Liquid antifouling detergent composition and antifouling method

Abstract

To provide a liquid stain-resistant cleaner composition that is applied to hard surfaces in general and can protect the treated hard surfaces against soiling for a long time regardless of whether the treated surfaces are hydrophilic or hydrophobic ones, and to provide a method for antifouling treatment.SOLUTION: A liquid stain-resistant cleaner composition for hard surfaces contains a) xanthan gum: 0.01-5 wt.%, b) a surfactant in a cationic state: 0.02-10 wt.%, and c) an inorganic acid and / or organic acid: 0.003-10 wt.%, with a pH of 5.5 or less. There is also provided a method for antifouling treatment in which the liquid, which contains a) xanthan gum: 0.01-5 wt.%, b) a surfactant in a cationic state: 0.02-10 wt.%, and c) an inorganic acid and / or organic acid: 0.003-10 wt.%, with a pH of 5.5 or less, is used to treat a hard surface composed of a hydrophilic or hydrophobic material.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid antifouling detergent composition and an antifouling method that can treat hard surfaces to inhibit fouling. [Background technology]

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

[0003] In particular, areas around water such as kitchens, bathrooms, sinks, and toilets are frequently used and are the places in a home that are most prone to dirt.As a result, they require frequent cleaning and are the most time-consuming to maintain cleanliness.

[0004] Against this backdrop, many products have been proposed to make cleaning easier for toilets, etc. Among these is the automatic flush cleaner, which is installed under the faucet of the toilet hand-washing tank and dispenses a small amount of detergent when water is flushed, cleaning the inside of the toilet bowl and making it less likely to get dirty.

[0005] Alternatively, cleaning agents are also available that can be sprayed directly onto the inside, outside, and surrounding areas of the toilet bowl to remove dirt and make it less likely to get dirty.

[0006] Numerous techniques have been developed to make it difficult for such stains to adhere, so-called antifouling techniques.

[0007] For example, Japanese Patent Application Laid-Open No. 2002-060784 describes a germicidal cleaner for hard surfaces that contains a polymer having a molecular weight of 1,000 to 6,000,000 and in which the ratio of monomer units having a quaternary ammonium group is 10 to 100 mol% relative to the total monomers, and a germicidal agent having a quaternary ammonium group and a molecular weight of 1,000 or less.

[0008] JP 2002-146395 A describes a cleaning agent for hard surfaces that contains one or more surfactants selected from nonionic surfactants and amphoteric surfactants, and a polymer containing a monomer unit having a quaternary ammonium group or a tertiary amino group.

[0009] Japanese Patent Application Laid-Open No. 2003-313600 describes an antifouling detergent for hard surfaces that contains a monomer having one or more groups selected from an amino group and a quaternary ammonium group in the molecule, and a monomer represented by -SO2-.

[0010] As mentioned above, a variety of products have been proposed for toilets, which mainly have hydrophilic hard surfaces (ceramic tiles), but there are almost no products that can adsorb to the surfaces of bathtubs and sinks, which mainly have hydrophobic hard surfaces (artificial marble, plastic, stainless steel, etc.), make the surfaces hydrophilic, and prevent the adhesion of oil and sebum stains.

[0011] Hydrophobic surfaces have a high affinity for oil and 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.

[0012] For example, JP-A-2008-523184 describes a cleaning adjuvant containing a cationic acrylic polymer containing a hydrophobic group.

[0013] JP-A-2009-545642 describes a composition comprising an amphiphilic block copolymer.

[0014] 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).

[0015] However, when it comes to antifouling hydrophobic surfaces, there are issues with achieving sufficient antifouling effect and durability of the effect in practical use, and few such products have been put into practical use. Furthermore, for example, bathroom 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 have a single detergent that can achieve antifouling properties on all hard surfaces, from hydrophilic to hydrophobic.

[0016] 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.

[0017] 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.

[0018] Patent No. 5637586 discloses a cleaning agent that 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 stains on plastic surfaces.

[0019] 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.

[0020] 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]

[0021] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-60784 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-146395 [Patent Document 3] Special Publication No. 2008-523184 [Patent Document 4] Special Publication No. 2009-545642 [Patent Document 5] Japanese Patent Application Laid-Open No. 2015-206020 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-206021 [Patent Document 7] Japanese Patent Application Laid-Open No. 2016-199679 [Patent Document 8] Japanese Patent Application Laid-Open No. 2016-222773 [Patent Document 9] Patent No. 2963065 [Patent Document 10] Patent No. 5779390 [Patent Document 11] Patent No. 5637586 [Patent Document 12] Japanese Patent Application Laid-Open No. 2017-78134 [Patent Document 13] Patent No. 6584004 Summary of the Invention [Problem to be solved by the invention]

[0022] An object of the present invention is to provide a liquid antifouling detergent composition for hard surfaces and an antifouling method which can maintain the antifouling properties of the treated hard surfaces for a long time, regardless of whether they are hydrophilic or hydrophobic. [Means for solving the problem]

[0023] The present invention can be expressed, for example, as follows. a) Xanthan gum: 0.01 to 5% by weight b) Surfactant in a cationic state: 0.02 to 10% by weight c) Inorganic acid and / or organic acid: 0.003 to 10% by weight A liquid antifouling detergent composition for hard surfaces, comprising:

[0024] The present invention can also be expressed as follows. a) Xanthan gum: 0.01 to 5% by weight b) Surfactant in a cationic state: 0.02 to 10% by weight c) Inorganic acid and / or organic acid: 0.003 to 10% by weight A stain-proofing method for treating a hard surface made of a hydrophilic or hydrophobic material using a liquid composition containing the above compound and having a pH of 5.5 or less. [Effects of the Invention]

[0025] According to the present invention, the antifouling properties of the treated hard surfaces can be maintained for a long time, regardless of whether they are hydrophilic or hydrophobic. This antifouling effect reduces the frequency of cleaning, for example, when cleaning bathrooms, toilets, sink areas, etc., and makes it easier to maintain hard surfaces clean by simply washing or rinsing with water without using detergent, making the present invention also useful from an environmental perspective. DETAILED DESCRIPTION OF THE INVENTION

[0026] (1) The liquid antifouling detergent composition for hard surfaces of the present invention and the liquid composition used in the antifouling method for treating hard surfaces made of a hydrophilic or hydrophobic material of the present invention are a) Xanthan gum: 0.01 to 5% by weight b) Surfactant in a cationic state: 0.02 to 10% by weight c) Inorganic acid and / or organic acid: 0.003 to 10% by weight and its pH is 5.5 or less.

[0027] (1-1) In the present invention, the antifouling function is exhibited by the above-mentioned "a) xanthan gum."

[0028] Xanthan gum is a polysaccharide represented by the following general formula (I), with a molecular weight of approximately 2 million or 13 to 50 million, and a main chain consisting of two glucose molecules and a side chain consisting of repeating units consisting of two mannose molecules and one glucuronic acid molecule.

[0029] [ka] ....(I)

[0030] Xanthan gum is a water-soluble polymer that is negatively charged due to the carboxyl group contained in glucuronic acid and the pyruvic acid that may be present in the terminal mannose residue. When the liquid composition of the present invention (hereinafter also referred to as "liquid composition" including "liquid antifouling detergent composition") is applied to a hard surface, this negative charge is presumed to hydrophilize the hard surface.

[0031] There are various types of polysaccharides, but xanthan gum is the only one that can modify hydrophilic hard surfaces such as ceramic tiles as well as hydrophobic hard surfaces such as plastics and stainless steel, thereby exhibiting excellent stain resistance, which has not been previously known.

[0032] For hydrophilic hard surfaces such as ceramic tiles, porcelain, glass, and enamel, xanthan gum alone can adsorb to the surface to provide anti-fouling properties. However, to provide anti-fouling properties on hydrophobic hard surfaces such as plastics (synthetic resins) such as polyethylene resin, polypropylene resin, polycarbonate resin, polystyrene resin, acrylic resin (acrylic ester resin, methacrylic ester resin, etc.), polyester resin (polyethylene terephthalate resin, etc.), polyvinyl chloride resin, urethane resin, and polyamide resin, as well as stainless steel, aluminum, and aluminum alloys, it is necessary to use xanthan gum in combination with the above-mentioned "b) surfactant in a cationic state."

[0033] However, because xanthan gum has a carboxylic acid in its side chain, when xanthan gum is used in combination with a significant amount of a surfactant in a cationic state (hereinafter also referred to as a "cationic surfactant"), an insoluble complex is immediately formed, making it unusable as a cleaning agent or antifouling agent. Therefore, it is necessary to further add an inorganic or organic acid to adjust the pH to 5.5 or less to suppress the formation of an insoluble complex.

[0034] When the liquid composition of the present invention is used to treat such a hydrophobic hard surface, it is believed that the hydrophobic moieties, such as alkyl or alkenyl groups, of the cationic surfactant are adsorbed to the hydrophobic hard surface through hydrophobic interaction, and that the cationic groups of the cationic surfactant and the anionic groups of xanthan gum are electrostatically attracted to each other, thereby adsorbing xanthan gum to the hydrophobic hard surface. This is thought to modify the hydrophobic hard surface to be hydrophilic, making it less susceptible to oily stains.

[0035] When the liquid composition of the present invention is used to treat a hydrophilic hard surface, the hydrophilic hard surface is negatively charged, due to the presence of silicon dioxide or the like, and thus electrostatically adsorbs the cationic surfactant. Furthermore, it is presumed that the anionic groups of xanthan gum are electrostatically attracted to the cationic groups of the cationic surfactant, resulting in xanthan gum being adsorbed onto the hydrophilic hard surface. This is believed to result in a more excellent antifouling effect on the hydrophilic hard surface than when the surface is treated with xanthan gum alone.

[0036] (1-2) As described above, the liquid antifouling detergent composition of the present invention and the antifouling method 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 acrylic, polypropylene, and vinyl chloride, stainless steel, aluminum, and aluminum alloys, found, for example, inside and outside a residence in general, particularly in wet areas such as bathrooms, bathtubs, washbasins, drains, sinks, and toilets, thereby exhibiting an antifouling effect that continuously inhibits the adhesion of hydrophobic stains such as oily stains, sebum stains, soap scum, and protein and makes the adhered stains easier to remove.

[0037] Cationic surfactants are thought to have the effect of making it easier to break down dirt by undergoing a substitution reaction with calcium phosphate, the main component of urinary stones, a typical toilet stain, and metal ions in fatty acid metal salts known as soap scum, a typical bathroom and bathtub stain.

[0038] Furthermore, by applying the liquid antifouling detergent composition and method of the present invention to hydrophobic hard surfaces such as various plastics, stainless steel, aluminum, or aluminum alloys commonly used in bathtubs, xanthan gum can be adsorbed onto the hard surface, thereby achieving a sustained antifouling effect. Even when the hydrophobic hard surface is repeatedly rinsed with water, the surface of the plastic, stainless steel, aluminum, or aluminum alloy remains hydrophilic, and adhesion of soap scum, sebum, and other oily stains is inhibited. Furthermore, when the liquid antifouling detergent composition and method are applied to hydrophilic hard surfaces made of silicon dioxide, such as ceramic tiles and mirrors used on bathroom walls, floors, and sinks, the hydrophilicity of the hydrophilic hard surface is increased, and adhesion of oily stains can be sustained.

[0039] (2) Xanthan gum

[0040] The concentration of "a) xanthan gum" in the liquid composition of the present invention is 0.01 to 5% by weight.

[0041] If the content is less than 0.01% by weight, a sufficient antifouling effect will not be exhibited. If the content exceeds 5.0% by weight, the viscosity will be too high, impairing the handleability of the detergent. The content is preferably 0.025 to 3% by weight, more preferably 0.1 to 1% by weight, and even more preferably 0.25 to 0.6% by weight.

[0042] The xanthan gum used in the present invention is a type of polysaccharide, and among various polysaccharides, it has excellent antifouling properties on hydrophobic hard surfaces (especially hydrophobic hard surfaces made of plastic) such as plastic (synthetic resin), stainless steel, aluminum, or aluminum alloy.

[0043] Furthermore, compared to other polysaccharides, xanthan gum exhibits high viscosity at low concentrations, while its viscosity drops sharply 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 the detergency of detergents and the antifouling properties of antifouling agents.

[0044] (3) Surfactants in a cationic state

[0045] (3-1) In the liquid composition of the present invention, "b) a surfactant in a cationic state" is used.

[0046] The term "surfactant in a cationic state" includes not only cationic surfactants but also surfactants that have cationic properties when, for example, the pH is within a certain range. For example, it includes amphoteric surfactants that have only cationic properties when the pH is within a certain range, but does not include amphoteric surfactants that have both cationic and anionic properties in one molecule.

[0047] In the liquid composition, as described above, the cationic surfactant functions as a fixing agent that can prevent xanthan gum from being adsorbed onto a hydrophobic hard surface or a hydrophilic hard surface and from being removed even by rinsing with water to a certain extent (to an extent that can exert an antifouling effect, for example, to an extent that can form a thin coating on the hard surface).

[0048] The concentration of "b) surfactant 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 a hydrophobic surface will be insufficient, and if it exceeds 10.0% by weight, it will be an excessive amount.

[0049] Anionic groups (-COO) in xanthan gum - ) and the molar concentration of the cationic groups (N + ) molar concentration ratio (COO - / N + ) is preferably 0.02 to 15, more preferably 0.05 to 6.5, and even more preferably 0.1 to 3.5.

[0050] Anionic groups (-COO) in xanthan gum - ) is calculated as follows. The structure of one unit of xanthan gum (a repeating unit whose main chain is composed of two glucose molecules and whose side chain is composed of two mannose molecules and one glucuronic acid molecule) is represented by general formula (I). Calculations are made on the assumption that all units in xanthan gum have two carboxylic acids derived from pyruvic acid linked to glucuronic acid and the terminal mannose. Sodium (Na), potassium (K), and calcium (Ca) also exist as counter ions to the carboxylic acids, but these are calculated as -COOH here. In this case, the chemical formula per unit is C 35 H 49 O 29 The molecular weight is 933. Therefore, the carboxylic acid equivalent is 466.5. From these, the anion group (-COO - ) to calculate the molar concentration.

[0051] On the other hand, the cationic group (N + The molar concentration of the cationic surfactant (N) is calculated from the molecular weight of the cationic surfactant. For example, the molecular weight of dodecylamine oxide is 229.4, and the molecular weight of dodecyltrimethylammonium salt is 263.9. + ) to calculate the molar concentration.

[0052] (3-2) The "b) surfactant in a cationic state" in the present invention is preferably, but is not limited to, an alkylamine oxide or alkenylamine oxide used at a pH of 8 or less, as well as an alkylamine salt type or alkenylamine salt type, a quaternary ammonium salt type, or a pyridine ring salt-containing type. The surfactant in a cationic state can be used alone or in combination.

[0053] (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.

[0054] [ka]

[0055] In order to allow one or both of an alkylamine oxide and an alkenylamine oxide to function as a fixing agent that adsorbs xanthan gum to a hard surface made of a hydrophilic or hydrophobic material in the liquid composition of the present invention, i.e., to contain them as surfactants in a cationic state (cationic state), the pH of the liquid composition is preferably adjusted to 5.5 or less, more preferably 4.5 or less. An organic acid or an inorganic acid can be used as an agent for adjusting the pH to the neutral to acidic side.

[0056] 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.

[0057] (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.

[0058] 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.

[0059] (iii) As the quaternary amine salt type, tetraalkyl (or tetraalkenyl) ammonium salts or benzyltrialkyl (or trialkenyl) ammonium salts are preferred.

[0060] The number of carbon atoms in the alkyl group or alkenyl group in the quaternary amine 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. Specific examples of preferred compounds include dodecyltrimethyl quaternary ammonium chloride, tetradecyltrimethyl quaternary ammonium chloride, hexadecyltrimethyl quaternary ammonium chloride, benzalkonium chloride having an alkyl group with 8 to 17 carbon atoms, benzethonium chloride, didecyldimethylammonium chloride, and N,N-didecyl-N-methylpoly(oxyethyl)ammonium propionate.

[0061] (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.

[0062] (4) Inorganic and / or organic acids

[0063] (4-1) In the liquid composition of the present invention, "c) an inorganic acid and / or an organic acid", that is, one or both of an inorganic acid and an organic acid, is used to adjust the pH to 5.5 or less.

[0064] As described above, when xanthan gum, which is anionic and has a carboxylic acid in its side chain, is mixed with a cationic surfactant, 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 an inorganic acid and / or an organic acid.

[0065] The concentration of "c) inorganic acid and / or organic acid" in the liquid composition of the present invention is 0.003 to 10% by weight, and depends on the concentrations of xanthan gum and cationic surfactant. The concentration of the inorganic acid and / or organic acid is adjusted appropriately to adjust the pH of the liquid composition to an appropriate level depending on the intended use.

[0066] The pH of the liquid composition of the present invention is 5.5 or less. More preferably, it is 4.5 or less, even more preferably 3.5 or less, and particularly preferably 2 or less. By adjusting the pH to a level that allows use with bare hands, the composition can be used easily and safely without particular concern about irritation to the skin, eyes, etc. Furthermore, when the detergent is simply applied, or applied and then scrubbed using a tool such as a sponge or brush with a handle, a cleaner with a lower pH can be provided. In general, when cleaning toilet urinary stones, limescale, bathroom limescale, soap scum, limescale in the washroom, soap scum, limescale in the kitchen sink, etc., a cleaner (liquid composition) with a lower pH, i.e., a stronger acidity, will remove dirt more effectively.

[0067] (4-2) Preferred examples of "c) inorganic acid and / or organic acid" in the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid, and organic acids such as formic acid, acetic acid, butyric acid (butanoic acid), and hexanoic acid, aromatic carboxylic acids such as salicylic acid, benzoic acid, and phthalic acid, sulfamic acid, oxalic acid, lactic acid, maleic acid, malonic acid, succinic acid, glutaric acid, malic acid, and citric acid. Among these, hydrochloric acid or sulfuric acid is preferred as an inorganic acid, and from the viewpoint of pH stability, sulfamic acid, lactic acid, and citric acid, which are organic acids, are particularly preferred.

[0068] The "c) inorganic acid and / or organic acid" may be used singly or in combination of two or more.

[0069] (5) Examples of components other than a), b) and c) that may be contained in the liquid composition of the present invention

[0070] (5-1) In the present invention, in addition to a cationic surfactant, a nonionic surfactant or an amphoteric surfactant is preferably used 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 a sponge or brush.

[0071] (i) The nonionic surfactant is preferably at least one selected from polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, polyoxypropylene alkyl ethers, polyoxypropylene alkenyl 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.

[0072] 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 (II): R 1 -(OR 2 )nGm ....(II) [In formula (II), R 1 is an alkyl group having 8 to 16 carbon atoms, R 2 represents an alkylene group having 2 to 4 carbon atoms, G represents a group derived from a reducing sugar, n represents the average number of moles added (0 to 5), and m represents the average degree of condensation (1 to 3). The reducing sugar may be either an aldose or a ketose, but is preferably glucose.]

[0073] Examples of alkyl glucosides include octyl polyglucoside, 2-ethylhexyl polyglucoside, decyl polyglucoside, lauryl polyglucoside, myristyl polyglucoside, palmityl polyglucoside, stearyl lauryl polyglucoside, and oleyl polyglucoside, with alkyl glucosides having an alkyl group with 14 or less carbon atoms being particularly preferred.

[0074] The liquid composition of the present invention preferably contains 0.5 to 10% by weight of alkyl glucoside. 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 will not change.

[0075] (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, lauryl hydroxysulfobetaine, etc.

[0076] (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 polyoxyalkylene alkyl ether sulfates and fatty acid salts (soaps).

[0077] In addition, since anionic surfactants may form insoluble complexes with the above-mentioned "b) surfactants in a cationic state," it is necessary to suppress the formation of insoluble complexes and obtain a uniform liquid composition by adding a polycarboxylic acid and / or its salt having metal chelating ability depending on the set pH.

[0078] (5-2) The liquid composition of the present invention preferably contains a water-soluble solvent in order to further enhance the ability to clean soap scum and sebum stains.

[0079] Specific examples include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, polyoxyethylene / polyoxypropylene glycol dimethyl ether, polyoxyethylene glycol phenyl ether, phenyl carbitol, phenyl cellosolve, and benzyl carbitol. Among these, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, and dipropylene glycol monobutyl ether are preferred in terms of uniform solubilization of the components contained in the liquid composition, detergency, odor, and feel. Diethylene glycol monobutyl ether is particularly preferred. The water-soluble solvent is preferably contained in the liquid composition in an amount of 2 to 15% by weight. If the amount is less than 2%, the detergency for oily stains is insufficient. If the amount is more than 15% by weight, foaming ability and foam retention are reduced, and the odor can be unpleasant.

[0080] The liquid composition of the present invention may contain a metal chelating agent in order to improve the cleaning properties of soap scum, urinary stones, and limescale. Specific examples of metal chelating agents include malonic acid, succinic acid, glutaric 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 citric acid and / or its sodium salt, and ethylenediaminetetraacetic acid and / or its sodium salt.

[0081] (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, or 0.5 to 10 wt % of ethanol or isopropyl alcohol to improve the refreshing feeling and adjust the viscosity of the detergent. In addition, chelating agents, disinfectants, bleaches, preservatives, deodorizers, fragrances, colorants, pigments, thickeners other than xanthan gum, water, etc. may be contained.

[0082] (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.

[0083] 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]

[0084] Example 1

[0085] Liquid antifouling detergents having the compositions shown in Examples 1-1 to 1-4 in Table 1 were prepared using xanthan gum (trade name: KELZAN AP-AS ["KELZAN" is a trademark], manufactured by CP KELCO), lauryl dimethylamine oxide (trade name: Amphitol 20N ["Amphitol" is a trademark], manufactured by Kao Corporation) and dodecyltrimethyl quaternary ammonium chloride (trade name: Nissan Cation BB ["Nissan Cation" is a trademark], manufactured by NOF Corporation) as cationic surfactants, hydrochloric acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) as an inorganic acid, and sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) as an organic acid.

[0086] The pH of each sample was then measured and the appearance was observed, after which an antifouling test and evaluation were carried out using each liquid antifouling detergent. The results are shown in Table 1.

[0087] Comparative Example 1

[0088] Liquid antifouling detergents having the compositions shown in Comparative Examples 1-1 to 1-4 in Table 1 were prepared using the xanthan gum of Example 1 and the following surfactants that were not cationic [i.e., did not fall under the category of surfactants in a cationic state (b)]. Comparative Example 1-1: Lauryl glucoside (trade name: Mydol 12 ["Mydol" is a trademark], manufactured by Kao Corporation) Comparative Example 1-2: Sodium polyoxyethylene dodecyl sulfate (trade name: EMAL 20CM ["EMAL" is a trademark], manufactured by Kao Corporation) Comparative Example 1-3: Sodium laurate (trade name: Nonsal LN-1 ["Nonsal" is a trademark], manufactured by NOF Corporation) Comparative Example 1-4: Lauryl hydroxysulfobetaine (trade name: Amphitol 20HD, manufactured by Kao Corporation)

[0089] Furthermore, a liquid antifouling detergent having the composition shown in Comparative Example 1-5 in Table 1 was prepared using only the xanthan gum of Example 1.

[0090] Next, the pH of Comparative Examples 1-1 to 1-5 was measured, and the appearance was observed. Then, an antifouling test was conducted using each liquid antifouling detergent, and an antifouling test was conducted for Comparative Example 1-6 without using any liquid antifouling detergent, and each was evaluated. The results are shown in Table 1.

[0091] <Stain resistance test and evaluation>

[0092] The hard surface test panels prepared were a 45mm x 45mm x 7mm white ceramic tile (white mosaic tile), a 50mm x 50mm x 5mm transparent polyester plate (Petec ["Petec" is a trademark], manufactured by Takiron C.I.), a 50mm x 50mm x 5mm transparent acrylic plate (Comoglass ["Comoglass" is a trademark], manufactured by Kuraray), a 50mm x 50mm x 5mm transparent polyvinyl chloride plate (manufactured by Takiron C.I.), and a 50mm x 50mm x 5mm stainless steel plate (SUS304 sheet No. 1 shearing cut).

[0093] The hard surface of each test plate was treated with antifouling by dripping 2 ml of the prepared liquid antifouling detergent onto the top surface of the test plate. After leaving it for 3 minutes (180 seconds), the test plate was tilted vertically to rinse off the liquid antifouling detergent, and the treated hard surface was rinsed with 20 ml of ion-exchanged water and then air-dried at room temperature.

[0094] After drying, the test plate was rinsed by spraying tap water onto the center of the top surface at a flow rate of 25 ml / sec for 8 seconds (total 200 ml), and then dried for 30 minutes in a constant temperature dryer maintained at 50°C.

[0095] This rinsing with running tap water and drying at a constant temperature of 50°C was repeated three times (200 ml x 3 times = 600 ml equivalent rinsing).

[0096] In this way, a test plate was obtained that had undergone the antifouling treatment, rinsing with ion-exchanged water, and air drying at room temperature once, followed by rinsing with running tap water three times and drying at a constant temperature of 50° C. In the antifouling test of Comparative Example 1-6 for an untreated test plate that had not been subjected to the antifouling treatment with a liquid antifouling detergent, the test plate was obtained by rinsing with ion-exchanged water and air drying at room temperature once, followed by rinsing with running tap water three times and drying at a constant temperature of 50° C., in the same manner as in Example 1 and Comparative Examples 1-1 to 1-5, except for the antifouling treatment.

[0097] Of the obtained test plates, for polyester plates, acrylic plates, and vinyl chloride plates (i.e., other than ceramic tiles and stainless steel plates), the back side of each antifouling treated surface was attached to one side of a 50 mm × 50 mm × 5 mm glass plate using double-sided tape so that the outlines of the two plates matched. This was to prevent the test plate from floating when it was placed at the bottom of a beaker and tap water was poured down the side of the beaker.

[0098] Each of the obtained test plates and the test plates bonded to the glass plate was placed in the center of the bottom of a 600 ml transparent glass beaker with the top surface, which was the anti-fouling treated surface, facing up, and 0.5 ml of model soil (a mixture of 50 g of oleic acid and 50 g of rapeseed oil to which 0.04 g of methyl red had been added and heated to dissolve) was dropped onto the center of the top surface of the test plate.

[0099] In this state, tap water was slowly filled in the beaker, running down the walls. As the water level in the beaker rose, the top surface of the test plate (the anti-fouling treated surface) became wet from all sides. As this progressed, the rolling up of the model dirt was promoted, and eventually most of the model dirt separated from the top surface of the test plate and floated to the surface of the water.

[0100] Immediately after the model dirt floating on the water surface was collected with a dropper, the condition of the dirt remaining on the top surface of the test plate was photographed from above, and then, five minutes after the photograph from above, the condition of the dirt remaining on the top surface of the test plate was photographed from a horizontal direction.

[0101] The removal of dirt was evaluated by approximately determining the remaining area ratio on the top surface of the test plate from a planar photograph taken from above, and then determining the contact angle of the dirt remaining on the top surface of the test plate underwater from a cross-sectional photograph (horizontal photograph). The contact angle was calculated by θ = tan -1 It was estimated using the formula 2a / b.

[0102] The level of antifouling property was ranked based on the following index. AAA: No stains remain. AA: Residual area ratio (S) ≦ 1.0% and contact angle of dirt (θ) ≧ 30° A: Residual area rate (S) ≦ 2.0% and contact angle of dirt (θ) ≧ 20° BBB: Residual area rate (S) ≦ 3.0% and contact angle of dirt (θ) ≧ 15° BB: Residual area rate (S) ≦ 4.0% and contact angle of dirt (θ) ≧ 15° B: Residual area rate (S) ≦ 5.0% and contact angle of dirt (θ) ≧ 10° CCC: Residual area rate (S) ≦ 7.5% and contact angle of dirt (θ) ≧ 5° CC: Residual area rate (S) ≦ 10% and contact angle of dirt (θ) ≧ 0° C: Residual area rate (S) ≦ 20% and contact angle of dirt (θ) ≧ 0° D: Residual area rate (S) ≦ 100% and contact angle of dirt (θ) ≧ 0° (not falling into any of the above levels)

[0103] The results are shown in Table 1

[0104] [Table 1]

[0105] The antifouling treatment using the liquid antifouling detergent of Example 1 exhibited excellent antifouling effects on test panels of each material when compared with untreated (Comparative Example 1-6), treatment with xanthan gum alone (Comparative Example 1-5), and treatment with a treatment agent containing xanthan gum and a non-cationic surfactant (Comparative Examples 1-1 to 1-4).

[0106] Example 2

[0107] Liquid antifouling detergents having the compositions shown in Examples 2-1 to 2-8 in Table 2 were prepared using xanthan gum (trade name: KELZAN AP-AS, manufactured by CP KELCO), dodecyltrimethyl quaternary ammonium chloride (trade name: NISSAN CATION BB, manufactured by NOF Corporation), and sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), and the pH of each was measured and the appearance was observed.

[0108] Thereafter, using each liquid antifouling cleaner, antifouling tests and evaluations were carried out on white ceramic tiles, transparent polyester (PET) boards, and transparent acrylic boards in the same manner as in Example 1.

[0109] In addition, the anionic groups (-COO - ) and the molar concentration of cationic groups (N + ) molar concentration ratio (COO - / N + ) was calculated using the above method.

[0110] The results are shown in Table 2.

[0111] [Table 2]

[0112] The ratio of the molar concentrations (COO - / N + ) was 0.123 to 12.6, which is included in the range of 0.02 to 15, and all of the test plates treated with the liquid antifouling detergent exhibited antifouling performance.

[0113] Example 3

[0114] Liquid antifouling detergents having the compositions shown in Examples 3-1 to 3-5 in Table 3 were prepared using xanthan gum (trade name: KELZAN AP-AS, manufactured by CP KELCO), dodecyltrimethyl quaternary ammonium chloride (trade name: NISSAN CATION BB, manufactured by NOF Corporation), and sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), and the pH of each was measured and the appearance was observed.

[0115] Thereafter, using each liquid antifouling cleaner, antifouling tests and evaluations were carried out on white ceramic tiles, transparent polyester (PET) boards, and transparent acrylic boards in the same manner as in Example 1.

[0116] The results are shown in Table 3.

[0117] Comparative Example 2

[0118] Using the xanthan gum of Example 3, lauryl glucoside (trade name: Mydol 12 ["Mydol" is a trademark], manufactured by Kao Corporation) that does not have cationic properties (i.e., does not fall under the category of surfactants in a cationic state (b)), and sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), liquid antifouling detergents with the compositions shown in Comparative Examples 2-1 to 2-6 in Table 4 were prepared.

[0119] Next, the pH of Comparative Examples 2-1 to 2-6 was measured and the appearance was observed, and then an antifouling test was carried out using each liquid antifouling detergent, and each was evaluated. The results are shown in Table 4.

[0120] [Table 3]

[0121] [Table 4]

[0122] In Example 3, excellent antifouling properties were exhibited in the pH range of 1.87 to 5.23, which was equal to or less than pH 5.5. In Comparative Example 2, antifouling properties were not exhibited in the pH range of 1.46 to 4.88, particularly on plastic plates.

[0123] Example 4

[0124] Liquid antifouling cleaners with the compositions shown in Table 5 were prepared using xanthan gum (trade name: KELZAN AP-AS, manufactured by CP KELCO), various cationic surfactants, and sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), and the pH of each was measured and the appearance was observed.

[0125] The surfactants used in a cationic state are as follows: Octyldimethylamine oxide [C8 alkylamine oxide in Table 5] (trade name: Barlox8S ["Barlox8S" is a trademark], manufactured by LONZA) Decyldimethylamine oxide [C10 alkylamine oxide in Table 5] (trade name: Barlox 10S ["Barlox 10S" is a trademark], manufactured by LONZA) Lauryl-rich dimethylamine oxide [C12 alkylamine oxide in Table 5] (trade name: Barlox 12 ["Barlox 12" is a trademark], manufactured by LONZA) Myristyl-rich dimethylamine oxide [C14 alkylamine oxide in Table 5] (trade name: Barlox 14 ["Barlox 14" is a trademark], manufactured by LONZA) Hexadecyldimethylamine oxide [C16 alkylamine oxide in Table 5] (trade name: Barlox16S ["Barlox16S" is a trademark], manufactured by LONZA) Alkyldimethylbenzylammonium chloride (trade name: Hyamine 3500J ["Hyamine" is a trademark], manufactured by LONZA) Cetylpyridinium chloride (Vertellus Health & Specialty Products) Dioctyldimethylammonium chloride (trade name: BardacLF80 ["BardacLF80" is a trademark], manufactured by LONZA) Dodecyldipropylamine (trade name: Lonzabac12 ["Lonzabac12" is a trademark], manufactured by LONZA)

[0126] Thereafter, a stain-proofing test and evaluation were carried out on a transparent acrylic plate in the same manner as in Example 1 using each liquid stain-proofing cleaner.

[0127] The results are shown in Table 5.

[0128] [Table 5]

[0129] The liquid antifouling cleaner of Example 4, which was a blend of a surfactant in a cationic state, sulfamic acid, and xanthan gum, exhibited good antifouling properties on acrylic plates.

[0130] Example 5

[0131] Liquid antifouling cleaners having the compositions shown in Examples 5-1 and 5-2 in Table 6 were prepared using xanthan gum (trade name: KELZAN AP-AS, manufactured by CP KELCO), lauryl dimethylamine oxide (trade name: Amphitol 20N, manufactured by Kao Corporation), alkyl dimethyl benzyl ammonium chloride (trade name: Hyamine 3500J, manufactured by LONZA), sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), lauryl glucoside (trade name: Mydol 12, manufactured by Kao Corporation), butyl diglycol (manufactured by Nippon Nyukazai Co., Ltd.), ethanol (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), and Blue No. 1 (Brilliant Blue FCF, manufactured by Tokyo Chemical Industry Co., Ltd.) as a colorant. The pH and viscosity of each liquid were measured, and the appearance was observed.

[0132] Thereafter, the spreadability, adhesion, and cleaning power of each liquid antifouling cleaner were evaluated as described below, and antifouling tests and evaluations were carried out on white ceramic tiles, transparent polyvinyl chloride boards, transparent polyester (PET) boards, transparent acrylic boards, and stainless steel boards using the same methods as in Example 1. <Evaluation of the spreadability and adhesion of liquid antifouling cleaners when dispensed>

[0133] 150g of each liquid antifouling cleaner was placed in an empty commercially available squeeze container (Look Disinfectant and Deodorizer EX product container for toilets manufactured by Lion Corporation) and squeezed around the entire back of the rim of a Western-style toilet to dispense it.The liquid antifouling cleaner then dripped down into the bowl, and its spreadability and adhesion were observed and evaluated according to the following criteria.

[0134] [Evaluation criteria for spreadability] ○: The liquid antifouling cleaner has spread and adhered from the back of the rim to almost the entire bowl. △: Liquid antifouling cleaner drips from the back of the rim to the bowl, but does not spread to the entire bowl surface. ×: Almost no liquid antifouling cleaner drips from the underside of the rim to the bowl.

[0135] [Adhesion evaluation criteria] ○: Even 30 minutes after the liquid antifouling detergent was dispensed, the liquid antifouling detergent remained on the entire periphery of the back of the rim and the entire surface of the bowl. △: 30 minutes after the liquid antifouling detergent was dispensed, some of the liquid antifouling detergent was observed to be stagnating in the bowl, but no detergent was observed to be stagnating around the entire periphery of the back of the rim. ×: 30 minutes after the liquid antifouling detergent was dispensed, the liquid antifouling detergent was not sufficiently retained on both the back of the rim and the bowl, and most of the liquid antifouling detergent dripped down into the water seal. <Cleaning power evaluation>

[0136] Two adult men, two adult women, and one junior high school boy used a Western-style toilet in a real home every day for four weeks without cleaning the inside of the toilet, allowing actual dirt to accumulate inside the toilet.

[0137] In this state, each liquid anti-fouling cleaner was dispensed onto the entire back of the rim of the Western-style toilet, and after checking the spread and adhesion of the liquid anti-fouling cleaner to the bowl, it was left to stand, and after 7 hours it was rinsed with a flush, and the removal of dirt from inside the toilet was observed according to the following criteria, and the cleaning power of the actual dirt was evaluated. [Criteria for evaluating cleaning power] 〇: Yellowing and black stains are completely removed, and the entire surface of the toilet bowl is glossy. △: A small amount of yellowing or black stains remain, and the entire surface of the toilet bowl lacks luster. ×: Yellowing and blackening remain noticeable, and the toilet bowl surface lacks luster. These results are shown in Table 6.

[0138] [Table 6]

[0139] When dispensed onto the underside of the rim of a Western-style toilet, each liquid anti-fouling cleaner had excellent spreadability and adhesion from the underside of the rim to the entire bowl. Furthermore, by adding appropriate amounts of lauryl glucoside and water-soluble solvents, the cleaning properties and finish were improved, and excellent anti-fouling performance was demonstrated on the hard surfaces of both hydrophilic and hydrophobic materials.

[0140] Example 6

[0141] Liquid antifouling detergents having the compositions shown in Example 6-1 in Table 7 were prepared using xanthan gum (trade name: KELZAN AR, manufactured by CP KELCO), alkyldimethylbenzylammonium chloride (trade name: HYAMINE 3500J, manufactured by LONZA), sulfamic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), lauryl glucoside (trade name: Mydol 12, manufactured by Kao Corporation), butyl diglycol (manufactured by Nippon Nyukazai Co., Ltd.), and ethanol (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), and the pH and viscosity of each agent were measured, and the appearance was observed.

[0142] The liquid antifouling cleaner was placed in a commercially available trigger spray container (a Fresh Breeze spray container ["Fresh Breeze" is a trademark], manufactured by Yamazaki Sangyo Co., Ltd.), and tests were conducted on the foaming properties when sprayed, the adhesion of the foam to vertical surfaces, and the cleaning power for model bathtub stains. In addition, antifouling tests and evaluations were conducted on white ceramic tiles, transparent vinyl chloride boards, transparent polyester boards, transparent acrylic boards, and stainless steel boards using methods similar to those used in Example 1.

[0143] <Evaluation of foaming when spraying>

[0144] 100 g of the liquid antifouling detergent was placed in the commercially available trigger spray container, and a 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.) was placed upright. The tip of the trigger nozzle was set 20 cm away from the plate, and the foaming and adhesion of the foam when the liquid antifouling detergent was sprayed were observed according to the following criteria.

[0145] [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.

[0146] [Evaluation criteria for foam adhesion]

[0147] The state of foam adhesion is observed and evaluated 30 seconds after spraying. A: Immediately after spraying, the foam remains on the surface. 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.

[0148] <Cleaning power evaluation>

[0149] 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.

[0150] 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.

[0151] After the stained test plate was allowed to dry naturally at room temperature, 0.5 ml of the liquid antifouling detergent of Example 6 was applied in a circular pattern onto the test plate, and the test plate was gently scrubbed five times with a sponge cut to a width of 1 cm, length of 2 cm, and thickness of 2 cm.

[0152] 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 and evaluated according to the following criteria.

[0153] [Criteria for evaluating cleaning power] 〇: Dirt is removed cleanly △: Slight dirt remains ×: noticeable residue

[0154] [Table 7]

[0155] By adding an appropriate amount of lauryl glucoside and a water-soluble solvent to the liquid antifouling detergent, the foaming properties, foam adhesion, and cleaning power were improved, and the detergent also exhibited excellent antifouling performance on hard surfaces of hydrophilic or hydrophobic materials.

Claims

1. a) Xanthan gum: 0.01 to 5% by weight b) Surfactant in a cationic state: 0.02 to 10% by weight c) Inorganic acid and / or organic acid: 0.003 to 10% by weight A liquid antifouling detergent composition for hard surfaces, which contains the above and has a pH of 5.5 or less, excluding those containing an anionic surfactant.

2. 2. The composition according to claim 1, wherein the surfactant in a cationic state of 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.

3. 3. The composition according to claim 1 or 2, wherein the surfactant in a cationic state of b) has at least one linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms.

4. Anionic groups in xanthan gum (-COO － ) (however, the molar concentration is calculated assuming that each repeating unit has two carboxylic acids, each of which has two glucose molecules as the main chain and two mannose molecules and one glucuronic acid molecule as the side chain) and the cationic group (N ＋ ) molar concentration ratio (COO － / N ＋ 4. The composition according to claim 1, wherein the saturation coefficient (μm) is 0.02 to 15.

5. 5. The composition according to claim 1, wherein the inorganic acid and / or organic acid in c) is one or more acidic agents selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, formic acid, acetic acid, butyric acid, hexanoic acid, salicylic acid, benzoic acid, phthalic acid, sulfamic acid, oxalic acid, lactic acid, maleic acid, malonic acid, succinic acid, glutaric acid, malic acid, and citric acid.

6. 6. The composition according to claim 1, which contains 0.5 to 10% by weight of alkyl glucoside.

7. 7. The composition according to claim 1, which contains 2 to 15% by weight of diethylene glycol monobutyl ether.

8. 8. The composition according to claim 1, wherein the hard surface is made of a hydrophilic or hydrophobic material.

9. 8. The composition according to claim 1, wherein the hard surface is made of synthetic resin, ceramic, stainless steel, aluminum, or an aluminum alloy.

10. 8. The composition according to claim 1, wherein the hard surface is made of a synthetic resin.

11. 11. The composition according to claim 10, wherein the synthetic resin is a polyethylene resin, a polypropylene resin, a polycarbonate resin, a polystyrene resin, an acrylic resin, a polyester resin, a polyvinyl chloride resin, a polyamide resin, or a urethane resin.

12. 8. The composition according to claim 1, wherein the hard surface is made of ceramic.

13. a) Xanthan gum: 0.01 to 5% by weight b) Surfactant in a cationic state: 0.02 to 10% by weight c) Inorganic acid and / or organic acid: 0.003 to 10% by weight A stain-proofing method for treating a hard surface made of a hydrophilic or hydrophobic material using a liquid composition containing the above compound and having a pH of 5.5 or less, excluding those containing an anionic surfactant.

14. 14. The method according to claim 13, wherein the hard surface is made of synthetic resin, ceramic, stainless steel, aluminum or an aluminum alloy.

15. A composition described in any one of claims 1 to 12, wherein the concentration of a) xanthan gum is 0.25 to 0.6% by weight.

16. A method according to claim 13 or 14, wherein the concentration of a) xanthan gum is 0.25 to 0.6% by weight.

17. A composition described in any one of claims 1 to 12 and 15, wherein the inorganic acid and / or organic acid in c) above is hydrochloric acid and / or sulfamic acid.

18. A method according to any one of claims 13, 14 and 16, wherein the inorganic acid and / or organic acid in c) above is hydrochloric acid and / or sulfamic acid.

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