JP2023077597A - Liquid detergent composition for hard surfaces - Google Patents

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

The present invention relates to hard surface liquid cleaning compositions.

Bathroom cleaners are required to be easier to clean in a series of steps from washing to rinsing and to alleviate discomfort such as sliminess.
In the cleaning process, from the viewpoint of reducing the effort on the hands and fingers when spraying the cleaning agent on the bathtub, etc., a cleaning agent that can be sprayed over a wide area with one spray, and from the viewpoint of easy cleaning, remove dirt from the target surface. However, there is a demand for a cleaning agent that suppresses the generation of water spots, which are a kind of stain.
In the rinsing process, it is desirable to reduce the sliminess derived from the cleaning agent component from the viewpoint of alleviating discomfort.

From this point of view, a liquid detergent composition that has a large spray diameter and a wide spray pattern, has the function of maintaining the ability to suppress the occurrence of water spots, and can reduce the sliminess derived from detergent components. Development is underway.
For example, Patent Literatures 1 and 2 disclose a liquid detergent composition that is improved in detergency while reducing sliminess by using two or more types of surfactants in specific amounts.
Patent Document 3 discloses a liquid cleaning solution that suppresses the occurrence of water spots and reduces sliminess derived from cleaning agent components by combining glyceryl ether, magnesium, an anionic surfactant, and a water-soluble polymer in a specific ratio. An agent composition is disclosed.
Patent Document 4 discloses a spray-type cleaning product capable of spraying a liquid cleaning composition over a wide area by using a specific amount of an anionic surfactant and an amphoteric surfactant in combination.

JP 2008-143947 A JP 2005-325167 A JP-A-2005-264009 Japanese Patent Application Laid-Open No. 2004-322078

However, no liquid detergent composition is known which satisfies all the requirements at the same time.
An object of the present invention is to provide a hard surface liquid detergent composition that has a large spray diameter and a wide spray pattern, can suppress the occurrence of water spots on hard surfaces, and can reduce sliminess.

The present invention has the following aspects.
[1] Component (A): a non-soap anionic surfactant;
(B) component: cationized cellulose;
(C) component: containing an alkyl polyglucoside represented by the following general formula (C1),
The mass ratio represented by the component (A)/component (B) is 0.5 to 300,
The mass ratio represented by the component (C)/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 polymerization of sugar, representing a number from 1 to 5.)
[2] Component (A) is α-olefin sulfonic acid or its salt, linear alkylbenzene sulfonic acid or its salt, alkanesulfonic acid or its salt, alkyl sulfate ester or its salt, polyoxyalkylene alkyl ether sulfuric acid or its salt The hard surface liquid detergent composition of [1], which is at least one selected from:
[3] The content of component (B) is 0.01 to 1.0% by mass, more preferably 0.01 to 0.5% by mass, relative to the total mass of the hard surface liquid cleaning composition. %, more preferably 0.01 to 0.1% by mass.
[4] The content of component (A) is 0.1 to 5.0% by mass, more preferably 0.1 to 3.0% by mass, relative to the total mass of the liquid cleaning composition for hard surfaces. %, more preferably 0.5 to 1.5% by mass.
[5] The content of component (C) is 0.1 to 2.0% by mass, more preferably 0.1 to 1.5% by mass, relative to the total mass of the hard surface liquid cleaning composition. %, more preferably 0.5 to 1.5% by mass.
[6] The hard surface liquid detergent composition according to any one of [1] to [5], which has a pH of 9.0 to 11.0 at 25°C.
[7] The hard surface liquid detergent composition according to any one of [1] to [6], which is for bathroom use.

According to the present invention, it is possible to provide a hard surface liquid detergent composition that has a large spray diameter and a wide spray pattern, can suppress the occurrence of water spots on hard surfaces, and can reduce sliminess.

The present invention will be described in detail below.
The hard surface liquid cleaning composition of the present invention is a composition containing the following components (A), (B) and (C). The hard surface liquid cleaning composition may contain water. Moreover, the hard-surface liquid cleaning composition may further contain components (optional components) other than the components (A), (B), (C) and water, if necessary.

<(A) Component>
Component (A) is a non-soap anionic surfactant.
By including the component (A) in the hard surface liquid detergent composition, effective detergency can be exerted on hard surface stains, sebum stains, protein stains, and the like.
In the present invention, the "non-soap anionic surfactant" is an anionic surfactant other than higher fatty acids or salts thereof (so-called soap). A "higher fatty acid" is a saturated or unsaturated fatty acid having 8 to 24 carbon atoms. That is, component (A) is an anionic surfactant excluding saturated or unsaturated fatty acids having 8 to 24 carbon atoms or salts thereof.

Component (A) includes, for example, α-olefin sulfonic acid or its salt, linear alkylbenzene sulfonic acid or its salt, alkanesulfonic acid or its salt, α-sulfo fatty acid ester or its salt, internal olefin sulfonic acid or its salt, Sulfonic acid or its salt such as hydroxyalkanesulfonic acid or its salt; Sulfuric acid ester such as alkyl sulfate or its salt, polyoxyalkylene alkyl ether sulfuric acid or its salt, polyoxyalkylene alkenyl ether sulfate or its salt or its salt; 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, acylaminocarboxylic acids or salts thereof phosphoric acid or salts thereof such as alkyl phosphates or salts thereof, polyoxyalkylene alkyl phosphates or salts thereof, polyoxyalkylene alkylphenyl phosphates or salts thereof, glycerin fatty acid ester monophosphates or salts thereof; mentioned.
Salt forms of non-soap anionic surfactants include, for example, alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). ) and the like.
Among these, the component (A) is preferably sulfonic acid or its salt, sulfuric acid ester or its salt, α-olefin sulfonic acid or its salt, linear alkylbenzene sulfonic acid or its salt, from the viewpoint of further increasing detergency. , alkanesulfonic acid or its salt, alkyl sulfate ester or its salt, polyoxyalkylene alkyl ether sulfuric acid or its salt are more preferable, and α-olefinsulfonic acid or its salt is more preferable.
(A) Component may be used individually by 1 type, and may be used in combination of 2 or more types.

Commercially available products of component (A) include, for example, sodium α-olefin sulfonate under the trade name “Liporan LJ441 (manufactured by Lion Specialty Chemicals Co., Ltd.)”, and linear alkyl (C12-C14) benzene sulfonate under the trade name. "Lipon PS-230 (manufactured by Lion Specialty Chemicals Co., Ltd.)", trade name "HOSTAPUR SAS 93 (manufactured by Clariant)" as sodium alkanesulfonate, trade name "Alscope LS-30 (Toho Chemical Co., Ltd.)" as sodium alkyl sulfate Kogyo Co., Ltd.)”, and as sodium polyoxyethylene alkyl ether sulfate, trade name “Shinoline SPE-1250 (manufactured by Shin Nippon Rika Co., Ltd.)”.
The number after "C" such as "C12" means the number of carbon atoms, and the same applies hereinafter.

The content of component (A) is preferably 0.1 to 5.0% by mass, more preferably 0.1 to 3.0% by mass, more preferably 0.5% by mass, based on the total mass of the hard surface liquid cleaning composition. ~1.5% by mass is more preferable. (A) If content of a component is more than the said lower limit, detergency will increase more. If the content of the component (A) is equal to or less than the above upper limit, it is possible to further reduce the sliminess derived from the detergent components. In addition, when the liquid detergent composition is sprayed onto a hard surface, the diameter of the spray is less likely to become small, and a wide area can be sprayed with one spray.

<(B) Component>
Component (B) is cationized cellulose.
Since the hard-surface liquid cleaning composition contains the component (B), hydrophilicity is imparted to the hard surface when the hard-surface liquid cleaning composition is sprayed onto the hard surface. As a result, water tends to form a film on the hard surface during the rinsing process, and water is removed in the form of a film during drying. In particular, it is possible to effectively suppress the occurrence of water spots on hydrophobic hard surfaces such as glass fiber reinforced plastic (FRP) used in bathtubs and the like. Although the reason for this is not clear, it is considered as follows.
When the hard-surface liquid cleaning composition contains the component (B) in addition to the component (A), a complex is formed by the component (A) and the component (B) during spraying. Components (A) and (B) each show hydrophilicity by themselves, but when they form a complex, they also show hydrophobicity, and the complex easily adheres uniformly to a hydrophobic hard surface. At the same time, hydrophilicity, which is the original property of the components (A) and (B), is imparted to the hard surface. As a result, as described above, water tends to form a film on the hard surface during the rinsing process, and water is removed in the form of a film during drying, so that water droplets are less likely to remain.

As the component (B), for example, cationized cellulose having a structural unit represented by the following general formula (B1) (hereinafter sometimes referred to as "(B1) component"), and represented by the following general formula (B2) cationized cellulose having a structural unit (hereinafter sometimes referred to as "(B2) component"), cationized cellulose having a structural unit represented by the following general formula (B3) (hereinafter referred to as "(B3) component" ), cationized cellulose having a structural unit represented by the following general formula (B4) (hereinafter sometimes referred to as “(B4) component”), and the like.
Among these, the component (B1) is preferable from the viewpoint of further suppressing the occurrence of water spots on hard surfaces (especially hydrophobic hard surfaces).
(B) component may be used individually by 1 type, and may be used in combination of 2 or more type.

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

The degree of cationization of component (B) is preferably 0.5 to 2.2% by mass, more preferably 1.5 to 2.2% by mass. If the degree of cationization is within the above range, the occurrence of water spots on hard surfaces (especially hydrophobic hard surfaces) can be further suppressed.
Here, the "degree of cationization" means the content (% by mass) of nitrogen atoms derived from the cationizing agent in the molecule of component (B), that is, the number of nitrogen atoms relative to the total mass of component (B). means percentage of mass.

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

Component (B) preferably has a viscosity of 1 to 60 mPa·s, more preferably 5 to 55 mPa·s, and even more preferably 10 to 50 mPa·s as a 1% by mass aqueous solution at 25°C. , 15 to 45 mPa·s. If the viscosity of the 1% by mass aqueous solution of the component (B) is within the above range, it is rinsed with running water such as a shower, and when the concentration of the liquid cleaning composition for hard surfaces becomes low, the drainage property is excellent.
The viscosity is a value obtained by measuring a 1% by mass aqueous solution of component (B) at 25° C. with a Brookfield viscometer. The viscosity measurement conditions are as follows.

Measurement condition:
[rotor]
The rotor numbers and rotor rotation speeds corresponding to the viscosities to be measured are as follows.
- Viscosity is less than 100 mPa·s: Rotor No. No. 1, 60 rpm.
- Viscosity of 100 mPa·s or more and less than 500 mPa·s: Rotor No. No. 2, 60 rpm.
- Viscosity of 500 mPa·s or more and less than 2000 mPa·s: Rotor No. No. 3, Rotation speed 60rpm.
- Viscosity of 2000 mPa·s or more and less than 10000 mPa·s: Rotor No. No. 4, 60 rpm.
- Viscosity of 10,000 mPa·s or more and less than 50,000 mPa·s: Rotor No. No. 4, number of revolutions 12rpm.
[Read Number]
60 seconds after the start of rotation of the rotor.

Specific examples of cationized cellulose include hydroxytrimethylammoniopropyl hydroxyethyl cellulose chloride as component (B1) and cation-modified hydroxyethyl cellulose such as hydroxyethyl cellulose dimethyl diallyl ammonium chloride polymer as component (B2).

Commercially available products of component (B1) include, for example, the trade name “Leogard GP (quaternary nitrogen content of 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)” and the trade name “Leogard MGP (quaternary nitrogen Content rate 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)”, trade name “Leogard MLP (quaternary nitrogen content 0.6% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)”, trade name "SUPRACARE 133 (quaternary nitrogen content 0.8% by mass, manufactured by Dow Chemical Japan Co., Ltd.)", trade name "SUPRACARE 212 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Japan Co., Ltd.) ”, trade name “SUPRACARE 240 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Japan Co., Ltd.)”, trade name “SUPRACARE 241 (quaternary nitrogen content 1.0% by mass, Dow Chemical Japan Co., Ltd.)”, trade name “UCARE JR125 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Japan Co., Ltd.)”, trade name “UCARE JR400 (quaternary nitrogen content 1.9 mass %, Dow Chemical Japan Co., Ltd.)”, trade name “UCARE LR30M (quaternary nitrogen content 1.0% by mass, Dow Chemical Japan Co., Ltd.)”, trade name “SoftCAT SL-5 (4th class nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan Co., Ltd.)”, trade name “SoftCAT SL-60 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan Co., Ltd.)”, Trade name “SoftCAT SL-100 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan Co., Ltd.)”, trade name “SoftCAT SX-400X (quaternary nitrogen content 2.1% by mass, Dow Chemical Japan Co., Ltd.)”, trade name “SoftCAT SX-1300X (quaternary nitrogen content 2.1% by mass, Dow Chemical Japan Co., Ltd.)”, trade name “SoftCAT SX-400H (4th Grade 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.)”, trade name “Catinal LC-100 (quaternary nitrogen content 1.0% by mass, Toho Chemical Kogyo Co., Ltd.)”, trade name “Catinal LC-200 (quaternary nitrogen content 1.0% by mass, Toho Chemical Industry Co., Ltd.)”. Among these, "SUPRACARE212" is preferable from the viewpoint of imparting hydrophilicity.

Commercially available products of component (B4) include, for example, the trade name “SoftCAT SL-5 (quaternary nitrogen content of 1.0% by mass, manufactured by Dow Chemical Japan Co., Ltd.)” and the trade name “SoftCAT SL-60 (No. Quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan Co., Ltd.)”, trade name “SoftCAT SL-100 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Japan Co., Ltd.)” , trade name “SoftCAT SX-400X (quaternary nitrogen content 2.1% by mass, manufactured by Dow Chemical Japan Co., Ltd.)”, trade name “SoftCAT SX-1300X (quaternary nitrogen content 2.1% by mass) , Dow Chemical Japan Co., Ltd.)”, trade name “SoftCAT SX-400H (quaternary nitrogen content 2.1% by mass, Dow Chemical Japan Co., Ltd.)”.
Among them, the (B1) components "SUPRACARE 133", "SUPRACARE 212", and "SUPRACARE 240" are selected from the viewpoint of excellent drainage performance and ability to further suppress the occurrence of water spots on hard surfaces (especially hydrophobic hard surfaces). Preferred are "SUPRACARE212" and "SUPRACARE240".

The content of component (B) is preferably 0.01 to 1.0% by mass, more preferably 0.01 to 0.5% by mass, more preferably 0.01%, based on the total mass of the liquid cleaning composition for hard surfaces. ~0.1% by mass is more preferable. If the content of the component (B) is at least the above lower limit, the occurrence of water spots on hard surfaces (especially hydrophobic hard surfaces) can be further suppressed. In addition, the diameter of the sprayed hard surface liquid detergent composition is less likely to become small, and a wide area can be sprayed with one spray. If the content of the component (B) is equal to or less than the above upper limit, it is possible to further reduce the sliminess derived from the detergent component.

The mass ratio represented by component (A)/component (B) (hereinafter also referred to as “A/B ratio”) is 0.5 to 300, preferably 1 to 150, more preferably 5 to 30. If the A/B ratio is within the above range, the formation of water spots on hard surfaces (especially hydrophobic hard surfaces) can be suppressed.

<(C) Component>
Component (C) is an alkyl polyglucoside represented by the following general formula (C1).
By containing the (C) component in the hard-surface liquid cleaning composition, it is possible to reduce sliminess derived from the cleaning component.
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 polymerization of sugar, representing a number from 1 to 5.)

The number of carbon atoms in the alkyl group for R ¹ is 8 to 20, preferably 8 to 16, more preferably 8 to 14. Alkyl groups may be linear or branched.
G is a glucosidic residue. The reducing sugar used as a raw material for glucoside may be either an aldose or a ketose, and triose, tetrose, pentose and hexose having 3 to 6 carbon atoms may be mentioned. Specific examples of aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, galose, aldose, idose, talose and xylose, and examples of ketose include fructose. Among these, aldopentose or aldohexose having 5 or 6 carbon atoms are preferred, and glucose is most preferred.
z indicates the degree of polymerization of sugar, and represents 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.

As the component (C), an alkyl polyglucoside represented by the following general formula (C1-1) (hereinafter sometimes referred to as “(C1-1) component”) is preferable.

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

(C) Component may be used individually by 1 type, and may be used in combination of 2 or more types.
As component (C), a mixture of two or more types of alkyl polyglycosides having different numbers of carbon atoms in the alkyl group (R ¹ ) may be used. In that case, the average carbon number of R ¹ is preferably 8-16, more preferably 8-14.

Commercially available products of component (C1-1) include, for example, trade name "Glucopon (registered trademark) 215 UP (manufactured by BASF)", "Glucopon (registered trademark) 600 CSUP (manufactured by BASF)", trade name "Glucopon ( registered trademark) 650 EC (manufactured by BASF)", trade name "Glucopon (registered trademark) 600 CSUP/MB (manufactured by BASF)", trade name "Glucopon (registered trademark) 650 EC/MB (manufactured by BASF)", etc. is mentioned.

The content of component (C) is preferably 0.1 to 2.0% by mass, more preferably 0.1 to 1.5% by mass, more preferably 0.5% by mass, based on the total mass of the hard surface liquid cleaning composition. ~1.5% by mass is more preferable. If the content of the component (C) is within the above range, it is possible to further reduce the sliminess derived from the cleaning agent components. In addition, when the liquid detergent composition is sprayed onto a hard surface, the diameter of the spray is less likely to become small, and a wide area can be sprayed with one spray.

The mass ratio represented by component (C)/component (B) (hereinafter also referred to as “C/B ratio”) is 1-100, preferably 3-75, more preferably 5-30. If the C/B ratio is within the above range, the diameter of the spray when the liquid detergent composition is sprayed onto a hard surface is unlikely to become small, and a wide range can be sprayed with one blow. In particular, when the C/B ratio is at least the above lower limit, it is possible to further reduce nulliness derived from detergent components.

<Water>
The hard surface liquid detergent composition preferably contains water as a solvent from the viewpoint of improving ease of handling and rinsability.
As water, ion-exchanged water, distilled water, tap water, or the like can be used.
One type of water may be used alone, or two or more types may be used in combination as appropriate.

The water content is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 95% by mass, relative to the total mass of the hard surface liquid cleaning composition. If the content of water is within the above range, it is easy to prepare the hard surface liquid cleaning composition. In addition, when using the hard surface liquid cleaning composition, the solubility in water is improved.

<Optional component>
Optional components include, for example, higher fatty acids or salts thereof, water-soluble organic solvents, sequestering agents, other surfactants, pH adjusters, bactericides, preservatives, antifungal agents, pigments, antioxidants, and thickeners. , ultraviolet absorbers, solubilizers, emulsifiers, fragrances, and the like.

Examples of higher fatty acids include stearic acid, linoleic acid, oleic acid, myristic acid, and coconut oil fatty acid.
Salt forms of higher fatty acids include, for example, alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.), and the like. .
Higher fatty acids or salts thereof may be used singly or in combination of two or more.

The content of the higher fatty acid or its salt is preferably 0.05 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, more preferably 0.1 to 2.0% by mass, based on the total mass of the hard surface liquid cleaning composition. 2 to 1.0% by mass is more preferable.

A water-soluble organic solvent is an organic solvent that dissolves in 1 L of water at 25° C. in an amount of 50 g or more.
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, and propylene glycol monopropyl ether. , and solfit.
The water-soluble organic solvents may be used singly or in combination of two or more.

The content of the water-soluble organic solvent is preferably 0.1 to 5.0% by mass, more preferably 1.0 to 3.0% by mass, based on the total mass of the liquid cleaning composition for hard surfaces.

Examples of the sequestering agent include organic carboxylic acids, aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, phosphoric acids and the like.
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, gluconic acid and the like.
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, aminotrimethylenephosphonic acid and the like.
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 agents may be used singly or in combination of two or more.

The content of the sequestering agent is preferably 1.0 to 5.0% by mass, more preferably 1.5 to 3.5% by mass, based on the total mass of the liquid cleaning composition for hard surfaces.

Other surfactants are surfactants other than components (A), (C), and higher fatty acids and salts thereof.
Other surfactants include nonionic surfactants other than component (C), cationic surfactants, amphoteric surfactants, and semipolar surfactants.
Other surfactants may be used singly or in combination of two or more.

The total content of all surfactants (excluding higher fatty acids and salts thereof) contained in the hard-surface liquid cleaning composition (total surfactant content) is the total amount of the hard-surface liquid cleaning composition. 0.2 to 30.0% by mass is preferable, 0.5 to 10.0% by mass is more preferable, 1.0 to 5.0% by mass is more preferable, and 1.0 to 3.0% by mass based on the mass % is particularly preferred.

Examples of pH adjusters include inorganic acids such as hydrochloric acid and sulfuric acid; alkaline 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 singly or in combination of two or more.

In addition, the total amount of the components constituting the hard surface liquid cleaning composition is 100% by mass.

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

The viscosity of the hard surface liquid cleaning composition can be adjusted by adjusting the water content, adding a thickening agent, and the like.
The viscosity of the hard-surface liquid cleaning composition was measured at 25° C. using a Brookfield viscometer. 1. A value measured 60 seconds after the start of rotation of the rotor at a rotor speed of 60 rpm.

(pH)
The pH of the hard surface liquid cleaning composition at 25°C is preferably 6.0 or higher, more preferably 9.0 or higher, still more preferably 9.0 to 12.0, and particularly preferably 9.0 to 11.0. , 10.0 to 11.0 are most preferred. If the pH at 25° C. is within the above range, the detergency against scale stains increases.

The pH of the hard-surface liquid cleaning composition can be adjusted by adding an appropriate amount of pH adjuster.
The pH of the hard surface liquid cleaning composition is a value measured at 25°C by a method conforming to JIS Z 8802:2011 "pH measurement method".

<Manufacturing method>
A hard-surface liquid detergent composition is manufactured by a conventionally well-known manufacturing method. For example, water is added with components (A), (B) and (C), and if necessary optional components other than a pH adjuster. obtained by adjusting.

<How to use>
The method of using the liquid hard surface cleaning composition includes, for example, a method of impregnating a cleaning tool such as a sponge with the liquid hard surface cleaning composition, and scrubbing the hard surface to be cleaned with a sponge. The hard surface liquid detergent composition is contained in a discharge container, and an appropriate amount of the hard surface liquid detergent composition is sprayed from this discharge container onto the hard surface. and how to use it.
In particular, the liquid cleaning composition for hard surfaces of the present invention does not easily reduce the diameter of the spray when the liquid cleaning composition is sprayed on a hard surface, and can be sprayed over a wide area with one spray, so it is used for "washing without rubbing." A method is preferred.

Materials of hard surfaces to be cleaned include plastics, tiles, stainless steel, ceramics, glass, marble, and concrete. Among these, the hard surface liquid detergent 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 (eg, polyethylene, polypropylene, etc.), polyethylene terephthalate, and the like.
Specific examples of hard surfaces include bathtubs in bathrooms, floors and walls in bathrooms, bathroom incidental equipment (for example, bath lids, bathroom mats (drainboards), chairs for bathrooms, soap stands, perforated drains, hair catchers, etc.) , faucets and faucets, bathtub lids, bathroom doors, mirrors, drains, toilet bowls, etc.

A spray container, a squeeze container, etc. are mentioned as a discharge container which accommodates a hard-surface liquid detergent composition. Among them, a spray container is preferable as the discharge container for containing the liquid cleaning composition for hard surfaces because of its excellent applicability to the object to be cleaned.
The spray container includes, for example, an aerosol spray container, a trigger spray container (direct pressure type or pressure accumulation type), a dispenser spray container, and the like. These containers may be manually operated or electrically operated.
Examples of the aerosol spray container include those described in JP-A-9-3441 and JP-A-9-58765. When filling an aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc. can be used as the propellant. The propellants may be used singly or in combination of two or more.
Examples of the trigger spray container include those described in JP-A-9-268473 and JP-A-10-76196.
Examples of dispenser spray containers include those described in, for example, JP-A-9-256272.
Examples of the pressure accumulation type trigger spray container include those described in JP-A-2013-154276.
Among these, the trigger spray container is preferable because it has good spray properties and spray pattern, and good coatability can be obtained.

The hard-surface liquid detergent composition of the present invention does not easily reduce the diameter of the spray when sprayed onto a hard surface, can be sprayed over a wide area with one spray, and is effective against sebum and protein stains adhering to the floors and walls of bathtubs and bathrooms. It has a high detergency against hard surfaces, and can suppress the occurrence of water spots on hard surfaces, and can reduce sliminess derived from detergent components, so it is suitable for bathrooms.
In addition, the hard-surface liquid detergent composition for bathrooms is also particularly referred to as "liquid detergent composition for bathrooms."

<Effect>
The hard surface liquid cleaning composition of the present invention described above contains the above-described components (A), (B), and (C) in a specific mass ratio, and has a viscosity of 30 mPa· at 25°C. Since it is less than s, the spray diameter is large and the spray pattern is wide when sprayed, the occurrence of water spots on hard surfaces (especially hydrophobic hard surfaces) can be suppressed, and nulls derived from detergent components It can reduce sticking.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited by the following description.

"Raw materials used"
(A) The compound shown below was used as a component.
A-1: AOS, sodium α-olefin sulfonate having 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Liporan LJ441”).

As the component (B) or its comparative product (component (B')), the compounds shown below were used.
B-1: Cationized cellulose (manufactured by Dow Chemical Japan Co., Ltd., 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: Cationized cellulose (manufactured by Dow Chemical Japan Co., Ltd., product 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: Cationized cellulose (manufactured by Dow Chemical Japan Co., Ltd., 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 Co., Ltd., trade name "Merquat 550PR Polymer").
· B'-5: cationized 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).

As the component (C), the compounds shown below were used.
· C-1: Alkyl (C8-10) polyglucoside (manufactured by BASF, trade name "Glucopon215UP", in the above general formula (C1-1), R ¹ is a linear alkyl group having 8 to 10 carbon atoms and m=1.5, product viscosity at 20° C. 3500 mPa·s).
· C-2: Alkyl (C8-14) polyglucoside (manufactured by BASF, trade name "Glucopon650EC", in the above general formula (C1-1), R ¹ is a linear alkyl group having 8 to 14 carbon atoms Yes, m is 1.5 compound, product viscosity at 20 ° C. 2250 mPa s)

The following compounds were used as water and optional components.
- Water: deionized water.
· Coconut oil fatty acid K: Coconut oil fatty acid potassium (Lion Specialty Chemicals Co., Ltd., trade name "coconut oil fatty acid potassium", soap-based anionic surfactant).
· K myristate: Potassium myristate (manufactured by NOF Corporation, trade name "Nonsul 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 Akzo Nobel Co., Ltd., trade name "Disolvin 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.).

"Examples 1 to 23, Comparative Examples 1 to 9"
<Preparation of Hard Surface Liquid Cleaning Composition>
According to the compositions shown in Tables 1 to 7, the components (A), (B) and (C), and optional components other than the pH adjuster were added to water and mixed. A pH adjuster was used to adjust the pH to the values shown in 1 to 7 to obtain a hard surface liquid cleaning composition of each example. Tables 1 to 7 show the composition (ingredients, content (% by mass)) and viscosity of the obtained hard surface liquid cleaning composition of each example.
In addition, the mass % shows a pure content unless otherwise specified. In the table, when there is a blank compounding component, that compounding component is not blended. In the table, the "appropriate amount" of the pH adjuster is the amount required to adjust the pH of the hard surface liquid cleaning composition of each example to the value shown in the table. In the table, the water content "balance" means that water is blended so that the total amount (% by mass) of all the ingredients contained in the hard surface liquid cleaning composition is 100% by mass. means. That is, the blending amount of water is the remainder after subtracting the total blending amount (in terms of pure content) of the blending components other than water from the total mass of the hard surface liquid cleaning composition. In addition, "A/B ratio" in the table is the mass ratio represented by component (A)/component (B). "C/B ratio" is a mass ratio represented by component (C)/component (B).

The pH of the hard surface liquid cleaning composition of each example was adjusted to 25° C. and then measured using a glass electrode pH meter (manufactured by Toa DKK Co., Ltd., trade name “HM-25R”). The measurement method was performed in accordance with JIS Z 8802:1984 "pH measurement method".
The viscosity of the liquid cleaning composition for hard surfaces in each example was adjusted to 25° C., and then measured using a Brookfield viscometer (manufactured by Toki Sangyo Co., Ltd.). 1. At a rotor rotation speed of 60 rpm, the value after 60 seconds from the start of rotation of the rotor was measured as the viscosity.
In addition, the hard surface liquid cleaning composition of each example was evaluated in terms of detergency, water spot reduction effect, sliminess, and spray pattern as follows. The results are shown in Tables 1-7.

<Evaluation>
(Evaluation of scale detergency)
After fixing five 2 cm x 10 cm glass fiber reinforced plastic (FRP) test pieces (manufactured by Nitto Shinko Co., Ltd.) on the inner wall surface of a bathtub in a general household, four adult men took turns performing one test per day. The bathing was repeated for 3 days to attach dirt to the test piece. During this time, only the bath water was changed, and the bathtub was used without being washed.
After sufficiently drying the five test pieces to which the dirt adhered, a hard surface liquid detergent composition was applied to the test pieces in a trigger spray container (manufactured by Lion Corporation, trade name) so that the entire surface of the test pieces was wet. The container of "Look Plus Bathtub Cleansing") was filled and sprayed, left in a horizontal state for 1 minute, and then rinsed with 15°C tap water at 120 mL/s for 10 seconds. After that, the test pieces were sufficiently dried, and the state of removal of stains from the surfaces of the five test pieces was visually and finger-touched to evaluate the scale detergency based on the following evaluation criteria. In the following evaluation criteria, ⊚ and ∘ were regarded as acceptable.
≪Evaluation Criteria≫
⊚: Very good stain removal (out of the five test pieces, no stains were visually observed on all five test pieces, and the entire surface of the five test pieces was smooth to the touch).
○: Good stain removal (out of the 5 test pieces, no stains were visually observed in one or more test pieces, and a smooth finger touch was obtained on the entire surface of the test piece, and among the 5 test pieces, At least one test piece feels rough to the touch).
△: Uneven stain removal (out of 5 test pieces, stains are visually observed on all 5 test pieces, and a rough touch is felt on all 5 pieces, but the stain and rough touch by visual inspection are , less than before washing)
×: almost no stains removed (out of 5 test pieces, stains were visually observed on all 5 pieces, and a rough touch was felt on all 5 pieces; same as before)

(Evaluation of water spot reduction effect)
0.5 mL of the hard surface liquid cleaning 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 washed with tap water at 15°C to 120 mL/s. and rinsed off for 10 seconds.
After rinsing, the degree of wetting and spreading of the water film on the surface of the test piece, that is, the proportion of the surface of the test piece covered with the water film was visually observed. The water spot reduction effect was evaluated based on the following evaluation criteria, because the more the water film spreads, the higher the water spot reduction effect. In the following evaluation criteria, ⊚, ∘ and Δ were regarded as acceptable.
≪Evaluation Criteria≫
⊚: 80% or more of the surface of the test piece is covered with a water film.
◯: The proportion covered with water film is 50% or more and less than 80% of the surface of the test piece.
Δ: The proportion covered with water film is 30% or more and less than 50% of the surface of the test piece.
x: Less than 30% of the surface of the test piece is covered with a water film.

(Null evaluation)
0.1 g of the hard surface liquid detergent composition was placed on the index finger, sandwiched between the thumbs, and immersed in 200 mL of tap water at 25° C., and the index finger and thumb were rubbed together with a constant force at a pace of 4 times per second. . The time required for the hard-surface liquid detergent composition to become non-slippery and to feel finger friction was measured, and the slipperiness was evaluated based on the following evaluation criteria. In the following evaluation criteria, ⊚, ⊙ and ◯ were regarded as passed.
≪Evaluation Criteria≫
⊚: The required time is less than 15 seconds, and the removal of nulliness is very good.
⊚: Required time is 15 seconds or more and less than 18 seconds, and the degree of removal of nulliness is quite good.
Good: The required time is 18 seconds or more and less than 20 seconds, and the degree of removal of nulliness is good.
Δ: The required time is 20 seconds or more and less than 25 seconds, and there is unevenness in the removal of nulliness.
x: Required time is 25 seconds or longer, and nulliness is very difficult to remove.

(Evaluation of spray pattern)
The hard-surface liquid detergent composition was filled in a trigger spray container (manufactured by Lion Corporation, product name “Look Plus Bathtub Cleansing” container) and sprayed from a point 20 cm away from the vertical surface of the FRP bathtub in one blow. The diameter of the spray range (spray diameter) was measured, and the spray pattern was evaluated based on the following evaluation criteria. In the following evaluation criteria, ⊚ and ∘ were regarded as acceptable.
≪Evaluation Criteria≫
A: The spray diameter is 13 cm or more.
○: The spray diameter is 12.5 cm or more and less than 13 cm.
x: The spray diameter is less than 12.5 cm.

As is clear from Tables 1 to 7, the hard surface liquid cleaning composition of each example has a large spray diameter and a wide range of spray patterns, can suppress the occurrence of water spots on hydrophobic hard surfaces, and can prevent scalding. High detergency and reduced sliminess.

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

Claims (7)

(A) component: a non-soap anionic surfactant;
(B) component: cationized cellulose;
(C) component: containing an alkyl polyglucoside represented by the following general formula (C1),
The mass ratio represented by the component (A)/component (B) is 0.5 to 300,
The mass ratio represented by the component (C)/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 polymerization of sugar, representing a number from 1 to 5.) The component (A) is selected from α-olefin sulfonic acid or its salt, linear alkylbenzene sulfonic acid or its salt, alkanesulfonic acid or its salt, alkyl sulfate ester or its salt, polyoxyalkylene alkyl ether sulfuric acid or its salt. The hard surface liquid cleaning composition of claim 1, which is at least one. 3. The liquid cleaning composition for hard surfaces according to claim 1, wherein the content of component (B) is 0.01 to 0.1% by mass relative to the total mass of the liquid cleaning composition for hard surfaces. thing. The hard surface according to any one of claims 1 to 3, wherein the content of component (A) is 0.5 to 1.5% by mass with respect to the total mass of the hard surface liquid cleaning composition. A surface liquid cleaning composition. The hard surface according to any one of claims 1 to 4, wherein the content of the component (C) is 0.5 to 1.5% by mass with respect to the total mass of the hard surface liquid cleaning composition. A surface liquid cleaning composition. The hard surface liquid cleaning composition according to any one of claims 1 to 5, which has a pH of 9.0 to 11.0 at 25°C. The hard surface liquid cleaning composition according to any one of claims 1 to 6, which is for bathroom use.