Hard surface liquid cleaning composition

Abstract

To provide a liquid detergent composition for hard surfaces, which has a large spray diameter and a spray pattern of which covers a wide area, which can suppress occurrence of water spots on the hard surfaces, and which can reduce sliminess.SOLUTION: Provided is a liquid detergent composition for hard surfaces, comprising (A) Component: a non-soap-based anionic surfactant, (B) Component: cationized cellulose, and (C) Component: an alkyl polyglucoside represented by the following general formula (C1), where a mass ratio represented by the (A) Component / the (B) Component is 0.5-300, a mass ratio represented by the (C) Component / the (B) Component is 1-100, and a viscosity of the composition at 25°C is less than 30 mPa s; R1-O-[G]z (C1) (in the formula (C1), R1 represents a C8-20 alkyl group; G represents a glucoside residue; and z represents a degree of polymerization of sugar, which is a number of 1-5).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hard surface liquid cleaner composition. [Background technology]

[0002] Bathroom cleaners are required to make cleaning easier in the series of steps from washing to rinsing and to reduce unpleasant feelings such as sliminess. In the cleaning process, there is a demand for cleaners that can be sprayed over a wider area with one spray, reducing the effort required to spray cleaner into bathtubs and other areas, and cleaners that can remove dirt from the target surface while preventing the formation of water spots, a type of dirt, for easier cleaning. In the rinsing step, it is desirable to reduce the sliminess caused by the detergent components in order to alleviate discomfort.

[0003] From this perspective, development is underway to develop liquid detergent compositions that have a large spray diameter, a wide range of spray patterns, and the ability to suppress the occurrence of water spots, while also reducing the sliminess caused by detergent ingredients. For example, Patent Documents 1 and 2 disclose liquid detergent compositions that use specific amounts of two or more surfactants in combination to reduce sliminess and improve cleaning properties. Patent Document 3 discloses a liquid detergent composition that suppresses the occurrence of water spots while reducing the sliminess caused by the detergent ingredients by combining glyceryl ether, magnesium, anionic surfactants, and water-soluble polymers in a specific ratio. Patent Document 4 discloses a spray-type cleaning product that can spray a liquid detergent composition over a wide range by using a specific amount of an anionic surfactant and an amphoteric surfactant in combination. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-143947 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-325167 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-264009 [Patent Document 4] Japanese Patent Application Laid-Open No. 2004-322078 Summary of the Invention [Problem to be solved by the invention]

[0005] However, no liquid detergent composition is known that meets all of these requirements simultaneously. An object of the present invention is to provide a hard surface liquid cleaner composition that has a large spray diameter, a wide range of spray patterns, can suppress the occurrence of water spots on hard surfaces, and can reduce sliminess. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] Component (A): a non-soap anionic surfactant, (B) component: cationized cellulose, (C) component: an alkyl polyglucoside represented by the following general formula (C1), the mass ratio of the component (A) to the component (B) is 0.5 to 300; the mass ratio of the component (C) to the component (B) is 1 to 100; A hard surface liquid cleaning composition having a viscosity of less than 30 mPa·s at 25°C. R 1 -O-[G]z (C1) (In formula (C1), R 1 represents an alkyl group having 8 to 20 carbon atoms, G represents a glucoside residue, and z represents the degree of sugar polymerization, a number from 1 to 5. [2] The hard surface liquid detergent composition according to [1], wherein the component (A) is at least one selected from α-olefin sulfonic acid or a salt thereof, linear alkylbenzene sulfonic acid or a salt thereof, alkanesulfonic acid or a salt thereof, alkyl sulfate ester or a salt thereof, and polyoxyalkylene alkyl ether sulfate or a salt thereof. [3] The hard surface liquid detergent composition according to [1] or [2], wherein the content of the component (B) is 0.01 to 1.0 mass%, more preferably 0.01 to 0.5 mass%, and even more preferably 0.01 to 0.1 mass%, relative to the total mass of the hard surface liquid detergent composition. [4] The hard surface liquid detergent composition according to any one of [1] to [3], wherein the content of the component (A) is 0.1 to 5.0 mass%, more preferably 0.1 to 3.0 mass%, and even more preferably 0.5 to 1.5 mass%, relative to the total mass of the hard surface liquid detergent composition. [5] The hard surface liquid detergent composition according to any one of [1] to [4], wherein the content of the component (C) is 0.1 to 2.0 mass%, more preferably 0.1 to 1.5 mass%, and even more preferably 0.5 to 1.5 mass%, relative to the total mass of the hard surface liquid detergent composition. [6] The hard surface liquid cleaner composition according to any one of [1] to [5] above, which has a pH of 9.0 to 11.0 at 25°C. [7] The hard surface liquid cleaner composition according to any one of [1] to [6] above, which is for use in a bathroom. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a hard surface liquid cleaner composition that has a large spray diameter, a wide range of spray patterns, can suppress the occurrence of water spots on hard surfaces, and can reduce sliminess. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention will be described in detail below. The hard surface liquid detergent composition of the present invention is a composition containing the following components (A), (B), and (C). The hard surface liquid detergent composition may contain water. Furthermore, the hard surface liquid detergent composition may further contain components (optional components) other than the components (A), (B), (C), and water, as necessary.

[0009] <Component (A)> Component (A) is a non-soap anionic surfactant. By including component (A), the hard surface liquid cleaner composition can exhibit effective cleaning power against limescale stains, sebum stains, protein stains, and the like adhering to hard surfaces. In the present invention, "non-soap anionic surfactant" refers to an anionic surfactant excluding higher fatty acids or salts thereof (so-called soaps). "Higher fatty acids" refer to saturated or unsaturated fatty acids having 8 to 24 carbon atoms. In other words, component (A) is an anionic surfactant excluding saturated or unsaturated fatty acids having 8 to 24 carbon atoms or salts thereof.

[0010] Examples of component (A) include sulfonic acids or salts thereof, such as α-olefin sulfonic acid or salts thereof, linear alkylbenzene sulfonic acid or salts thereof, alkanesulfonic acid or salts thereof, α-sulfofatty acid ester or salts thereof, internal olefin sulfonic acid or salts thereof, and hydroxyalkanesulfonic acid or salts thereof; sulfates or salts thereof, such as alkyl sulfates or salts thereof, polyoxyalkylene alkyl ether sulfates or salts thereof, and polyoxyalkylene alkenyl ether sulfates or salts thereof; carboxylic acids or salts thereof, such as alkyl ether carboxylic acids or salts thereof, polyoxyalkylene ether carboxylic acids or salts thereof, alkylamide ether carboxylic acids or salts thereof, alkenylamide ether carboxylic acids or salts thereof, and acylaminocarboxylic acids or salts thereof; and phosphoric acids or salts thereof, such as alkyl phosphates or salts thereof, polyoxyalkylene alkyl phosphates or salts thereof, polyoxyalkylene alkylphenyl phosphates or salts thereof, and glycerin fatty acid ester monophosphates or salts thereof. Examples of salt forms of non-soap anionic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). Among these, from the viewpoint of further enhancing detergency, sulfonic acid or a salt thereof, or a sulfate ester or a salt thereof is preferred as component (A), α-olefin sulfonic acid or a salt thereof, linear alkylbenzene sulfonic acid or a salt thereof, alkanesulfonic acid or a salt thereof, alkyl sulfate ester or a salt thereof, or polyoxyalkylene alkyl ether sulfate or a salt thereof is more preferred, and α-olefin sulfonic acid or a salt thereof is even more preferred. The component (A) may be used alone or in combination of two or more.

[0011] Commercially available products of component (A) include, for example, sodium α-olefin sulfonate under the trade name "Lipolan LJ441 (manufactured by Lion Specialty Chemicals Co., Ltd.)," sodium linear alkyl (C12-C14) benzenesulfonate under the trade name "Lipon PS-230 (manufactured by Lion Specialty Chemicals Co., Ltd.)," sodium alkanesulfonate under the trade name "HOSTAPUR SAS 93 (manufactured by Clariant)," sodium alkyl sulfate under the trade name "Alscope LS-30 (manufactured by Toho Chemical Industry Co., Ltd.)," and sodium polyoxyethylene alkyl ether sulfate under the trade name "Shinoline SPE-1250 (manufactured by New Japan Chemical Co., Ltd.)." The number after "C" in "C12" etc. means the number of carbon atoms, and the same applies below.

[0012] The content of component (A) is preferably 0.1 to 5.0 mass%, more preferably 0.1 to 3.0 mass%, and even more preferably 0.5 to 1.5 mass%, relative to the total mass of the hard surface liquid detergent composition. When the content of component (A) is equal to or greater than the above-mentioned lower limit, the detergency is further enhanced. When the content of component (A) is equal to or less than the above-mentioned upper limit, the sliminess caused by the detergent components can be further reduced. In addition, when the liquid detergent composition is sprayed onto a hard surface, the spray diameter is less likely to become small, allowing it to be sprayed over a wide area with a single spray.

[0013] <(B) component> Component (B) is a cationized cellulose. By including component (B) in the hard surface liquid detergent composition, spraying the hard surface with the liquid detergent composition imparts hydrophilicity to the hard surface. As a result, water is more likely to form a film on the hard surface during the rinsing process, and the film-like water dissipates during drying, leaving fewer water droplets, thereby preventing water spots. This effectively prevents water spots from forming on hydrophobic hard surfaces, such as those made of glass fiber reinforced plastic (FRP) used in bathtubs. While the reason for this is unclear, it is believed to be as follows. When the hard surface liquid cleaner composition contains component (B) in addition to component (A), a complex is formed between components (A) and (B) upon spraying. Components (A) and (B) are hydrophilic when used alone, but when they form a complex, they also exhibit hydrophobicity. This facilitates uniform adhesion of the complex to hydrophobic hard surfaces, and imparts the inherent hydrophilic properties of components (A) and (B) to the hard surfaces. As a result, as described above, water tends to form a film on the hard surface during the rinsing process, and the water dissipates in the film state during drying, leaving fewer water droplets.

[0014] Examples of the component (B) include cationized cellulose having a structural unit represented by the following general formula (B1) (hereinafter sometimes referred to as "component (B1)"), cationized cellulose having a structural unit represented by the following general formula (B2) (hereinafter sometimes referred to as "component (B2)"), cationized cellulose having a structural unit represented by the following general formula (B3) (hereinafter sometimes referred to as "component (B3)"), and cationized cellulose having a structural unit represented by the following general formula (B4) (hereinafter sometimes referred to as "component (B4)"). Among these, the component (B1) is preferred from the viewpoint of being able to further suppress the occurrence of water spots on hard surfaces (particularly hydrophobic hard surfaces). The component (B) may be used alone or in combination of two or more.

[0015] [ka]

[0016] [ka]

[0017] [ka]

[0018] [ka]

[0019] In the formula (B1), s and t are the average number of moles of oxyethylene groups added. In the formula (B4), v and w are the average number of moles of oxyethylene groups added. The mass average molecular weight of the component (B1) is 10,000 to several million. The mass average molecular weight of the component (B2) is 10,000 to several hundred thousand. The mass average molecular weight of the component (B3) is 10,000 to several hundred thousand. The mass average molecular weight of the component (B4) is 10,000 to several million.

[0020] The degree of cationization of component (B) is preferably 0.5 to 2.2 mass%, more preferably 1.5 to 2.2 mass%. If the degree of cationization is within the above range, the occurrence of water spots on hard surfaces (particularly hydrophobic hard surfaces) can be further suppressed. Here, the "degree of cationization" refers to the content (mass %) of nitrogen atoms derived from the cationizing agent in the molecules of component (B), i.e., the ratio of the mass of nitrogen atoms to the total mass of component (B).

[0021] The degree of cationization of component (B) can be calculated based on the identified chemical structure. When the chemical structure of component (B) is not identified, such as when the ratio of structural units in component (B) is unknown, the degree of cationization of component (B) is calculated from the experimentally determined nitrogen content. The nitrogen content of component (B) can be measured by the Kjeldahl method, but other methods may also be used for convenience.

[0022] The viscosity of a 1% by mass aqueous solution of component (B) at 25°C is preferably 1 to 60 mPa·s, more preferably 5 to 55 mPa·s, even more preferably 10 to 50 mPa·s, and particularly preferably 15 to 45 mPa·s. If the viscosity of a 1% by mass aqueous solution of component (B) is within the above range, the composition will have excellent drainage properties when rinsed with running water from a shower or the like, resulting in a decrease in the concentration of the hard surface liquid cleaner composition. The viscosity was measured using a Brookfield viscometer on a 1% by mass aqueous solution of component (B) at 25° C. The viscosity was measured under the following conditions.

[0023] Measurement conditions: [rotor] The rotor numbers and rotor rotation speeds corresponding to the viscosities to be measured are as follows: Viscosity less than 100 mPa·s: Rotor No. 1, rotation speed 60 rpm. Viscosity 100 mPa·s or more but less than 500 mPa·s: Rotor No. 2, rotation speed 60 rpm. Viscosity between 500 mPa·s and 2000 mPa·s: Rotor No. 3, rotation speed 60 rpm. Viscosity of 2000 mPa·s or more but less than 10000 mPa·s: Rotor No. 4, rotation speed 60 rpm. Viscosity of 10,000 mPa·s or more but less than 50,000 mPa·s: Rotor number 4, rotation speed 12 rpm. [Read Numeric Values] 60 seconds after the rotor starts spinning.

[0024] Specific examples of cationized cellulose include cation-modified hydroxyethyl cellulose such as hydroxytrimethylammoniopropyl hydroxyethyl cellulose chloride, which is the component (B1), and hydroxyethyl cellulose dimethyl diallyl ammonium chloride polymer, which is the component (B2).

[0025] Commercially available products of component (B1) include, for example, the trade names "Leoguard GP (quaternary nitrogen content 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", "Leoguard MGP (quaternary nitrogen content 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", "Leoguard MLP (quaternary nitrogen content 0.6% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", and "SUPRACARE 133 (quaternary nitrogen content 0.8 mass%, manufactured by Dow Chemical Japan Co., Ltd.)", trade name "SUPRACARE212 (quaternary nitrogen content 1.9 mass%, manufactured by Dow Chemical Japan Co., Ltd.)", trade name "SUPRACARE240 (quaternary nitrogen content 1.9 mass%, manufactured by Dow Chemical Japan Co., Ltd.)", trade name "SUPRACARE241 (quaternary nitrogen content 1.0 mass%, manufactured by Dow Chemical Japan Co., Ltd.)", trade name "UCARE Product name "UCARE JR125 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Japan)", product name "UCARE JR400 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Japan)", product name "UCARE LR30M (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan)", product name "SoftCAT SL-5 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan)", product name "SoftCAT SL-60 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan)", product name "SoftCAT SL-100 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan)", product name "SoftCAT SX-400X (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Japan)", product name "SoftCAT SX-1300X (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Japan Co., Ltd.)", product name "SoftCAT SX-400H (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Japan Co., Ltd.)", product name "Catinal HC-100 (quaternary nitrogen content 1.5% by mass, manufactured by Toho Chemical Industry Co., Ltd.)", product name "Catinal HC-200 (quaternary nitrogen content 1.5% by mass, manufactured by Toho Chemical Industry Co., Ltd.)", product name "Catinal LC-100 (quaternary nitrogen content 1.0% by mass, manufactured by Toho Chemical Industry Co., Ltd.)", product name "Catinal LC-2 ...0% by mass, manufactured by Toho Chemical Industry Co., Ltd. Among these, "SUPRACARE212" is preferred from the viewpoint of imparting hydrophilicity.

[0026] Examples of commercially available products of component (B4) include products under the trade name "SoftCAT SL-5 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan)", "SoftCAT SL-60 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan)", "SoftCAT SL-100 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan)", "SoftCAT SX-400X (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Japan)", "SoftCAT SX-1300X (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Japan)", and "SoftCAT SX-400H (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Japan)". Among these, the (B1) component "SUPRACARE133", "SUPRACARE212", and "SUPRACARE240" are preferred, with "SUPRACARE212" and "SUPRACARE240" being more preferred, from the viewpoint of their excellent water-shedding properties and their ability to further suppress the occurrence of water spots on hard surfaces (particularly hydrophobic hard surfaces).

[0027] The content of component (B) is preferably 0.01 to 1.0 mass%, more preferably 0.01 to 0.5 mass%, and even more preferably 0.01 to 0.1 mass%, relative to the total mass of the hard surface liquid detergent composition. When the content of component (B) is equal to or greater than the above-mentioned lower limit, the occurrence of water spots on hard surfaces (particularly hydrophobic hard surfaces) can be further suppressed. In addition, the spray diameter when sprayed with the hard surface liquid detergent composition is less likely to become small, allowing it to be sprayed over a wide area with a single spray. When the content of component (B) is equal to or less than the above-mentioned upper limit, the stickiness caused by the detergent components can be further reduced.

[0028] The mass ratio of component (A) to component (B) (hereinafter also referred to as "A / B ratio") is 0.5 to 300, preferably 1 to 150, and more preferably 5 to 30. When the A / B ratio is within the above range, the occurrence of water spots on hard surfaces (particularly hydrophobic hard surfaces) can be suppressed.

[0029] <(C) component> Component (C) is an alkyl polyglucoside represented by the following general formula (C1). By including component (C) in the hard surface liquid detergent composition, the sliminess caused by the detergent components can be reduced. R 1 -O-[G]z ···(C1) (In formula (C1), R 1 represents an alkyl group having 8 to 20 carbon atoms, G represents a glucoside residue, and z represents the degree of sugar polymerization, a number from 1 to 5.

[0030] R 1 The number of carbon atoms in the alkyl group is 8 to 20, preferably 8 to 16, and more preferably 8 to 14. The alkyl group may be linear or branched. G is a glucoside residue. The reducing sugar used as the raw material for glucoside may be either an aldose or a ketose, and examples thereof include trioses, tetroses, pentoses, and hexoses having 3 to 6 carbon atoms. Specific examples of aldoses include apiose, arabinose, galactose, glucose, lyxose, mannose, galose, aldose, idose, talose, and xylose, and examples of ketoses include fructose. Among these, aldopentoses or aldohexoses having 5 or 6 carbon atoms are preferred, and glucose is most preferred. z represents the degree of polymerization of the sugar, and is a number of 1 to 5 on average, preferably a number of 1 to 3 on average, and more preferably a number of 1.2 to 1.6 on average.

[0031] The component (C) is preferably an alkyl polyglucoside represented by the following general formula (C1-1) (hereinafter sometimes referred to as "component (C1-1)").

[0032] [ka]

[0033] In formula (C1-1), R 1 represents an alkyl group having 8 to 20 carbon atoms, and m is a number of 1 or 2. R 1 The number of carbon atoms in the alkyl group is 8 to 20, preferably 8 to 16, and more preferably 8 to 14. The alkyl group may be linear or branched.

[0034] The component (C) may be used alone or in combination of two or more. The component (C) may be an alkyl group (R 1 A mixture of two or more alkyl polyglycosides with different carbon numbers in R may be used. 1 The average carbon number is preferably 8 to 16, and more preferably 8 to 14.

[0035] Examples of commercially available products of the component (C1-1) include products under the trade names "Glucopon (registered trademark) 215 UP (manufactured by BASF)", "Glucopon (registered trademark) 600 CSUP (manufactured by BASF)", "Glucopon (registered trademark) 650 EC (manufactured by BASF)", "Glucopon (registered trademark) 600 CSUP / MB (manufactured by BASF)", and "Glucopon (registered trademark) 650 EC / MB (manufactured by BASF)".

[0036] The content of component (C) is preferably 0.1 to 2.0% by mass, more preferably 0.1 to 1.5% by mass, and even more preferably 0.5 to 1.5% by mass, based on the total mass of the hard surface liquid detergent composition. When the content of component (C) is within the above range, the stickiness caused by the detergent components can be further reduced. In addition, the spray diameter when sprayed onto a hard surface is less likely to become small, allowing for a wide range of coverage with a single spray.

[0037] The mass ratio of component (C) to component (B) (hereinafter also referred to as "C / B ratio") is 1 to 100, preferably 3 to 75, and more preferably 5 to 30. If the C / B ratio is within the above range, the spray diameter when sprayed onto a hard surface is less likely to become small, and the liquid detergent composition can be sprayed over a wide area with one spray. In particular, if the C / B ratio is equal to or greater than the above lower limit, the sliminess caused by the detergent components can be further reduced.

[0038] <Water> The hard surface liquid detergent composition preferably contains water as a solvent from the viewpoint of ease of handling and improved rinsing properties. The water that can be used includes ion-exchanged water, distilled water, tap water, etc. The water may be used alone or in combination of two or more types.

[0039] The water content is preferably 50 to 99 mass%, more preferably 60 to 95 mass%, and even more preferably 70 to 95 mass%, based on the total mass of the hard surface liquid detergent composition. If the water content is within the above range, the hard surface liquid detergent composition can be easily prepared. In addition, when the hard surface liquid detergent composition is used, the solubility in water is good.

[0040] <Optional ingredients> Examples of optional components include higher fatty acids or salts thereof, water-soluble organic solvents, sequestering agents, other surfactants, pH adjusters, disinfectants, preservatives, antifungal agents, pigments, antioxidants, thickeners, UV absorbers, solubilizers, emulsifiers, and fragrances.

[0041] Examples of higher fatty acids include stearic acid, linoleic acid, oleic acid, myristic acid, and coconut oil fatty acid. Examples of salt forms of higher fatty acids include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.). The higher fatty acid or salt thereof may be used alone or in combination of two or more.

[0042] The content of the higher fatty acid or its salt is preferably 0.05 to 3.0 mass %, more preferably 0.1 to 2.0 mass %, and even more preferably 0.2 to 1.0 mass %, relative to the total mass of the hard surface liquid detergent composition.

[0043] A water-soluble organic solvent is an organic solvent that dissolves 50 g or more in 1 L of water at 25°C. Examples of water-soluble organic solvents include diethylene glycol monobutyl ether (also known as butyl carbitol), triethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, diethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, propylene glycol monopropyl ether, and Solfit. The water-soluble organic solvent may be used alone or in combination of two or more kinds.

[0044] The content of the water-soluble organic solvent is preferably 0.1 to 5.0 mass %, more preferably 1.0 to 3.0 mass %, based on the total mass of the hard surface liquid cleaner composition.

[0045] Examples of the sequestering agent include organic carboxylic acids, aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, and phosphoric acids. Examples of organic carboxylic acids include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, and gluconic acid. Examples of aminocarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, hydroxyethyleneiminodiacetic acid, and diethylenetriaminepentaacetic acid. Examples of phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and derivatives thereof, 1-hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, and aminotrimethylenephosphonic acid. Examples of phosphonocarboxylic acids include 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, and α-methylphosphonosuccinic acid. Examples of phosphoric acids include condensed phosphoric acids such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, and phytic acid. The sequestering agent may be used alone or in combination of two or more.

[0046] The content of the sequestering agent is preferably 1.0 to 5.0 mass %, more preferably 1.5 to 3.5 mass %, based on the total mass of the hard surface liquid cleaner composition.

[0047] The other surfactants are surfactants other than component (A), component (C), and higher fatty acids and salts thereof. Examples of other surfactants include nonionic surfactants other than component (C), cationic surfactants, amphoteric surfactants, and semi-polar surfactants. The other surfactants may be used singly or in combination of two or more.

[0048] The total content (total surfactant amount) of all surfactants (excluding higher fatty acids and their salts) contained in the hard surface liquid detergent composition is preferably 0.2 to 30.0 mass%, more preferably 0.5 to 10.0 mass%, even more preferably 1.0 to 5.0 mass%, and particularly preferably 1.0 to 3.0 mass%, relative to the total mass of the hard surface liquid detergent composition.

[0049] Examples of pH adjusters include inorganic acids such as hydrochloric acid and sulfuric acid, and alkali agents selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, and derivatives thereof. Among these, hydrochloric acid, sulfuric acid, sodium hydroxide, and potassium hydroxide are preferred. The pH adjusters may be used alone or in combination of two or more.

[0050] The total amount of the components constituting the hard surface liquid cleaner composition is 100% by mass.

[0051] <Physical properties> (viscosity) The viscosity of the hard surface liquid detergent composition at 25°C is less than 30 mPa·s, preferably 1 mPa·s or more but less than 30 mPa·s, more preferably 1 to 20 mPa·s, and even more preferably 3 to 15 mPa·s. If the viscosity at 25°C is within the above range, the composition can be easily sprayed from a discharge container such as a spray container. In addition, the spray diameter when sprayed onto a hard surface is less likely to become small, allowing the composition to be sprayed over a wide area with a single spray.

[0052] The viscosity of the hard surface liquid cleaner composition can be adjusted by the water content, addition of a thickener, etc. The viscosity of the hard surface liquid detergent composition is measured at 25°C using a B-type viscometer with rotor number 1 and a rotor rotation speed of 60 rpm, 60 seconds after the rotor starts rotating.

[0053] (pH) The pH of the hard surface liquid detergent composition at 25° C. is preferably 6.0 or higher, more preferably 9.0 or higher, even more preferably 9.0 to 12.0, particularly preferably 9.0 to 11.0, and most preferably 10.0 to 11.0. If the pH at 25° C. is within the above range, the detergency against limescale stains is enhanced.

[0054] The pH of the hard surface liquid cleaner composition can be adjusted by adding an appropriate amount of a pH adjuster. The pH of the hard surface liquid cleaner composition is a value measured at 25°C by a method in accordance with JIS Z 8802:2011 "pH measurement method."

[0055] <Manufacturing method> The hard surface liquid detergent composition can be produced by a conventional method, for example, by adding components (A), (B), and (C) and, if necessary, any optional components other than the pH adjuster to water, and adjusting the pH to the desired level with the pH adjuster, if necessary.

[0056] <How to use> Examples of methods for using the hard surface liquid detergent composition include a method in which a cleaning tool such as a sponge is impregnated with the hard surface liquid detergent composition and the hard surface to be cleaned is scrubbed with the sponge, and a method in which the hard surface liquid detergent composition is placed in a dispensing container, an appropriate amount of the hard surface liquid detergent composition is sprayed onto the hard surface from this dispensing container, and after a certain period of time, the hard surface is rinsed with a shower or the like, thereby performing "non-scrubbing washing." In particular, the hard surface liquid detergent composition of the present invention is suitable for use in "washing without scrubbing" because the spray diameter is less likely to become small when sprayed onto a hard surface and the liquid detergent composition can be sprayed over a wide area with a single spray.

[0057] Examples of materials for hard surfaces to be cleaned include plastics, tiles, stainless steel, ceramics, glass, marble, concrete, etc. Among these, the hard surface liquid cleaner composition of the present invention is particularly suitable for cleaning the surfaces of plastics. Examples of plastics include glass fiber reinforced plastics (FRP), acrylic resins, polyolefins (such as polyethylene and polypropylene), and polyethylene terephthalate. Specific examples of hard surfaces include bathroom bathtubs, bathroom floors and walls, bathroom accessories (such as bath covers, bathroom mats (slatted floors), bathroom chairs, soap dispensers, drain strainers and hair catchers, etc.), faucets, bathtub covers, bathroom doors, mirrors, drains, and toilets.

[0058] Examples of the dispensing container for containing the hard surface liquid detergent composition include a spray container, a squeeze container, etc. Among them, a spray container is preferred as the dispensing container for containing the hard surface liquid detergent composition because of its excellent applicability to the object to be cleaned. Examples of spray containers include aerosol spray containers, trigger spray containers (direct pressure type or pressure accumulation type), dispenser spray containers, etc. These containers may be manual or electric. Examples of aerosol spray containers include those described in JP-A-9-3441 and JP-A-9-58765. When filling an aerosol spray container, propellants that can be used include LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, and nitrous oxide gas. The propellants may be used alone or in combination of two or more. Examples of trigger spray containers include those described in JP-A Nos. 9-268473 and 10-76196. Examples of dispenser spray containers include those described in JP-A-9-256272. An example of a pressure-accumulating trigger spray container is described in JP-A-2013-154276. Among these, trigger spray containers are preferred because they have good spray properties and spray patterns and provide good application properties.

[0059] The hard surface liquid cleaner composition of the present invention is suitable for use in bathrooms because the spray diameter does not easily become small when sprayed onto a hard surface, it can be sprayed over a wide area with one spray, it has high detergency against sebum and protein stains adhering to the floor and walls of a bathtub or bathroom, it can also suppress the occurrence of water spots on hard surfaces, and it can reduce the sliminess caused by the cleaner components. In addition, the hard surface liquid cleaner composition for bathroom use is also referred to as "liquid cleaner composition for bathroom use."

[0060] <Action and effect> The hard surface liquid detergent composition of the present invention described above contains the above-mentioned components (A), (B), and (C) in a specific mass ratio, and has a viscosity of less than 30 mPa·s at 25°C. Therefore, when sprayed, the spray diameter is large and the spray pattern covers a wide range, making it possible to suppress the occurrence of water spots on hard surfaces (especially hydrophobic hard surfaces) and reduce the sliminess caused by the detergent components. [Example]

[0061] The present invention will be described in more detail below by showing examples, but the present invention is not limited to the following description. Examples 3, 4, 6, 10, 12, and 16 to 19 are reference examples.

[0062] "Raw materials used" The following compounds were used as component (A). A-1: AOS, sodium α-olefin sulfonate with 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipolan LJ441").

[0063] The compounds shown below were used as component (B) or its comparative product (component (B')). B-1: Cationic cellulose (manufactured by Dow Chemical Japan, trade name "Supracare 212", quaternary nitrogen content 1.9% by mass, viscosity of 1% by mass aqueous solution at 25°C 18 mPa·s). B-2: Cationic cellulose (manufactured by Dow Chemical Japan, trade name "Supracare 133", quaternary nitrogen content 0.8% by mass, viscosity of 1% by mass aqueous solution at 25°C 7 mPa·s). B-3: Cationic cellulose (manufactured by Dow Chemical Japan, trade name "Supracare 240", quaternary nitrogen content 1.9% by mass, viscosity of 1% by mass aqueous solution at 25°C 42 mPa·s). B'-4: Dimethyldiallylammonium chloride-acrylamide copolymer (manufactured by Matsumoto Trading Co., Ltd., product name "Merquat 550PR Polymer"). B'-5: Cationic guar gum (manufactured by Sansho Co., Ltd., trade name "JAGURAR C-17K"). B'-6: Polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., trade name "SP-200", mass average molecular weight (Mw) 20,000).

[0064] The following compounds were used as component (C). C-1: alkyl (C8-10) polyglucoside (manufactured by BASF, trade name "Glucopon 215UP"; in the above general formula (C1-1), R 1 is a linear alkyl group having 8 to 10 carbon atoms, m is 1.5, and the product viscosity at 20°C is 3500 mPa·s. C-2: alkyl (C8-14) polyglucoside (manufactured by BASF, trade name "Glucopon 650EC"; in the above general formula (C1-1), R 1 is a linear alkyl group having 8 to 14 carbon atoms, m is 1.5, and the product viscosity at 20°C is 2250 mPa·s)

[0065] Water and the compounds shown below were used as optional components. Water: Ion-exchanged water. Coconut oil fatty acid potassium: Potassium coconut oil fatty acid (manufactured by Lion Specialty Chemicals Co., Ltd., product name "Potassium coconut oil fatty acid", soap-based anionic surfactant). Myristate K: Potassium myristate (manufactured by NOF Corporation, product name "NonSal MK-1", soap-based anionic surfactant). Butyl carbitol: Diethylene glycol monobutyl ether (manufactured by Nippon Nyukazai Co., Ltd., trade name "Butyl Diglycol", water-soluble organic solvent). EDTA: Ethylenediaminetetraacetic acid (manufactured by AkzoNobel, trade name "Dissolvin Z", metal sequestering agent). pH adjuster: at least one of 1N sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) and 1N hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.).

[0066] "Examples 1 to 23, Comparative Examples 1 to 9" <Preparation of hard surface liquid cleaner composition> According to the compositions shown in Tables 1 to 7, components (A), (B), and (C) and any optional components other than the pH adjuster were added to water and mixed, and then the pH was adjusted using the pH adjuster so that the pH at 25°C would be the value shown in Tables 1 to 7, thereby obtaining hard surface liquid detergent compositions of each example. The compositions (compounded components, content (mass%)) and viscosities of the obtained hard surface liquid detergent compositions of each example are shown in Tables 1 to 7. Unless otherwise specified, mass % indicates pure content. In the tables, blank columns for ingredients indicate that the ingredient is not included. In the tables, the "appropriate amount" of pH adjuster content is the amount required to adjust the pH of each example of the hard surface liquid cleaner composition to the value in the table. In the tables, the "balance" water content means that water is added so that the total amount (mass %) of all ingredients contained in the hard surface liquid cleaner composition is 100 mass %. In other words, the amount of water added is the remainder after subtracting the total amount (in pure content) of ingredients other than water from the total mass of the hard surface liquid cleaner composition. In addition, the "A / B ratio" in the tables is the mass ratio expressed as component (A) / component (B). The "C / B ratio" is the mass ratio expressed as component (C) / component (B).

[0067] The pH of each hard surface liquid cleaner composition was measured using a glass electrode pH meter (manufactured by DKK-TOA Corporation, product name "HM-25R") after adjusting it to 25°C. The measurement method was in accordance with JIS Z 8802:1984 "pH measurement method." The viscosity of each hard surface liquid cleaning composition was adjusted to 25°C and then measured using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.) with rotor number 1 and a rotor rotation speed of 60 rpm, with the viscosity measured 60 seconds after the rotor started rotating. Furthermore, the hard surface liquid detergent compositions of each example were evaluated for scale removal power, water spot reduction effect, slipperiness, and spray pattern as follows. The results are shown in Tables 1 to 7.

[0068] <Evaluation> (Evaluation of limescale removal power) Five 2cm x 10cm glass fiber reinforced plastic (FRP) test pieces (manufactured by Nitto Shinko Co., Ltd.) were fixed to the inside wall of a typical household bathtub, and four adult males took turns bathing in the test pieces, once per day, for three days, allowing dirt to adhere to the test pieces. During this time, only the bath water was replaced, and the bathtub was used without being washed. After the five test pieces with the stains attached were thoroughly dried, the hard surface liquid detergent composition was filled into a trigger spray container (manufactured by Lion Corporation, product name "Look Plus Bathtub Cleansing") and sprayed onto the test pieces so that the entire surface was wet, and the test pieces were left horizontally for 1 minute, and then rinsed with 15°C tap water at 120 mL / s for 10 seconds. The test pieces were then thoroughly dried, and the state of stain removal on the surfaces of the five test pieces was confirmed visually and by touch, and the scale removal power was evaluated based on the following evaluation criteria. In the following evaluation criteria, ⊚ and ◯ were considered to be acceptable. <Evaluation Criteria> ⊚: Very good stain removal (no stains were observed visually on any of the five test pieces, and all five test pieces were smooth to the touch). ○: Good stain removal (one or more of the five test pieces had no visible stains, and the entire surface of the test piece felt smooth to the touch, and at least one of the five test pieces felt rough to the touch). △: Stain removal was uneven (all five of the five test pieces were visually stained and all five felt rough to the touch, but the visual staining and roughness were reduced compared to before washing). ×: Almost no stains were removed (all five of the five test pieces were visually stained and all five felt rough to the touch, and the visual stains and roughness to the touch were the same as before cleaning)

[0069] (Evaluation of water spot reduction effect) 0.5 mL of the hard surface liquid detergent composition was applied to the surface of a 5 cm x 10 cm FRP test piece (manufactured by LIXIL Corporation), left in a horizontal position for 1 minute, and then rinsed with 15°C tap water at 120 mL / s for 10 seconds. After rinsing, the degree of wetting and spreading of the water film on the surface of the test piece, i.e., the proportion of the surface of the test piece covered with the water film, was visually observed. Since the more the water film spreads, the greater the effect of reducing water spots, the effect of reducing water spots was evaluated based on the following evaluation criteria. In the following evaluation criteria, ◎, ○, and △ were considered to be acceptable. <Evaluation Criteria> ⊚: The proportion of the surface of the test piece covered with a water film is 80% or more. ◯: The proportion of the surface of the test piece covered with a water film is 50% or more and less than 80%. △: The proportion of the surface of the test piece covered with a water film is 30% or more but less than 50%. ×: The proportion of the surface of the test piece covered with a water film is less than 30%.

[0070] (Evaluation with null) 0.1 g of the hard surface liquid detergent composition was placed on the index finger, held between the thumb, and immersed in 200 mL of tap water at 25°C. The index finger and thumb were rubbed together with a constant force at a rate of 4 times per second. The time required for the hard surface liquid detergent composition to lose its sliminess and become palpable with friction between the fingers was measured, and the sliminess was evaluated based on the following evaluation criteria. In the following evaluation criteria, ◎◎, ◎, and ○ were considered to be acceptable. <Evaluation Criteria> ⊚◎: The required time was less than 15 seconds, and the slippery texture was removed very well. ⊚: The required time is 15 seconds or more and less than 18 seconds, and the degree of removal of the slippery feeling is quite good. ◯: The required time was 18 seconds or more and less than 20 seconds, and the slippery feeling was removed satisfactorily. △: The required time was between 20 and 25 seconds, and the degree of removal of the slippery coating was uneven. ×: The required time is 25 seconds or more, and the stickiness is very difficult to remove.

[0071] (Spray pattern evaluation) The hard surface liquid cleaner composition was filled into a trigger spray container (a container under the trade name "Look Plus Bathtub Cleansing" manufactured by Lion Corporation), and the diameter of the spray area (spray diameter) was measured when sprayed in one blast onto the vertical surface of an FRP bathtub from a distance of 20 cm, and the spray pattern was evaluated based on the following evaluation criteria. In the following evaluation criteria, ◎ and ○ were considered to be acceptable. <Evaluation Criteria> ◎: Spray diameter is 13cm or more. ○: Spray diameter is 12.5 cm or more and less than 13 cm. ×: Spray diameter is less than 12.5 cm.

[0072] [Table 1]

[0073] [Table 2]

[0074] [Table 3]

[0075] [Table 4]

[0076] [Table 5]

[0077] [Table 6]

[0078] [Table 7]

[0079] As is clear from Tables 1 to 7, the hard surface liquid cleaning composition of each example had a large spray diameter and a wide range of spray patterns, was able to suppress the occurrence of water spots on hydrophobic hard surfaces, had high scale cleaning power, and was able to reduce sliminess.

[0080] On the other hand, as is clear from Table 7, the hard surface liquid cleaner composition of Comparative Example 1, which did not contain component (C), had a small spray diameter when sprayed and was prone to being slimy. The hard surface liquid detergent compositions of Comparative Examples 2 to 4, which did not contain component (B) but instead used component (B'), had small spray diameters when sprayed. In particular, the hard surface liquid detergent compositions of Comparative Examples 2 and 3, which used B'-4 or B'-5, were prone to sliminess. The hard surface liquid detergent composition of Comparative Example 4, which used B'-6, was prone to water spots. The hard surface liquid cleaner composition of Comparative Example 5, which did not contain component (B), had a small spray diameter when sprayed and was prone to water spots. The hard surface liquid detergent composition of Comparative Example 6, in which the A / B ratio was less than 0.5, was prone to water spots. The hard surface liquid detergent composition of Comparative Example 7, which had an A / B ratio of more than 300, was prone to water spots. The hard surface liquid cleaner composition of Comparative Example 8, in which the C / B ratio was less than 1, had a small spray diameter when sprayed, was prone to water spots, and was prone to slimy feel. The hard surface liquid cleaner composition of Comparative Example 9, which had a C / B ratio of more than 100, had a small atomization diameter when sprayed.

Claims

1. Component (A): a non-soap anionic surfactant; (B) component: cationized cellulose; (C) component: an alkyl polyglucoside represented by the following general formula (C1), the mass ratio of the component (A) to the component (B) is 0.5 to 300; the mass ratio of the component (C) to the component (B) is 5 to 30; A hard surface liquid cleaner composition having a viscosity of less than 30 mPa·s at 25°C. R １ -O-[G]z ・・・(C1) (In formula (C1), R １ represents an alkyl group having 8 to 20 carbon atoms, G represents a glucoside residue, and z represents the degree of sugar polymerization, a number from 1 to 5.

2. The hard surface liquid detergent composition according to claim 1, wherein the component (A) is at least one selected from α-olefin sulfonic acid or a salt thereof, linear alkylbenzene sulfonic acid or a salt thereof, alkanesulfonic acid or a salt thereof, alkyl sulfate ester or a salt thereof, and polyoxyalkylene alkyl ether sulfate or a salt thereof.

3. The hard surface liquid detergent composition according to claim 1 or 2, wherein the content of the component (B) is 0.01 to 0.1 mass % relative to the total mass of the hard surface liquid detergent composition.

4. The hard surface liquid detergent composition according to any one of claims 1 to 3, wherein the content of the component (A) is 0.5 to 1.5 mass% relative to the total mass of the hard surface liquid detergent composition.

5. The hard surface liquid detergent composition according to any one of claims 1 to 4, wherein the content of the component (C) is 0.5 to 1.5 mass% relative to the total mass of the hard surface liquid detergent composition.

6. The hard surface liquid cleaner composition according to any one of claims 1 to 5, having a pH of 9.0 to 11.0 at 25°C.

7. The hard surface liquid cleaner composition according to any one of claims 1 to 6, which is for use in a bathroom.

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