)

[0100] (Test Method)

[0101] As hard surface test plates, we prepared 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).

[0102] The hard surfaces of the test plates (acrylic plate: 50 mm × 50 mm, ceramic tile: 45 mm × 45 mm) were treated by applying 2 ml of each cleaner to cover the top surface. After leaving the test plate for 3 minutes (180 seconds), the entire top surface of the test plate was 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 dried at 50°C for 30 minutes to obtain treated test specimens.

[0103] 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.

[0104] The model sebum soil was heated to about 60°C and stirred to dissolve (into a liquid state). 80 ml of hot water was added to a 100 ml beaker for an acrylic plate, and 70 ml for a ceramic tile. When the water temperature reached 43°C, 0.104 g of the model sebum soil that had been heated and dissolved was added to the hot water. After addition, the oily model sebum soil was finely dispersed with vigorous stirring.

[0105] 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.

[0106] 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.

[0107] After drying, the specimens were conditioned for 30 minutes and weighed. The weight of the treated specimen was subtracted from the weight of the specimen before treatment with the detergent to calculate the amount of soiling. The same procedure was used to calculate the amount of soiling for the untreated (blank) specimen.

[0108] The adhesion rate of model sebum soil to each of the treated test piece and the untreated (blank) test piece was calculated using the following formula. Sebum stain adhesion rate (%) = [amount of stain adhesion (g) / amount of stain placed in beaker (0.104g)] x 100 (%)

[0109] The results are shown in Table 1.

[0110] [Table 1]

[0111] When treated with the detergent of Example 1, the treated test pieces of both the hydrophobic acrylic board and the hydrophilic ceramic tile board showed significantly less adhesion than the untreated (blank) test piece (control), demonstrating a significant inhibitory effect on the adhesion of sebum stains.

[0112] On the other hand, when treated with the cationic surfactant of Comparative Example 1 alone (Comparative Examples 1-1 and 1-2), the adhesion amount was close to that of the untreated (blank) test piece (control) for both the acrylic board and the ceramic tile test board, and no significant adhesion inhibitory effect was observed. When treated with xanthan gum alone (Comparative Examples 1-3 and 1-4), the adhesion amount for the acrylic board was close to that of the untreated (control), but the adhesion amount for the ceramic tile board was about half that of the untreated (control).

[0113] Example 2

[0114] Examples of water-soluble polymers having a carboxylic acid and / or a salt thereof include xanthan gum (trade name: KELZAN AR); As a cationic base, a cationic surfactant Lauryl dimethylamine oxide (Unisafe A-LM ["Unisafe" is a trademark] manufactured by NOF Corporation), Dodecyltrimethyl quaternary ammonium chloride (trade name: Nissan Cation BB), N,N-didecyl-N-methylpoly(oxyethyl)ammonium propionate (trade name: Bardap26 ["Bardap" is a trademark], manufactured by LONZA), N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (trade name: Lonzabac12 ["Lonzabac12" is a trademark], manufactured by LONZA), 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.), Citric acid (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) The cleaning agents having the compositions shown in Table 2 were prepared using the above. Note that the dimethylamine oxide in Test No. 1 was kept in a cationic state by making the liquid weakly acidic.

[0115] Next, the appearance of the cleaner was observed, and the pH was measured. Thereafter, a sebum stain adhesion test was conducted on the acrylic plates treated with each cleaner using the same test method as in Example 1.

[0116] The results are shown in Table 2.

[0117] [Table 2]

[0118] The hydrophobic acrylic plate treated with the cleaning agent of Example 2 showed significantly less adhesion than the untreated plate (control).

[0119] Example 3

[0120] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, Xanthan gum (trade 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) As a cationic base, a cationic surfactant Benzalkonium chloride (Product name: Hyamine 3500J) and Dodecyltrimethyl quaternary ammonium chloride (trade name: Nissan Cation BB), and 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.) A cleaning agent having the composition shown in Table 3 was prepared using the above.

[0121] Next, the pH of each was measured and the appearance was observed. After that, a sebum stain adhesion test was conducted on an acrylic plate using each detergent using the same test method as in Example 1. The results are shown in Table 3.

[0122] Comparative Example 2

[0123] As a water-soluble polymer that does not have a carboxylic acid, Guar gum (trade name: SUPERGEL CSA200, manufactured by Pakistan Gum & Chemicals), Hydroxyethyl cellulose (trade name: SANHEC ["SANHEC" is a trademark], manufactured by Sansho Co., Ltd.), As a cationic surfactant Benzalkonium chloride (Product name: Hyamine 3500J) and Dodecyltrimethyl quaternary ammonium chloride (product name: Nissan Cation BB) A cleaning agent having the composition shown in Table 3 was prepared using the above.

[0124] Next, the pH of each was measured and the appearance was observed. After that, a sebum stain adhesion test was conducted on an acrylic plate using each detergent using the same test method as in Example 1. The results are shown in Table 3.

[0125] [Table 3]

[0126] The hydrophobic acrylic plate treated with the cleaning agent of Example 3 showed a significantly smaller amount of adhesion than the untreated plate (control).

[0127] On the other hand, the cleaning agent containing guar gum (Comparative Example 2-1) of Comparative Example 2 did not achieve a uniformly dissolved state, and the acrylic plate treated with that cleaning agent showed an adhesion amount similar to that of the untreated acrylic plate. The acrylic plate treated with the cleaning agent containing hydroxyethyl cellulose (Comparative Example 2-2) showed an adhesion amount greater than that of the untreated acrylic plate (control).

[0128] Example 4

[0129] Examples of water-soluble polymers having a carboxylic acid and / or a salt thereof include xanthan gum (trade name: KELZAN AR); As a cationic base, a cationic surfactant Benzalkonium chloride (Product name: Hyamine 3500J) 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.), and Diethylene glycol monobutyl ether (product name: Butyldiglycol NO) as a water-soluble solvent Using the above, cleaning agents having compositions in which the cationic surfactant concentration was varied as shown in Table 4 were prepared.

[0130] Next, the pH of each was measured and the appearance was observed. After that, a sebum stain adhesion test was conducted on an acrylic plate using each detergent using the same test method as in Example 1. The results are shown in Table 4.

[0131] Comparative Example 3

[0132] A cleaning solution was prepared with the same composition as in Example 4, except that it did not contain benzalkonium chloride, a cationic surfactant. The composition is shown in Table 4.

[0133] The pH was then measured and the appearance was observed.Then, a sebum stain adhesion test was carried out on an acrylic plate using the cleaning agent in the same manner as in Example 1. The results are shown in Table 4.

[0134] [Table 4]

[0135] The hydrophobic acrylic plate treated with the cleaning agent containing the cationic surfactant in the range of 0.1 to 0.9 wt% in Example 4 showed significantly less adhesion than the untreated acrylic plate (control). On the other hand, the acrylic plate treated with the cleaning agent containing no cationic surfactant in Comparative Example 3 showed an adhesion amount close to that of the untreated acrylic plate.

[0136] Example 5

[0137] Examples of water-soluble polymers having a carboxylic acid and / or a salt thereof include xanthan gum (trade name: KELZAN AR); As a cationic base, a cationic surfactant Benzalkonium chloride (Product name: Hyamine 3500J) Trisodium citrate (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) as a polycarboxylic acid and / or its salt having metal chelating ability, and Diethylene glycol monobutyl ether (product name: Butyldiglycol NO) as a water-soluble solvent Using the above, detergents with different compositions containing xanthan gum at different concentrations were prepared as shown in Table 5.

[0138] Next, the pH of each was measured and the appearance was observed. After that, a sebum stain adhesion test was conducted on an acrylic plate using each detergent using the same test method as in Example 1. The results are shown in Table 5.

[0139] [Table 5]

[0140] The hydrophobic acrylic plate treated with the cleaning agent in Example 5, in which the xanthan gum concentration was in the range of 0.1 to 0.5 wt %, showed a significantly smaller amount of adhesion than the untreated plate (control).

[0141] Example 6

[0142] Examples of water-soluble polymers having a carboxylic acid and / or a salt thereof include xanthan gum (trade name: KELZAN AR); As a cationic base, a cationic surfactant Dodecyldimethylamine oxide (Unisafe A-LM ["Unisafe" is a trademark] manufactured by NOF Corporation), Benzalkonium chloride (Product 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.) and Sodium ethylenediaminetetraacetate (EDTA-4Na) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) As other surfactants Lauryl glucoside (trade name: Mydol 12, ["Mydol" is a trademark], manufactured by Kao Corporation; the same applies below), As a water-soluble solvent, diethylene glycol monobutyl ether (trade name: Butyl Diglycol NO), Using citric acid (anhydrous) (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) as a pH adjuster, the bathroom cleaner shown in Table 6 was prepared. The numerical values ​​for each component in Table 6 are in weight %.

[0143] Next, the appearance of each cleaner was observed, and the pH and viscosity were measured. The viscosity of the cleaner was measured using a B-type viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.) with a TM2 rotor at a speed of 60 rpm. Then, a sebum stain adhesion test was conducted on an acrylic plate and a ceramic tile plate using each cleaner in the same manner as in Example 1. Furthermore, the following evaluations were performed. The results are shown in Table 6.

[0144] 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. In addition, the cleaning power of bathtubs was evaluated, and antibacterial tests were conducted on acrylic boards and ceramic tiles treated with the detergent, as well as tests on the adhesion of sebum stains to acrylic boards and ceramic tile boards treated with the detergent.

[0145] <Evaluation of foaming when spraying>

[0146] 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.

[0147] [Evaluation criteria for foaming] ○: 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.

[0148] [Evaluation criteria for foam adhesion]

[0149] 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.

[0150] <Bathtub cleaning power test>

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] [Criteria for evaluating cleaning power] 〇: Dirt is removed cleanly △: Slight dirt remains ×: noticeable dirt remains

[0156] <Antibacterial testing and evaluation>

[0157] The antibacterial test and evaluation were carried out in accordance with JIS Z2801 antibacterial test for plastic products.

[0158] As hard surface test plates, a 50 mm × 50 mm × 2 mm white 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.

[0159] The top surfaces of these test plates (acrylic plate: 50 mm × 50 mm, ceramic tile: 45 mm × 45 mm) were treated by spraying 1.4 ml of each cleaner using the spray bottle. After leaving the test plates 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. For untreated (blank) test specimens, the same procedure was repeated except that tap water was sprayed on the entire top surface of the test plate at a flow rate of 25 ml / sec for 8 seconds (200 ml total).

[0160] <Antibacterial test>

[0161] 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.

[0162] 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.

[0163] The test samples sealed in petri dishes were cultured for 24 hours in a thermostatic chamber set at 35±1°C and 90% humidity.

[0164] After 24 hours of incubation, the test specimen, still covered with the film, was washed over the entire top surface with 9.6 ml of saline using a pipette, thereby washing out the bacteria that had been cultivated between the film and the top surface of the test specimen into the saline.

[0165] 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).

[0166] 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.

[0167] 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.

[0168] 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]

[0169] 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)

[0170] <Antifungal test>

[0171] The cleaning agent of Example 6-3 was subjected to an antifungal test.

[0172] 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.

[0173] 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.

[0174] In the same manner as in the antibacterial test of Example 6, test plates were sprayed with the solution (left for 3 minutes), rinsed, and dried to prepare treated test pieces (5 pieces) of acrylic plates.

[0175] 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.

[0176] <Antifungal test>

[0177] 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.

[0178] 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.

[0179] These test samples sealed in petri dishes were cultured in a thermostatic chamber set at 24±1°C and 95% humidity for 4 weeks.

[0180] The samples cultured in this antifungal test were then first observed with the naked eye, and then, if necessary, observed under a stereomicroscope.

[0181] The growth status of black mold was evaluated according to the following criteria in accordance with Appendix A of JIS Z2911:2018.

[0182] 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.

[0183] <Sebum stain adhesion test>

[0184] Using the trigger spray bottle described above, each cleaner was sprayed once (1.4 ml) onto the top surface of the test plate to treat the surfaces of the acrylic plate and the ceramic tile plate with the cleaner. The test plate was then rinsed with water and dried at 50°C for 30 minutes in the same manner as in Example 1 to prepare test specimens.

[0185] Thereafter, the amount of sebum soiling was measured in the same manner as in Example 1. For the blank (untreated), the results of the blank (acrylic plate) and blank (ceramic tile plate) in Example 1 were used.

[0186] The test evaluation results are shown in Table 6.

[0187] [Table 6]

[0188] The bathroom antifouling cleaner shown in Example 6 exhibited excellent performance in terms of foaming ability, foam adhesion, detergency for bathtub stains when sprayed onto hard surfaces using a spray bottle, the effect of inhibiting the adhesion of sebum stains on cleaned hard surfaces (acrylic boards, ceramic tile boards), and the effect of imparting antibacterial properties to cleaned hard surfaces (acrylic boards, ceramic tile boards). Furthermore, when treated by spray application with the cleaner of Example 6-3, the mold growth was 0, 0, 2, 2, 2 (N = 5), while the mold growth in the blank (untreated) was 4, 4, 4, 4, 4 (N = 5). This treatment significantly inhibited mold growth, demonstrating excellent antifungal properties. In particular, as shown in Example 6, the cleaner composition of the present invention not only exhibits excellent properties for inhibiting the adhesion of stains (especially sebum stains) to hard surfaces, but also has the function of imparting antibacterial and antifungal properties to hard surfaces.

[0189] Reference example

[0190] Next, test pieces were prepared and subjected to a sebum stain adhesion test in the same manner as in Example 1, except that five commercially available bathroom cleaners were sprayed onto the acrylic plate using a spray bottle from each manufacturer once to cover the top surface of each, thereby treating the hard surface. For the blank (untreated), the results of the blank (acrylic plate) from Example 1 were used.

[0191] The results are shown in Table 7. The product names were not disclosed and were indicated by symbols.

[0192] The following commercially available bathroom cleaners were used: Magiclean (trademark) foaming spray (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)

[0193] [Table 7]

[0194] Treatment with a commercial bathroom cleaner showed a rate of adhesion close to or even higher than that of an untreated hydrophobic acrylic panel, and no inhibitory effect on the adhesion of sebum stains was observed.

[0195] Example 7

[0196] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As a cationic base, Polyhexamethylene biguanide (trade name: ProxelIB), a cationic polymer having a biguanide skeleton; Another biguanide-based antibacterial agent is chlorhexidine gluconate (trade name: Spectradyne), a non-polymer biguanide compound. 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, Other surfactants include lauryl glucoside (trade name: Mydol 12), As a water-soluble solvent, diethylene glycol monobutyl ether (trade name: Butyl Diglycol NO) The cleaning agent shown in Example 7 of Table 8 was prepared using the above.

[0197] Comparative Example 4

[0198] Using the same components as in Example 7, a cleaning agent having the composition shown in Comparative Example 4 in Table 8 was prepared.

[0199] Next, the pH of each of the cleaners in Example 7 and Comparative Example 4 was measured, and the appearance was observed. Thereafter, a sebum stain adhesion test was conducted on an acrylic plate using each of the cleaners in the same manner as in Example 1. The results are shown in Table 8.

[0200] [Table 8]

[0201] The hydrophobic acrylic plates treated with the detergents containing the cationic polymer with a biguanide skeleton of Example 7 and the antibacterial agent with a biguanide skeleton other than a polymer showed significantly less sebum stain adhesion than the untreated plate (control).On the other hand, the acrylic plate treated with the detergent containing no xanthan gum of Comparative Example 4 showed an adhesion amount close to that of the untreated plate.

[0202] Example 8

[0203] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As a cationic base, a cationic surfactant is used. Coconut alkylbenzyldimethylammonium chloride (trade name: Hyamine 3500J), Dodecyltrimethylammonium chloride (trade name: Nissan Cation BB) 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.

[0204] The pH was then measured and the appearance was observed.Then, a sebum stain adhesion test was conducted on an acrylic plate using the cleaning agent in the same manner as in Example 1. The results are shown in Table 9.

[0205] [Table 9]

[0206] The hydrophobic acrylic plate treated with the cleaning agent containing a phosphate-based chelating agent and a monovalent or divalent water-soluble inorganic salt shown in Example 8 showed significantly less adhesion than the untreated plate (control).

[0207] Example 9

[0208] As the water-soluble polymer having a carboxylic acid and / or a salt thereof, xanthan gum (trade name: KELZAN AR) was used. As a cationic base, a cationic surfactant 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.

[0209] 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.

[0210] <Antibacterial testing and evaluation against Rhodotorula>

[0211] 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.

[0212] 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 6.

[0213] 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.

[0214] 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.

[0215] 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.

[0216] <Antibacterial test>

[0217] 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 antibacterial testing and evaluation were carried out in the same manner as in Example 6.

[0218] The results are shown in Table 10.

[0219] [Table 10]

[0220] 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.

[0221] 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.

[0222] Furthermore, the rate of sebum adhesion on the acrylic board treated with the cleaning agent was reduced by about 25% compared to the untreated acrylic board, demonstrating an excellent effect in inhibiting the adhesion of sebum stains.

[0223] Example 10

[0224] 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.

[0225] The appearance of the detergent was then observed, and the pH and viscosity were measured. The results are shown in Table 11.

[0226] <Bathtub model dirt adhesion test>

[0227] In Sebum Adhesion Test 1, similar to Example 6, the cleaner was sprayed onto the top surface of a black acrylic plate using a trigger spray container (Condor C spray container 500) and left for 3 minutes (180 seconds). Immediately afterwards, the top surface of the acrylic plate was rinsed with 200 ml of tap water, previously 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, also adjusted to 40°C. The treated test piece was then dried at 50°C for 30 minutes to obtain a treated test piece.

[0228] In Sebum Adhesion Test 2, a treated test piece obtained by the same procedure as in Sebum Adhesion Test 1 was immersed for 30 minutes in hot water (tap water) maintained at a temperature of 40°C, and then dried at 50°C for 30 minutes to obtain a treated test piece.

[0229] 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.

[0230] Using the obtained treated test piece and untreated (blank) test piece, a bathtub model soiling test was carried out in the same manner as in Example 1, and the effect of inhibiting the adhesion of soiling to the bathtub model was evaluated.

[0231] The results are shown in Table 11.

[0232] [Table 11]

[0233] The results of Sebum Stain Adhesion Tests 1 and 2 showed that the detergents of Example 10-2 (Test No. 2) and Example 10-3 (Test No. 3), which contained polyhexamethylene biguanide or chlorhexidine gluconate, demonstrated excellent sebum adhesion inhibitory effects even when the spray-applied top surface was rinsed with 200 ml of water at 40°C. Furthermore, they also demonstrated excellent sebum adhesion inhibitory effects when the top surface was rinsed with 200 ml of water at 40°C, dried once, and then immersed in hot water maintained at 40°C for 30 minutes. The sebum stain adhesion rate of the untreated (blank) test piece in this test was 25%.

[0234] In addition, the sebum stain adhesion rate on the acrylic plate treated with the cleaning agent of Comparative Example 4, which had the same composition as Test No. 2 except that it did not contain xanthan gum, remained almost the same as that of the untreated plate (blank) under both treatment conditions of Adhesion Tests 1 and 2.

[0235] Example 11

[0236] The acrylic and tile panels were treated with the cleaning agent of Example 9 in the following manner, and the sebum stain adhesion rate and antibacterial performance were evaluated. The results are shown in Table 12. The values ​​for each component in Table 12 are in weight percent. <Bathtub model dirt adhesion test>

[0237] 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 3 mm black acrylic plate and a 45 mm x 45 mm x 7 mm white ceramic tile) using the following procedure.

[0238] 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, the top surface of the test plate was immediately rinsed with 200 ml of tap water adjusted to 40°C using a wash bottle (product name: J wash bottle 500 ml) by pouring water onto the top surface of the test plate.The back surface was also rinsed with 20 ml of tap water adjusted to 40°C, and then dried in a thermostatic bath at 50°C for 30 minutes to prepare a detergent-treated plate.Next, the treatments for Sebum Adhesion Tests 1 to 4 were carried out as follows.

[0239] For Sebum Adhesion Test 1 (acrylic plate) and Sebum Adhesion Test 2 (tile plate), the top surface of the test plate was rinsed with tap water at room temperature (31°C) at a flow rate of 25 ml / sec for 80 seconds (2000 ml), and then dried in a constant temperature bath at 50°C for 30 minutes to obtain a treated test piece.

[0240] On the other hand, in Sebum Adhesion Test 3 (acrylic plate) and Sebum Adhesion Test 4 (tile plate), the test plate was immersed in hot water (tap water) maintained at 40°C for 30 minutes, and then dried in a thermostatic bath at 50°C for 30 minutes to obtain a treated test piece.

[0241] In Test No. 2, the test plate was placed upright and the top surface was sprayed with the detergent to cover the entire surface. The entire top surface was then 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 plate was then left for three minutes. The top and back surfaces were then rinsed and dried in the same manner as in Test No. 1 to prepare a detergent-treated plate. The test pieces were then subjected to the Sebum Adhesion Tests 1 to 4, yielding treated test pieces.

[0242] In addition, without treating with a detergent, tap water adjusted to a temperature of 40°C was similarly poured in a washing bottle (product name: J washing bottle 500 ml) onto the top surface of the test plate (acrylic plate and tile plate) to rinse, and 20 ml of water was poured onto the back surface to rinse, and then the plate was dried in a constant temperature bath at 50°C for 30 minutes to obtain an untreated (blank) test piece.

[0243] Thereafter, a sebum stain adhesion test was carried out on each treated test piece in the same manner as in Example 1. The results are shown in Table 12.

[0244] <Antibacterial testing and evaluation>

[0245] In Test Nos. 1 and 2, detergent-treated panels were prepared using the same procedures as in the bathtub model soil adhesion test. Next, the same treatments as in Sebum Adhesion Test 3 (acrylic panel) and Sebum Adhesion Test 4 (tile panel) were performed, and the test panels were placed in a sterilized petri dish with the treated surface facing up and dried for 12 hours in a constant temperature dryer maintained at 50°C to obtain treated test specimens for Antibacterial Test 3 and Antibacterial Test 4. Similarly to the above, the top surface of the test panel was rinsed by pouring 200 ml of water over it, and the back surface was also rinsed by pouring 20 ml of water over it. Then, the test panel was placed in a sterilized petri dish with the treated surface facing up and dried for 12 hours in a constant temperature dryer maintained at 50°C to obtain untreated (blank) test specimens.

[0246] Thereafter, each treated test piece was subjected to an antibacterial test and evaluation in the same manner as in Example 6. The results are shown in Table 12.

[0247] [Table 12]

[0248] In Test No. 1, based on Sebum Adhesion Tests 1 and 2, both the acrylic and tile panels treated with a detergent containing polyhexamethylene biguanide maintained excellent sebum adhesion inhibitory effects even when the detergent-treated surfaces were rinsed with a large amount of water (2000 ml). Furthermore, the sebum stain adhesion rate of the untreated (blank) test specimens in this test was 28.5% for the acrylic panel and 9.3% for the tile panel.

[0249] Furthermore, Sebum Adhesion Tests 3 and 4 showed that the excellent sebum adhesion inhibitory effect was maintained even after 30 minutes of immersion in hot water maintained at 40°C. Furthermore, the excellent antibacterial effect was maintained on both the acrylic board and the tile board, which were subjected to the same rinsing and immersion treatment.

[0250] On the other hand, in Test No. 2, the test board was placed vertically and the entire vertical top surface coated with the cleaner was scrubbed three times with a sponge. This is thought to have reduced the amount of cleaner applied to the test board compared to Test No. 1, but even under these application conditions, the excellent sebum adhesion inhibitory effect was maintained. Furthermore, both the acrylic board and the tile board, which had been subjected to similar rinsing and soaking treatments, maintained their excellent antibacterial effect. Bathroom cleaners typically involve scrubbing the surface with a tool such as a sponge, and these results suggest that even in this type of cleaning procedure, excellent sebum adhesion inhibitory effect and excellent antibacterial effect can be provided.

[0251] Example 12

[0252] To demonstrate the effect of inhibiting feces adhesion 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. The cleaner in Test No. 1 has the same composition as the cleaner in Example 9, while the cleaner in Test No. 2 has a composition in which the amount of xanthan gum is increased by 0.1 weight percent compared to the composition of No. 1.

[0253] The appearance of the detergent was then observed, and the pH and viscosity were measured. The results are shown in Table 13.

[0254] <Effective in preventing oily stain adhesion>

[0255] Since the dirt that deposits on toilet bowls is mainly oily dirt contained in feces, the bathroom model sebum dirt from Example 1 was used as a substitute for the test of the effect of inhibiting fecal adhesion. Furthermore, although ceramic is the main material used for toilet bowl base materials, acrylic resin-based materials are also being sold and are becoming more popular. Since oily dirt generally adheres more easily to plastic resin materials than to ceramic, this time the test was conducted using an acrylic plate.

[0256] As in Example 6, a trigger spray bottle (Condor C spray bottle 500) was used to spray a single coat of the cleaner onto a test plate (a 50 mm × 50 mm × 3 mm black acrylic plate) so that the top surface of the test plate was covered. After leaving the test plate for 3 minutes, the top surface of the test plate was immediately rinsed with tap water at room temperature (11°C) at a flow rate of 100 ml / sec for 150 seconds (15 L: Sebum Adhesion Test 1), 300 seconds (30 L: Sebum Adhesion Test 2), or 450 seconds (45 L: Sebum Adhesion Test 3). The backside of each test plate was then rinsed with tap water at the same flow rate and temperature for 5 seconds. The test plate was then dried in a constant temperature bath at 50°C for 30 minutes to obtain treated test pieces. Each treated test piece was subjected to a sebum adhesion test in the same manner as in Example 1. The results are shown in Table 13.

[0257] In addition, without treating with a detergent, the top surface of each test plate was rinsed with tap water at room temperature (11°C) at a flow rate of 100 ml / sec for 150 seconds (15 L: Sebum Adhesion Test 1), 300 seconds (30 L: Sebum Adhesion Test 2), or 450 seconds (45 L: Sebum Adhesion Test 3). The back surface of each test plate was then rinsed with tap water at the same flow rate and temperature for 5 seconds. The test plates were then dried in a constant temperature bath at 50°C for 30 minutes to obtain untreated (blank) test pieces. The sebum adhesion test was then performed on each of these untreated (blank) test pieces using the same method as in Example 1. The results are shown in Table 13.

[0258] [Table 13]

[0259] According to the Tokyo Metropolitan Government Waterworks Bureau's "Survey on Living Water Use," the average amount of water used per person per day at home is 214 liters (2019), of which 21% is used in the toilet (same survey in 2015). Therefore, this test was conducted with a rinse water volume of up to 45 liters.

[0260] Both the detergents in Test No. 1 and Test No. 2 maintained excellent sebum adhesion suppression effects compared to the untreated detergent, regardless of the amount of rinse water used. Detergent No. 2, which contained 0.1% more xanthan gum, maintained even better sebum adhesion suppression effects than detergent No. 1.

[0261] It was suggested that a good effect of inhibiting adhesion of sebum, i.e., oily dirt, can be provided even in an environment 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) A base in a cationic state, which comprises one or both of a surfactant and a polymer in a cationic state: 0.02 to 10% by weight c) Electrolyte: 0.1-15% by weight a pH of 3 to 12, a weight ratio of the water-soluble polymer of a) to the base in a cationic state of b) a) / b) of 0.167 to 5.00, and a viscosity of 20 to 500 mPa s as measured at 60 rpm with a Brookfield viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.) using a TM2 rotor; When applied to a hard surface and rinsed with water, the complex of the water-soluble polymer (a) and the base (b) in a cationic state becomes insolubilized and remains on the hard surface, thereby hydrophilizing the hard surface whether the hard surface is made of a hydrophilic or hydrophobic material, thereby imparting and maintaining anti-fouling properties against oily stains.

2. 10. The composition of claim 1, excluding those containing an anionic surfactant.

3. The base in a cationic state comprising one or both of the surfactant and polymer in a cationic state described in b) above, Alkylamine oxides, alkenylamine oxides, alkylamine salt surfactants, alkenylamine salt surfactants, quaternary ammonium salt surfactants, pyridine ring salt-containing 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 amine in the main chain, cationic polymers having an amino group in the side chain, and guanidine skeleton or biguanide skeleton compounds other than polymers 2. The composition according to claim 1, wherein the base is in a cationic state and comprises one or more selected from the group consisting of:

4. The base in a cationic state of b) above is 4. 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.

5. The composition according to any one of claims 1 to 3, 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.

6. 4. The composition according to claim 1, 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.

7. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.05 to 5% by weight b) A base in a cationic state, which comprises one or both of a surfactant and a polymer in a cationic state: 0.02 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 of a) to the base in a cationic state of b) of 0.167 to 5.00, and a viscosity of 20 to 500 mPa s as measured at 60 rpm using a Brookfield viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.) with a TM2 rotor; and applying the liquid composition to a hard surface. By rinsing the liquid composition applied to the hard surface with water, the complex of the water-soluble polymer of a) and the base in a cationic state of b) in the liquid composition is insolubilized and left on the hard surface, thereby making the hard surface hydrophilic regardless of whether the hard surface is made of a hydrophilic material or a hydrophobic material, thereby imparting and maintaining antifouling properties against oily stains. A method for inhibiting dirt adhesion to a hard surface, comprising:

8. The method of claim 7, wherein the liquid composition does not contain an anionic surfactant.

9. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.05 to 5% by weight b) A base in a cationic state consisting of one or both of a surfactant and a polymer in a cationic state, which contains one or more selected from polyhexamethylene guanidine or a salt thereof, polyaminopropyl biguanide or a salt thereof, polyhexamethylene biguanide or a salt thereof, chlorhexidine or a salt thereof, other cationic polymers having a guanidine skeleton or a biguanide skeleton in the main chain or side chain, and other guanidine skeleton or biguanide skeleton compounds other than polymers: 0.02 to 10% by weight c) Electrolyte: 0.1-15% by weight A liquid cleaning composition for inhibiting adhesion of dirt to hard surfaces, which contains

10. The composition according to claim 9, wherein the base in a cationic state of b) further comprises one or more selected from alkylamine oxides, alkenylamine oxides, alkylamine salt surfactants, alkenylamine salt surfactants, quaternary ammonium salt surfactants, pyridine ring salt-containing surfactants, cationic polymers having a quaternary ammonium salt in the main chain or side chain, cationic polymers having an amine in the main chain, and cationic polymers having an amino group in the side chain.

11. The composition according to claim 9 or 10, 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.

12. 11. The composition according to claim 9 or 10, 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.

13. a) Water-soluble polymer having a carboxylic acid and / or a salt thereof: 0.05 to 5% by weight b) A base in a cationic state consisting of one or both of a surfactant and a polymer in a cationic state, which contains one or more selected from polyhexamethylene guanidine or a salt thereof, polyaminopropyl biguanide or a salt thereof, polyhexamethylene biguanide or a salt thereof, chlorhexidine or a salt thereof, other cationic polymers having a guanidine skeleton or a biguanide skeleton in the main chain or side chain, and other guanidine skeleton or biguanide skeleton compounds other than polymers: 0.02 to 10% by weight c) Electrolyte: 0.1-15% by weight A method for inhibiting the adhesion of dirt, 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.

14. The method according to claim 13, wherein the base in a cationic state of b) further comprises one or more selected from alkylamine oxides, alkenylamine oxides, alkylamine salt surfactants, alkenylamine salt surfactants, quaternary ammonium salt surfactants, pyridine ring salt-containing surfactants, cationic polymers having a quaternary ammonium salt in the main chain or side chain, cationic polymers having an amine in the main chain, and cationic polymers having an amino group in the side chain.

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