JP7134086B2 - Bathroom cleaner composition - Google Patents

Description

The present invention relates to bathroom cleaning compositions.

Bathroom cleaning is usually carried out by scrubbing the walls of the bathroom, the surface of the bathtub, other bathroom accessories, etc. with a sponge impregnated with a bathroom liquid detergent.
In scrubbing, the object to be cleaned is directly rubbed with a sponge. For example, when cleaning a bathtub, it is necessary to bend forward, crouch down, or squat down to scrub the entire surface of the bathtub with the sponge, which is time-consuming. It takes a lot of effort and puts a lot of physical strain on you.

Various types of stains exist in bathrooms, such as hot water stains, which are a mixture of proteins, fatty acid metal salts, sebum, etc., and sebum stains derived from the human body. These stains stick to hard surfaces such as bathtubs when kept dry and require a great deal of effort to remove.

Conventionally, detergents have been proposed to reduce the labor and physical burden of such bathroom cleaning.
For example, in Patent Document 1, a surfactant including a non-soap anionic surfactant, a glycol-based solvent, and an aminocarboxylic acid-type chelating agent are contained in a predetermined amount ratio, and the pH is 10 to 12. Liquid bathroom cleaners have been proposed.
Patent Document 2 proposes a liquid detergent composition containing a glyceryl ether mixture, a surfactant, and a builder or an alkaline agent.
According to the invention of Patent Literature 1, detergency against scale stains (scale detergency) and rinsability are improved. According to the invention of Patent Document 2, it is intended to improve detergency against soap scum (scale detergency) and prevent damage to objects to be cleaned such as resin substrates (damage resistance).

JP 2016-124965 A JP-A-11-189796

However, bathroom cleaning compositions are required to further improve their detergency against sebum stains (sebum detergency) in addition to their detergency against hot water scale.
Bathroom detergent compositions are also required to foam well during scrubbing (foaming properties), and to quickly run off when the foam is washed away with shower water (rinsability).

Accordingly, an object of the present invention is to provide a bathroom cleaning composition which is excellent in detergency against scale and sebum, and which has good foamability and rinsability.

The present invention has the following aspects.
[1] (A) component: a surfactant containing the following (A1) component and the following (A2) component,
(B) component: a chelating agent;
(C) component: a glycol-based solvent;
A bathroom cleaning composition containing
(A1) Component: Non-soap anionic surfactant.
(A2) component: an amine-type surfactant represented by the following formula (A2-1).

[In the formula (A2-1), R ¹ , R ² and R ³ are substituents on N, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, , an aminoalkyl group having 1 to 4 carbon atoms, an alkyl group having 8 to 21 carbon atoms, or an alkenyl group having 8 to 21 carbon atoms; R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or a group represented by R ⁴ —X—(CH ₂ ) _m —; R ⁴ is a branched chain having 8 to 21 carbon atoms; X is —O—, —C(O)NR ⁵ —, or —NH—; R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group; Yes; m is an integer of 1 to 5; R ³ is an alkyl or alkenyl group having 8 to 21 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or R ⁴ —X—(CH ₂ ) _m — is a group represented by ]

[2] The bathroom cleaning composition according to [1], wherein the mass ratio of component (A1)/component (A2) is 8.5 to 30.
[3] The bathroom cleaning composition according to [1] or [2], wherein the component (A) further contains the following component (A3).
(A3) Component: Fatty acid salt having 8 to 24 carbon atoms.
[4] The bathroom cleaning composition according to any one of [1] to [3], wherein the content of component (A) is 0.5 to 5% by mass relative to the total mass.
[5] The bathroom cleaning composition according to any one of [1] to [4], wherein the component (A2) is an amine surfactant represented by the following formula (A2-3): .
R ¹¹ —N((CH ₂ ) _n NH ₂ ) ₂ (A2-3)
[In the formula (A2-3), R ¹¹ is a linear alkyl group having 8 to 18 carbon atoms, a branched alkyl group having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or a carbon It is a branched alkenyl group of number 8-18; n is an integer of 1-4. ]
[6] The bathroom cleaning agent according to any one of [1] to [5], wherein the mass ratio represented by component (B)/component (A) is 0.3 to 4.0. Composition.
[7] The bathroom cleaning composition according to any one of [1] to [6], which has a pH of 9 or higher at 25°C.

According to the bathroom cleaning composition of the present invention, it is possible to achieve excellent detergency against scale and sebum, as well as good foamability and rinsability.

<<Bathroom detergent composition>>
The bathroom cleaning composition of the present invention (hereinafter also simply referred to as "cleaning composition") is a composition containing components (A) to (C).

<(A) Component>
Component (A) is a surfactant containing component (A1) and component (A2) below. By containing the component (A), the detergent composition can demonstrate detergency against scale and sebum (hereinafter collectively referred to as "detergency").

((A1) component)
The (A1) component is a non-soap anionic surfactant. The component (A1) is used to exhibit effective detergency against scale stains, sebum stains, and the like adhering to the bathroom.
As used herein, the term "non-soap anionic surfactant" refers to anionic surfactants other than saturated or unsaturated fatty acid salts having 8 to 24 carbon atoms (so-called soaps).

Component (A1) includes, for example, alkylbenzenesulfonates, alkanesulfonates, alkyl sulfates, alkylpolyoxyethylene sulfates, α-olefinsulfonates, alkylphenoxyphenyl disulfonates, fatty acid salts other than soaps, α-sulfo fatty acid salts, ether carboxylates, alkyl phosphates, alkyl polyoxyethylene phosphates, dialkyl sulfosuccinates, alkyl sulfosuccinates, alkenyl succinates, N-acylamino acid salts, N-acylmethyl and taurine salts.
Among these, alkylbenzenesulfonates and α-olefinsulfonates are preferable, and α-olefinsulfonates are more preferable, from the viewpoint of excellent detergency.
Examples of salts include alkali metal salts such as sodium salts and potassium salts, and alkanolamine salts such as monoethanolamine salts and diethanolamine salts. Among these, alkali metal salts such as sodium salts and potassium salts are preferred.

Component (A1) preferably has an alkyl group having 8 to 18 carbon atoms. The alkyl group may be linear or branched.

The content of component (A1) is preferably 0.1 to 2.5% by mass, more preferably 0.5 to 1.5% by mass, relative to the total mass of the detergent composition. (A1) When the content of the component is at least the above lower limit, it is easy to improve detergency and foamability. (A1) When the content of the component is equal to or less than the above upper limit, it is easy to improve the rinsability.

The content of component (A1) in component (A) is preferably 50 to 99% by mass, more preferably 70 to 99% by mass, relative to the total mass of component (A). When the content of the component (A1) in the component (A) is within the above numerical range, the detergency tends to be improved.

((A2) component)
The (A2) component is an amine-type surfactant represented by the following formula (A2-1). The (A2) component can improve the sebum detergency and the foamability when used in combination with the (A1) component.

In formula (A2-1), R ¹ , R ² , and R ³ are substituents on N, and R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms. , an aminoalkyl group having 1 to 4 carbon atoms, an alkyl group having 8 to 21 carbon atoms, or an alkenyl group having 8 to 21 carbon atoms; R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, 1 a hydroxyalkyl group having 1 to 4 carbon atoms, an aminoalkyl group having 1 to ⁴ carbon atoms, or a group represented by R ⁴ —X—(CH ₂ ) _m —; an alkyl group or an alkenyl group; X is -O-, -C(O)NR ⁵ -, or -NH-; R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group; m is an integer of 1 to 5; R ³ is an alkyl or alkenyl group having 8 to 21 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or R ⁴ —X—(CH ₂ ) _m — It is a group represented.

The compound represented by formula (A2-1) preferably contains at least one alkyl group or alkenyl group having 8 to 21 carbon atoms in the molecule, more preferably 1 to 2 groups.

The component (A2) is preferably a compound represented by the following formula (A2-2), a compound represented by the formula (A2-3) described below, and more preferably a compound represented by the formula (A2-3). .

In formula (A2-2), R ⁶ is a linear alkyl group having 13 to 21 carbon atoms, a branched alkyl group having 13 to 21 carbon atoms, a linear alkenyl group having 13 to 21 carbon atoms, or a carbon number a 13-21 branched alkenyl group; R ⁷ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms; R ⁸ is a 1 to 4 carbon atom and R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In formula (A2-2), R ⁶ is preferably a linear or branched alkyl group having 13 to 21 carbon atoms. The number of carbon atoms in the alkyl group and the alkenyl group in R ⁶ is 13 to 21, respectively, and is preferably 15 to 21, more preferably 15 to 19, since sebum detergency is enhanced.
The number of hydroxy groups in the hydroxyalkyl group in ^R7 may be one or two or more. Among them, R ⁷ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
The alkylene group for R ⁸ has 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 2 or 3 carbon atoms, and particularly preferably 3 carbon atoms.
The number of carbon atoms in the alkyl groups in R ⁹ and R ¹⁰ is 1 to 4, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. Among them, each of R ⁹ and R ¹⁰ is preferably an alkyl group having 1 to 4 carbon atoms, and preferably the same alkyl group.

Examples of the compound represented by formula (A2-2) include dimethylaminopropylamide myristate, dimethylaminopropylamide palmitate, dimethylaminopropylamide stearate, and dimethylaminopropylamide behenate. Among these, stearic acid dimethylaminopropylamide is preferable from the viewpoint of excellent rinsability.

As the component (A2), a compound represented by the following formula (A2-3) is particularly preferable from the viewpoint of excellent rinsability.
R ¹¹ —N((CH ₂ ) _n NH ₂ ) ₂ (A2-3)
In formula (A2-3), R ¹¹ is a linear alkyl group having 8 to 18 carbon atoms, a branched alkyl group having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or a carbon number 8-18 branched alkenyl groups; n is an integer of 1-4.

Examples of compounds represented by formula (A2-3) include N-(3-aminopropyl)-N-decylpropane-1,3-diamine, N-(3-aminopropyl)-N-dodecylpropane- 1,3-diamine, N-(3-aminoethyl)-N-dodecylpropane-1,3-diamine, N-(3-aminopropyl)-N-tetradecylpropane-1,3-diamine, etc. . Among these, N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine is preferred from the viewpoint of excellent sebum detergency and foamability.

The content of component (A2) is preferably 0.01 to 3.0% by mass, more preferably 0.1 to 0.5% by mass, relative to the total mass of the detergent composition. (A2) When the content of the component is at least the above lower limit, it is easy to improve detergency and foamability. (A2) It is easy to make rinsability favorable as content of a component is below the said upper limit.

The content of component (A2) in component (A) is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, relative to the total mass of component (A). When the content of component (A2) in component (A) is within the above numerical range, the sebum detergency and rinsability are likely to be improved.

The mass ratio represented by component (A1)/component (A2) (hereinafter also referred to as “A1/A2 ratio”) is preferably 8.5-30, more preferably 9.5-21. When the A1/A2 ratio is at least the above lower limit, the rinsability is likely to be improved. When the A1/A2 ratio is equal to or less than the above upper limit value, the sebum detergency and foamability are likely to be improved.

Component (A) includes the components (A1) and (A2) described above, as well as other surfactants such as fatty acid salts (component (A3)), cationic surfactants, nonionic surfactants, and amphoteric surfactants. may contain.

((A3) component)
The (A3) component is a fatty acid salt having 8 to 24 carbon atoms. The (A3) component is a higher fatty acid salt, which is a so-called soap. By containing the component (A3), the cleansing composition has better foaming properties and tends to have better rinsing properties. In addition, the cleansing composition has an A1/A2 ratio of 8.5 to 30 and further contains component (A3), thereby making it easier to improve foamability and rinsability.

Component (A3) includes, for example, saturated or unsaturated fatty acid salts having 8 to 24 carbon atoms such as laurate, myristate and stearate, or a mixture of these, such as coconut oil fatty acid salt and hardened coconut oil. Fatty acid salts, palm oil fatty acid salts, hardened palm oil fatty acid salts, beef tallow fatty acid salts, hardened beef tallow fatty acid salts and the like.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine salts, diethanolamine salts and triethanolamine salts, and ammonium salts.

When the cleaning composition contains component (A3), the content of component (A3) is preferably 0.01 to 3.0% by mass, preferably 0.1 to 3.0% by mass, based on the total mass of the cleaning composition. 1.0% by mass is more preferred. (A3) When the content of the component is at least the above lower limit, it is easy to improve the rinsability. (A3) It is easy to make detergency favorable as content of a component is below the said upper limit.

When the detergent composition contains component (A3), the content of component (A3) in component (A) is preferably 10 to 50% by mass, preferably 20 to 50% by mass, based on the total mass of component (A). 40% by mass is more preferred. When the content of the component (A3) in the component (A) is within the above numerical range, the foamability and rinsability are likely to be improved.

Cationic surfactants include, for example, alkyltrimethylammonium salts, dialkyldimethylammonium salts, benzalkonium salts, benzethonium salts, pyridinium salts, imidazolium salts and the like. Counter ions of these salts include halide ions and the like.

Examples of nonionic surfactants include polyoxyalkylene-type nonionic surfactants obtained by adding alkylene oxide to higher alcohols, alkylphenols, higher fatty acids or higher amines, polyoxyethylene-polyoxypropylene block copolymers, fatty acid alkanolamides, and polyhydric surfactants. alcohol fatty acid esters or alkylene oxide adducts thereof, fatty acid polyglycerol esters, sugar fatty acid esters, alkyl (or alkenyl) amine oxides, amidoamine oxides, alkylene oxide adducts of hydrogenated castor oil, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, Alkyl polyglycosides, glyceryl ethers and the like can be mentioned.

Examples of amphoteric surfactants include alkylcarboxybetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylamidobetaines, imidazoliniumbetaines, and the like.

The content of component (A) is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass, relative to the total mass of the detergent composition. When the content of component (A) is at least the above lower limit, it is easy to improve detergency and foamability. (A) It is easy to make rinsability more favorable as content of a component is below the said upper limit.

<(B) Component>
(B) Component is a chelating agent. The chelating agent used in the present invention exerts excellent detergency against fatty acid metal salts, sebum and protein stains adhering to bathtubs and the like.

Component (B) includes, for example, 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, and glycolic acid, diglycolic acid, lactic acid, and tartaric acid. , carboxymethyltartaric acid, citric acid, malic acid, and gluconic acid.
Aminocarboxylic acids include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionacetic acid, triethylenetetrahexaacetic acid, ethylene glycol dietherdiaminetetraacetic acid, and hydroxyethylimino. diacetic acid, cyclohexane-1,2-diaminetetraacetic acid and the like.
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, aminotrimethylene phosphonic acid and the like.
Phosphonocarboxylic acids include 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid and the like.
Phosphoric acids include condensed phosphoric acids such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, and phytic acid.

Among these, as the component (B), aminocarboxylic acids are preferred, and ethylenediaminetetraacetic acid is more preferred, from the viewpoint of excellent detergency.
Component (B) may be used in the form of an acid or in the form of a salt with a basic substance. Salts with basic substances include salts with alkali metals such as potassium and sodium, and salts with alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.
These (B) components may be used individually by 1 type, and may use 2 or more types together.

The content of component (B) is preferably 0.1 to 5.0% by mass, more preferably 1.5 to 3.5% by mass, relative to the total mass of the detergent composition. When the content of the component (B) is within the above numerical range, it is easy to improve descaling power and foamability.

The mass ratio represented by component (B)/component (A) (hereinafter also referred to as "B/A ratio") is preferably 0.3 to 4.0, more preferably 1.0 to 3.0. . When the B/A ratio is within the above numerical range, it is easy to improve descaling power, foamability and rinsability.

<(C) Component>
Component (C) is a glycol-based solvent. By containing the component (C), the detergent composition tends to have good detergency against scale.
Component (C) is preferably selected from compounds represented by the following formula (I).

R ¹² —O—(C ₂ H ₄ O) _x —(C ₃ H ₆ O) _y —R ¹³ (I)
In formula (I), R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl or alkenyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group. x is a number representing the average number of repeating oxyethylene groups, preferably 0 to 5, more preferably 1 to 3, and even more preferably 1 or 2. y is a number representing the average number of repeating oxypropylene groups, preferably 0 to 5, more preferably 0 to 2. However, x and y cannot be 0 at the same time.

Component (C) includes, for example, ethylene glycol-based solvents such as ethylene glycol, diethylene glycol and triethylene glycol; propylene glycol-based solvents such as propylene glycol, dipropylene glycol, tripropylene glycol and isoprene glycol; ethylene glycol monomethyl ether and ethylene. Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether ethylene glycol-based ethers such as; Propylene glycol ethers such as dipropylene glycol monobutyl ether; dialkyl glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ethyl ether and dipropylene glycol methyl ethyl ether;

As component (C), among the above, diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monopropyl ether, and ethylene glycol monohexyl ether are preferred, and diethylene glycol monobutyl ether is particularly preferred.
These (C) components may be used individually by 1 type, and may use 2 or more types together.

The content of component (C) is preferably 0.1 to 5.0% by mass, more preferably 1.0 to 3.0% by mass, relative to the total mass of the cleaning composition. (C) It is easy to make detergency more favorable as content of a component is more than the said lower limit. (C) It is easy to make rinsing property more favorable as content of a component is below the said upper limit.

<Optional component>
The detergent composition of the present invention may, if necessary, contain components that are usually used in detergent compositions, in addition to the above components (A) to (C). Such optional components include, for example, water, disinfectants, preservatives, antifungal agents, pigments, antioxidants, thickeners, ultraviolet absorbers, solubilizers (excluding component (C)), Perfume, pH adjuster and the like.

From the viewpoint of improving ease of handling and rinsability, the cleaning composition preferably contains water as a solvent.
The content of water is not particularly limited, but is preferably 50 to 99.5% by mass, more preferably 70 to 99% by mass, and even more preferably 75 to 98% by mass, relative to the total mass of the cleaning composition.

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, and the like. Among these, hydrochloric acid, sulfuric acid, sodium hydroxide, and potassium hydroxide are preferred.
One of the pH adjusters may be used alone, or two or more of them may be used in combination.

When the detergent composition contains optional components, the content of the optional components is preferably 50 to 99.5% by mass based on the total mass of the detergent composition.

In addition, the total amount of the components constituting the cleaning composition of the present invention does not exceed 100% by mass.

<<Method for producing detergent composition>>
The cleaning composition is manufactured by a conventionally known manufacturing method. For example, a method of adding the above components (A) to (C) to water as a solvent, adding optional components as necessary, and mixing them.

The pH of the detergent composition at 25° C. is preferably 9 or higher, more preferably 9 to 12, even more preferably 9.5 to 12, and particularly preferably 10 to 11. When the pH is within the above numerical range, it is easy to improve descaling power and foamability.
The pH can be adjusted by adding an appropriate amount of pH adjuster.
The pH used herein is a value measured with a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) at 25°C.

The viscosity of the detergent composition at 25° C. is preferably 1 to 100 mPa·s, more preferably 1 to 50 mPa·s. When the viscosity at 25°C is at least the above lower limit, the adhesion of the cleaning composition to objects to be cleaned, such as a bathtub, is further improved. When the viscosity at 25°C is equal to or less than the above upper limit, the cleaning composition can be easily discharged from a discharge container such as a spray container, resulting in good handleability.
The viscosity of the cleaning composition can be adjusted by adjusting the water content, addition of a thickener, and the like.
Viscosity in the present specification is measured at 25° C. using a Brookfield viscometer, rotor No. 1. A value measured 60 seconds after the start of rotation of the rotor at a rotor speed of 60 rpm.

<<How to use the cleaning composition>>
As a method of using the detergent composition, for example, a cleaning tool such as a sponge is impregnated with the detergent composition, and the walls of the bathroom, the surface of the bathtub, and other bathroom accessories to be cleaned are scrubbed with the sponge. How to use, the cleaning composition is stored in a discharge container, an appropriate amount of the cleaning composition is applied from this discharge container to the above-mentioned object to be cleaned, and after a certain period of time has passed, it is rinsed with a shower, etc., and "washing without rubbing" is performed. and how to use it.

A spray container, a squeeze container, etc. are mentioned as a discharge container which accommodates a cleaning agent composition. Among them, a spray container is preferable as the discharge container for containing the cleaning composition because of its excellent applicability to the object to be cleaned.
Spray containers include aerosol spray containers, trigger spray containers (direct pressure type or pressure accumulation type), dispenser spray containers, 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. These propellants may be used alone or in combination of two or more.
Examples of trigger spray containers 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 pressure accumulation type trigger spray container is preferable because it has good spray property and spray pattern, and good coatability can be obtained.

The detergent composition of the present invention has a high detergency against fatty acid metal salts, sebum stains, and protein stains adhering to the bathtub, and has good foamability and rinsability, so it is used for scrubbing. is preferred.
In addition, when the detergent composition is excellent in rinsability, it may be applied to the entire surface of the bathtub, and after a certain period of time has passed, it may be rinsed in a shower or the like for "washing without rubbing". .

[EXAMPLES] Hereafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. Unless otherwise specified, "%" in the examples indicates pure "% by mass". Tables 1 to 3 show the composition of the bathroom cleaner composition of each example. The raw materials used in this example are as follows.
Each code|symbol in a table|surface shows the following.

≪Raw materials used≫
<(A) Component>
((A1) component)
A1-1: Sodium C14-α olefin sulfonate (AOS), manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Lipolan (registered trademark) LJ441”. The above "C14" means that the number of carbon atoms is 14, and the same applies hereinafter.
A1-2: Linear alkyl (C12-14) sodium benzenesulfonate (LAS), manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Lipon (registered trademark) PS-230”.
A1-3: Polyoxyethylene (2) sodium lauryl sulfate (AES). Manufactured by Shin Nippon Chemical Co., Ltd., trade name “Shinoline (registered trademark) SPE-1250”. Polyoxyethylene (2) means that the number of added moles of oxyethylene groups is "2".
A1-4: Lauryl sulfate (SDS), manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Sunnol (registered trademark) LM-1130".

((A2) component)
A2-1: N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine, manufactured by Lonza, trade name “Lonzabac 12.30” (formula (A2-3), where R ¹¹ has 12 carbon atoms and a straight-chain alkyl group of n is 3).
A2-2: Stearyldimethylaminopropylamide, manufactured by Toho Chemical Industry Co., Ltd., trade name “Catinal (registered trademark) MPAS” (formula (A2-2), where R ⁶ is a linear alkyl group having 17 carbon atoms, R ⁷ is a hydrogen atom, R8 is an alkylene group having ³ carbon atoms, and both ^R9 and ^R10 are methyl groups).
A2-3: n-dodecylamine, reagent "deer special grade" manufactured by Kanto Chemical Co., Ltd. (a compound of formula (A2-1) in which both R ¹ and R ² are hydrogen atoms and R ³ is an alkyl group having 12 carbon atoms ).
((A2′) component (comparative product of (A2) component))
A2′-1: Lauramidopropyl betaine (LPB), manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Enagicol (registered trademark) L-30B”.
A2′-2: n-dodecyldimethylamine oxide (AX), manufactured by Lion Specialty Chemicals Co., Ltd., trade name “AX-CS”.

((A3) component)
A3-1: 30% potassium coconut oil fatty acid aqueous solution (coconut fatty acid K), manufactured by Lion Specialty Chemicals Co., Ltd.

<(B) Component>
B-1: Disodium ethylenediaminetetraacetate (EDTA), manufactured by Akzo Nobel Co., Ltd., trade name "Disolvin (registered trademark) NA2".
B-2: Dihydroxyethylglycine (DHEG), manufactured by Cherest Co., Ltd., trade name "DHEG".

<(C) Component>
C-1: Butyl diglycol, manufactured by Nippon Nyukazai Co., Ltd. (Compound of formula (I) in which R ¹² is a hydrogen atom, R ¹³ is an alkyl group having 4 carbon atoms, x is 2, and y is 0).

<Optional component>
pH adjuster: 1N sodium hydroxide, 1N hydrochloric acid, manufactured by Kanto Kagaku Co., Ltd.
Water: deionized water.

[Examples 1 to 19, Comparative Examples 1 to 5]
≪Production of detergent composition≫
According to the formulations in Tables 1 to 3, after dissolving the (A2) component in the (C) component, the remaining (A) component, water, and (B) component are mixed, an appropriate amount of pH adjuster is added, and the pH is displayed. was adjusted to a value in the middle to obtain a detergent composition of each example.
In the table, the unit of "composition" is "% by mass" and indicates the amount in terms of pure content. In the table, "-" indicates that the component is not included. In the table, the water content "balance" indicates the amount required to bring the total weight of the cleaning composition to 100% by weight. In the table, the content "appropriate amount" of the pH adjuster indicates the amount required to adjust the pH of the detergent composition to the value shown in the table. In the table, "A total amount" indicates the content of component (A). In the table, "AB total amount" indicates the total content of the components (A) and (B). Examples 4, 5, 7, 8 and 11 are reference examples.

<<Evaluation method for detergent composition>>
The cleansing composition of each example was evaluated for detergency against scale, detergency against sebum, foamability, and rinsability as follows.

<Evaluation of scale detergency>
After fixing a glass fiber reinforced plastic (FRP) test piece (2 cm x 10 cm) to the inner wall surface of a bathtub in a general household, three adult males each bathed three times (one bath a day for three days, During this time, only the bath water was replaced, and the bathtub was used without being washed), and the test piece was stained.
After thoroughly drying the soiled test piece, the detergent composition of each example was dripped onto the test piece so that the entire surface of the test piece was wet, left to stand for 30 seconds, and then treated with tap water (15°C). rinsed off. The test pieces were sufficiently dried, and the state of removal of stains from the surface of the five test pieces was evaluated by visual inspection and finger touch according to the following evaluation criteria. In the following evaluation criteria, ⊚ and ◯ were regarded as acceptable. The results are shown in Tables 1-3.
"Evaluation criteria"
⊚: Stain removal is very good [out of five test pieces, no stains are visually observed on all five test pieces, and the entire surface of the five test pieces is 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. At least one test piece feels rough to the touch].
△: Stain hardly removed [Out of the 5 test pieces, 5 were visually observed to be soiled, and all 5 were felt to be rough to the touch. less than before washing].
×: No dirt removed [out of 5 test pieces, 5 were visually observed to be dirty, all 5 were rough to the touch, and the visual dirt and rough touch were not washed off. same as before].

<Evaluation of sebum detergency>
30 g of beef tallow (manufactured by Kanto Chemical Co., Ltd.), 20 g of soybean oil (manufactured by Kanto Chemical Co., Ltd.), and 0.05 g of Sudan IV (manufactured by Kanto Chemical Co., Ltd.) were mixed with 50 mL of chloroform (manufactured by Kanto Chemical Co., Ltd., special grade) for contamination. A sap was prepared. 50 mL of this dirt solution was placed in a glass bottle, and a 1×5 cm slide glass (manufactured by MATSUNAMI Co., Ltd.) was immersed and pulled out.
A 100 mL glass bottle was filled with 50 mL of the cleaning composition of each example, and the stain plate was immersed in this cleaning composition for 3 minutes. After that, the soiled plate was taken out, and the state of removal of the soil was visually observed and evaluated according to the following evaluation criteria. In the following evaluation criteria, if it is 0 or higher, the practical detergency of epithelial sebum is good. That is, in the following evaluation criteria, ⊚ and ∘ were regarded as acceptable. The results are shown in Tables 1-3.
"Evaluation criteria"
(double-circle): Stain removal is very good.
◯: Stain removal is good.
Δ: Stain removal is uneven.
x: Stain hardly comes off.

<Evaluation of foamability>
The cleaning agent composition of each example was filled in a trigger container of a commercially available bathroom detergent “Ofuro no Look” and sprayed 10 times at equal intervals in an FRP bathtub (100 x 75 x 65 cm). Then, using a urethane sponge, the entire inner surface of the bathtub was rubbed in a circular motion while applying a load of about 10 g/cm ² . The state of foam at that time was visually observed and evaluated according to the following evaluation criteria. In the following evaluation criteria, ⊚ and ◯ were regarded as acceptable. The results are shown in Tables 1-3.
"Evaluation criteria"
A: Foaming is very good.
◯: Good foaming.
Δ: Foaming is uneven.
x: Slightly foaming degree.

<Evaluation of rinsability>
After the evaluation of foamability, rinse with tap water using a shower (water temperature 15 ° C., flow rate 0.2 L / sec), measure the time until foam completely disappears from the drain port of the bathtub, and evaluate according to the following evaluation criteria. The rinsability of the detergent composition of each example was evaluated according to the following. In the following evaluation criteria, ⊚, ∘ and Δ were regarded as acceptable. The results are shown in Tables 1-3.
"Evaluation criteria"
A: Less than 20 seconds.
○: 20 seconds or more and less than 23 seconds.
Δ: 23 seconds or more and less than 30 seconds.
×: 30 seconds or more.

As shown in Tables 1 to 3, Examples 1 to 19 to which the present invention was applied passed all of the evaluation of detergency of scale, evaluation of sebum detergency, evaluation of foamability, and evaluation of rinsability.
On the other hand, Comparative Example 1, which did not contain the component (A1), was evaluated as "Poor" in the evaluation of detergency and foamability. Comparative Example 2, which does not contain the component (B), was evaluated as "x" for detergency of scale. Comparative Example 3, which did not contain the component (A2), was evaluated as "×" for sebum detergency and "Δ" for foamability. In Comparative Examples 4 and 5, in which the (A2) component was used as a comparative product, the evaluation of sebum detergency was "x".

From these results, it was confirmed that the cleansing composition to which the present invention is applied is superior in detergency against scale and sebum, and can improve foamability and rinsability.

Claims (6)

(A) component: a surfactant containing the following (A1) component and the following (A2) component;
(B) component: a chelating agent;
(C) component: a glycol-based solvent;
contains a
The content of the following (A1) component is 0.1 to 2.5% by mass with respect to the total mass,
A bathroom cleaning composition , wherein the mass ratio represented by component (A1) below/component (A2) below is from 9.5 to 21 .
Component (A1): A non-soap anionic surfactant containing one or more selected from alkylbenzenesulfonates and α-olefinsulfonates .
(A2) component: an amine-type surfactant represented by the following formula (A2-1).

[In the formula (A2-1), R ¹ , R ² and R ³ are substituents on N, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, , an aminoalkyl group having 1 to 4 carbon atoms, an alkyl group having 8 to 21 carbon atoms, or an alkenyl group having 8 to 21 carbon atoms; R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or a group represented by R ⁴ —X—(CH ₂ ) _m —; R ⁴ is a branched chain having 8 to 21 carbon atoms; X is —O—, —C(O)NR ⁵ —, or —NH—; R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group Yes; m is an integer of 1 to 5; R ³ is an alkyl or alkenyl group having 8 to 21 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or R ⁴ —X—(CH ₂ ) _m — is a group represented by ] The bathroom cleaning composition according to claim 1, wherein the component (A) further contains the following component (A3).
(A3) Component: Fatty acid salt having 8 to 24 carbon atoms. 3. The bathroom cleaning composition according to claim 1, wherein the content of component (A) is 0.5 to 5% by mass relative to the total mass. The bathroom cleaning composition according to any one of claims 1 to 3 , wherein the component (A2) is an amine surfactant represented by the following formula (A2-3).
R ¹¹ —N((CH ₂ ) _n NH ₂ ) ₂ (A2-3) [In the formula (A2-3), R ¹¹ is a linear alkyl group having 8 to 18 carbon atoms, 18 branched chain alkyl groups, straight chain alkenyl groups having 8 to 18 carbon atoms, or branched chain alkenyl groups having 8 to 18 carbon atoms; ] The bathroom cleaning composition according to any one of claims 1 to 4 , wherein the mass ratio represented by component (B)/component (A) is 0.3 to 4.0. The bathroom cleaning composition according to any one of claims 1 to 5 , which has a pH of 9 or higher at 25°C.