JP2024026937A - Liquid cleaning composition for hard surfaces - Google Patents

Abstract

The present invention provides a liquid cleaning composition for hard surfaces that can improve the workability of cleaning work, suppress the formation of complex stains, and increase the cleaning power for sebum stains. [Solution] Component (A): an anionic surfactant containing at least one selected from α-olefin sulfonic acid or its salt, linear alkylbenzenesulfonic acid or its salt, and secondary alkanesulfonic acid or its salt; , component (B): a copolymer containing a monomer unit having a quaternary ammonium group, component (C): a nonionic surfactant, and the content of component (A) is a liquid cleaning agent for hard surfaces. The content of component (B) is from 0.01 to 5.0% by mass based on the total mass of the liquid cleaning composition for hard surfaces. 2.0% by mass, and the content of component (C) is 0.1 to 5.0% by mass based on the total mass of the liquid cleaning composition for hard surfaces. [Selection diagram] None

Description

The present invention relates to liquid cleaning compositions for hard surfaces.

In the bathroom, hard components such as calcium and magnesium in tap water and soap components from shampoo and body soap accumulate on the surfaces of mirrors, faucets, bathtubs, and other components, forming limescale and mixed stains of soap components. .
For example, when composite dirt accumulates on a mirror, visibility deteriorates because the dirt causes fogging or the mirror becomes foggy due to steam.
It is not easy to remove limescale formed on parts. For this reason, it is desirable to prevent the formation of strong scales by simple daily care without leaving any water on the surface of the object to be cleaned.

In response to these demands, Patent Document 1 proposes a wettability imparting agent containing a water-soluble nitrogen-containing polymer and a surfactant. According to the invention of Patent Document 1, wettability is imparted to an object to be cleaned such as a bathtub, thereby reducing water spots.
Further, Patent Document 2 proposes a liquid cleaning composition for hard surfaces containing specific amounts of a specific polymer, an anionic surfactant, and a cationic surfactant. According to the invention of Patent Document 2, a quick drying effect is provided and water droplets are prevented from remaining on the surface of the object to be cleaned.

Japanese Patent Application Publication No. 2014-214182 Japanese Patent Application Publication No. 2007-308555

After taking a bath, sebum stains and the like adhere to the bathtub. Although sebum stains adhering to members such as bathtubs can be removed by applying mechanical force with a sponge or the like, there is a desire to clean them without applying mechanical force. Cleaning without applying mechanical force requires superior cleaning power. In addition, when cleaning without applying mechanical force, when the liquid cleaning composition is sprayed onto the object to be cleaned, it becomes a mist and spreads and adheres, reducing the burden of cleaning work. There is a need to reduce this (improve workability).
Therefore, the object of the present invention is to provide a liquid cleaning composition for hard surfaces that can improve the workability of cleaning operations, suppress the formation of complex stains, and increase the cleaning power for sebum stains.

The present inventor has discovered that by combining a specific copolymer, a specific non-soap anionic surfactant, and a nonionic surfactant, it is possible to suppress the formation of complex stains and increase the detergency of sebum stains. This discovery led to the completion of the present invention.

The present invention has the following aspects.
<1>
(A) Component: an anionic surfactant containing at least one selected from α-olefin sulfonic acid or its salt, linear alkylbenzenesulfonic acid or its salt, secondary alkanesulfonic acid or its salt,
Component (B): a copolymer containing a repeating unit (b1) derived from a monomer having a quaternary ammonium group,
(C) Component: Contains a nonionic surfactant,
The content of the component (A) is 0.1 to 5.0% by mass based on the total mass of the liquid cleaning composition for hard surfaces,
The content of the component (B) is 0.01 to 2.0% by mass based on the total mass of the liquid cleaning composition for hard surfaces,
A liquid cleaning composition for hard surfaces, wherein the content of component (C) is 0.1 to 5.0% by mass based on the total mass of the liquid cleaning composition for hard surfaces.
<2>
The liquid cleaning composition for hard surfaces according to <1>, wherein the mass ratio represented by the component (A)/component (B) is 0.1 to 24.
<3>
The liquid cleaning for hard surfaces according to <1> or <2>, wherein the mass ratio represented by (the (A) component + the (B) component)/the (C) component is 0.1 to 24. agent composition.
<4>
The component (B) has the repeating unit (b1) and the repeating unit (b2),
The repeating unit (b1) is at least one type selected from a repeating unit (b1-1) derived from a dimethyldiallylammonium salt and a repeating unit (b1-2) derived from a methacrylamide propyl trialkylammonium salt. ,
The repeating unit (b2) includes a repeating unit (b2-1) derived from acrylic acid, a repeating unit (b2-2) derived from acrylamide, and a repeating unit (b2-3) derived from methyl acrylate. ), and the liquid cleaning composition for hard surfaces according to any one of <1> to <3>.
<5>
The liquid cleaning composition for hard surfaces according to any one of <1> to <4>, wherein the weight average molecular weight of the component (B) is 10,000 to 2,000,000.
<6>
The liquid cleaning composition for hard surfaces according to any one of <1> to <5>, which is for bathroom use.

According to the liquid detergent composition for tableware of the present invention, the workability of cleaning work can be improved, the formation of complex stains can be suppressed, and the detergency against sebum stains can be improved.

(Liquid cleaning composition for hard surfaces)
The liquid cleaning composition for hard surfaces of the present invention (hereinafter sometimes simply referred to as "liquid cleaning composition") contains components (A) to (C).

<(A) component>
Component (A) is an anionic surfactant containing at least one selected from α-olefin sulfonic acid or its salt, linear alkylbenzenesulfonic acid or its salt, and secondary alkanesulfonic acid or its salt. By containing the component (A), the liquid detergent composition can increase its detergency against sebum stains.

Examples of the α-olefin sulfonic acid (AOS) include AOS having 14 to 16 carbon atoms. Examples of AOS salts include sodium salts.

Examples of the secondary alkanesulfonic acid (SAS) include SAS having 14 to 17 carbon atoms. Examples of SAS salts include sodium salts.

Examples of the linear alkylbenzenesulfonic acid (LAS) include LAS having an alkyl group having 10 to 14 carbon atoms. Examples of LAS salts include sodium salts, potassium salts, and the like.

Among them, AOS is preferable as component (A) because it can be sprayed over a wider area when the liquid cleaning composition is sprayed (excellent sprayability) and has an excellent cleaning effect on sebum stains.
These (A) components may be used alone or in combination of two or more.

The content of component (A) is 0.1 to 5% by weight, preferably 0.1 to 2% by weight, and more preferably 0.5 to 1% by weight, based on the total weight of the liquid cleaning composition. When the content of component (A) is at least the above lower limit, the detergency against sebum stains can be further enhanced and the formation of composite stains can be better suppressed. When the content of component (A) is below the above upper limit, sprayability is improved and workability is further improved.

<(B) component>
Component (B) is a copolymer containing a repeating unit (b1) derived from a monomer having a quaternary ammonium group. By containing the component (B), the liquid cleaning composition of the present invention can suppress the formation of complex stains.

Examples of the repeating unit (b1) include a repeating unit (b1-1) derived from a dimethyldiallylammonium salt and a repeating unit (b1-2) derived from a methacrylamide propyl trialkylammonium salt. Examples of monomer salts include chlorides.
The repeating unit (b1) is preferably at least one type selected from repeating units (b1-1) and repeating units (b1-2).

In component (B), the repeating unit (b1) is preferably 20 to 65 mol%, more preferably 20 to 45 mol%, based on the total number of moles of repeating units constituting component (B). When the mole fraction of the repeating unit (b1) is within the above range, sprayability can be improved and workability can be further improved.

Component (B) has a repeating unit (arbitrary repeating unit) other than repeating unit (b1).
As the optional repeating unit, repeating unit (b2) is preferred. That is, as component (B), a copolymer having a repeating unit (b1) and a repeating unit (b2) (sometimes referred to as "b1b2 polymer") is preferable. By using the b1b2 polymer as the component (B), complex stains can be better suppressed.

The repeating unit (b2) is a repeating unit derived from acrylic acid (b2-1), a repeating unit derived from acrylamide (b2-2), and a repeating unit derived from methyl acrylate (b2-3). At least one type is selected. Among these, copolymers containing repeating units (b2-2) are preferred as b1b2 polymers.
These repeating units (b2) may be used alone or in combination of two or more.

When component (B) is a b1b2 polymer, the molar ratio of the repeating unit (b2) to the repeating unit (b1) (b2/b1 ratio) is preferably more than 0 and 4 or less, more preferably 0.5 to 4, and 1 ~3.5 is more preferred. When the b2/b1 ratio is equal to or higher than the above lower limit, sprayability can be improved and workability can be further improved. When the b2/b1 ratio is less than or equal to the above upper limit, complex stains can be better suppressed.

When the b1b2 polymer contains a repeating unit (b2-1), the molar ratio of the repeating unit (b2-1) to the repeating unit (b1) (b2-1/b1 ratio) is preferably more than 0 and 1.5 or less, and 0 More preferably, it is more than 1.1 or less. When the b2-1/b1 ratio is equal to or higher than the above lower limit, sprayability can be improved and workability can be further improved. When the b2-1/b1 ratio is below the above upper limit, complex stains can be better suppressed.

When the b1b2 polymer contains a repeating unit (b2-2), the molar ratio of the repeating unit (b2-2) to the repeating unit (b1) (b2-2/b1 ratio) is preferably more than 0 and less than or equal to 4, and more than 0 and less than 3. .5 or less is more preferable. When the b2-2/b1 ratio is equal to or higher than the above lower limit, sprayability can be improved and workability can be further improved. When the b2-2/b1 ratio is less than or equal to the above upper limit, complex stains can be better suppressed.

When the b1b2 polymer contains a repeating unit (b2-3), the molar ratio of the repeating unit (b2-3) to the repeating unit (b1) (b2-3/b1 ratio) is preferably more than 0 and 0.5 or less, and 0 More preferably, it is more than 0.3. When the b2-3/b1 ratio is equal to or higher than the above lower limit, sprayability can be improved and workability can be further improved. When the b2-3/b1 ratio is below the above upper limit, complex stains can be better suppressed.

Among them, the b1b2 polymer has a b2-1/b1 ratio of 0 (that is, does not contain the repeating unit (b2-1)) to 1.5, a b2-2/b1 ratio of 1 to 4, and b2-3/b1. Copolymers with a ratio of 0 (ie not containing repeating units (b2-3)) to 0.5 are preferred.

In the b1b2 polymer, the total of repeating units (b1) and repeating units (b2) is preferably 100 mol%.

Examples of the component (B) include diallyldimethylammonium/acrylamide copolymer (b2-2/b1 ratio = 2 to 3.5).

The weight average molecular weight of component (B) is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, and even more preferably 100,000 to 1,000,000. When the weight average molecular weight of the component (B) is at least the above lower limit, the viscosity of the liquid cleaning composition can be increased and the residence time on the object to be cleaned can be made longer. When the weight average molecular weight of component (B) is below the above upper limit, the viscosity of the liquid cleaning composition can be lowered and the sprayability can be further improved.
The weight average molecular weight of the component (B) is, for example, a value measured by the SEC-MALLS-RI system (measurement conditions: column = Tosoh Corporation TSK gel α series α-M column 30 cm, solvent = 0.3M aqueous sodium nitrate solution). It is.

The content of component (B) is 0.01 to 2% by mass, preferably 0.01 to 1% by mass, and 0.01 to 0.5% by mass based on the total mass of the liquid cleaning composition. is more preferable. When the content of component (B) is at least the above lower limit, the formation of complex stains can be further suppressed and the detergency against sebum stains can be further enhanced. When the content of component (B) is below the above upper limit, sprayability can be further improved and detergency against sebum stains can be further improved.

In the liquid cleaning composition, the mass ratio of component (A) to component (B), expressed as component (A)/component (B) (A/B ratio), is 0.1 to 24. is preferable, 0.5 to 14 is more preferable, and 1 to 9 is even more preferable. When the A/B ratio is equal to or higher than the above lower limit, the detergency against sebum stains can be further enhanced. When the A/B ratio is below the above upper limit, the detergency against sebum stains can be further enhanced and the formation of composite stains can be further suppressed.

<(C) component>
Component (C) is a nonionic surfactant. By containing component (C), the liquid cleaning composition can improve sprayability.

Component (C) includes a polyoxyalkylene type nonionic surfactant, an alkyl polyglycoside having an alkyl group having 8 to 18 carbon atoms, a sucrose fatty acid ester having a fatty acid group having 8 to 18 carbon atoms, and a sucrose fatty acid ester having a fatty acid group having 8 to 18 carbon atoms. Examples include alkyl polyglyceryl ethers having an alkyl group. Among these, polyoxyalkylene type nonionic surfactants are preferred from the viewpoint of further improving sprayability.

Examples of the polyoxyalkylene type nonionic surfactant include a surfactant represented by the following formula (c).

R ¹ -X-[(EO) _s /(PO) _t ] ^-R2 ...(c)

(In formula (c), R ¹ represents a hydrocarbon group having 8 to 18 carbon atoms, X represents O, COO, or CONH, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number Represents an alkenyl group of 2 to 6. s represents the average repeating number of EO and is a number of 6 to 20. t represents the average repeating number of PO and is a number of 0 to 6. EO is an oxyethylene group , PO represents an oxypropylene group, and EO and PO may be arranged in a mixed manner.)

R ¹ is preferably an alkyl group. R ¹ may be linear or branched.
The number of carbon atoms in R ¹ is preferably 10 to 16, more preferably 12 to 14.

R ² is preferably hydrogen or an alkyl group, and more preferably hydrogen. When R ² is a hydrocarbon group, R ² may be a straight chain or a branched chain.
The number of carbon atoms in R ² is preferably 1 to 3, more preferably 1 (ie, methyl group).

s is preferably 4 to 20, more preferably 6 to 15.
t is preferably 0 to 5, more preferably 0.

X is preferably O or COO, and more preferably O.

Examples of polyoxyalkylene type nonionic surfactants include alcohols in which R ¹ is a linear alkyl group having 12 to 14 carbon atoms, R ² is hydrogen, s is 6 to 15, and t is 0; Ethoxylates are preferred.

The content of component (C) is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and further preferably 0.1 to 2% by mass based on the total mass of the liquid cleaning composition. preferable. When the content of component (C) is at least the above lower limit, sprayability can be further improved and formation of composite stains can be further suppressed. When the content of component (C) is below the above upper limit, sprayability can be further improved.

The total mass of components (A), (B), and (C) is preferably 0.21 to 12% by mass, and 0.21 to 6% by mass based on the total mass of the liquid cleaning composition. It is more preferably 0.61 to 3.5% by mass. When the total mass of component (A), component (B), and component (C) is at least the above lower limit, the detergency can be further enhanced. When the total mass of component (A), component (B), and component (C) is less than or equal to the above upper limit, the viscosity of the liquid cleaning composition can be reduced and the sprayability can be further improved.

It is the mass of the total amount of component (A) and component (B) with respect to component (C), and the mass ratio ((A+B)/ C ratio) is preferably from 0.1 to 24, more preferably from 0.3 to 5.1, even more preferably from 0.5 to 1.6. When the (A+B)/C ratio is at least the above lower limit, the formation of composite stains can be further suppressed and the detergency against sebum stains can be further enhanced. When the (A+B)/C ratio is below the above upper limit, sprayability can be further improved.

<Optional ingredients>
The liquid cleaning composition may contain optional components other than components (A) to (C) within a range that does not impair the effects of the present invention.
The optional component may be a component used in a liquid cleaning composition for hard surfaces. Optional ingredients include water, surfactants other than components (A) and (C) (optional surfactants), chelating agents, hydrotropes, preservatives, pH adjusters, fragrances, pigments, thickeners, etc. can be mentioned.

Water functions as a solvent for liquid cleaning compositions. The content of water is preferably 75 to 98% by mass based on the total mass of the liquid cleaning composition.

Examples of the optional surfactant include anionic surfactants other than component (A), cationic surfactants, amphoteric surfactants, semipolar surfactants, and the like.
Examples of anionic surfactants other than component (A) include soaps (fatty acid salts having 8 to 12 carbon atoms) and non-soap anionic surfactants other than component (A).
The total mass of the surfactant containing component (A) and component (C) (total surfactant amount) is preferably 0.5 to 6.5% by mass based on the total mass of the liquid cleaning composition.

Examples of the chelating agent include aminocarboxylic acid type chelating agents, organic acids or salts thereof, and the like.
Examples of the aminocarboxylic acid type chelating agent include ethylenediaminetetraacetic acid and its salts, methylglycine diacetic acid and its salts, and the like.
Examples of organic acids or salts thereof include glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, gluconic acid, and salts thereof.
The content of the chelating agent is preferably 0.1 to 5% by mass based on the total mass of the liquid cleaning composition.

Examples of the hydrotrope include orthotoluenesulfonic acid, metatoluenesulfonic acid, paratoluenesulfonic acid, or salts thereof, cumene sulfonic acid, cumene sulfonate, ethanol, butyl carbitol, and the like.
The content of the hydrotrope is preferably 0 to 1% by mass based on the total mass of the liquid cleaning composition.

Examples of preservatives include isothiazoline compounds, specifically benzisothiazolinone (1,2-benzisothiazolin-3-one) and methylisothiazolinone (2-methyl-4-isothiazolin-3-one). ), butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, and the like.
Examples of the pH adjuster include inorganic alkaline agents, organic alkaline agents, and inorganic acids.
Examples of inorganic alkali agents include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.
Examples of organic alkali agents include monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N-(β-aminoethyl)ethanolamine, diethylenetriamine, morpholine, N- Examples include amine compounds such as ethylmorpholine.
Examples of inorganic acids include hydrochloric acid and sulfuric acid.
Examples of organic acids include acetic acid and the like.

<Physical properties>
The pH at 25° C. of the liquid cleaning composition of the present invention is preferably 6 to 12, more preferably 7 to 12, and even more preferably 10 to 12.
The pH (25°C) of the liquid cleaning composition is a value measured by a method based on JIS Z 8802:1984 "pH measurement method".

The viscosity of the liquid detergent composition of the present invention at 25° C. is preferably 0.1 to 10 mPa·s. When the viscosity is at least the above lower limit, when sprayed onto the object to be cleaned, the residence time of the liquid detergent composition on the object to be cleaned is lengthened, and the cleaning power can be further enhanced. When the viscosity is below the above upper limit, sprayability can be further improved.

The viscosity of the liquid cleaning composition can be adjusted by adjusting the water content, the total surfactant content, the content of component (B), and the like.
The viscosity of the liquid cleaning composition was measured using a B-type viscometer with the object to be measured at 25°C, and the viscosity was measured using rotor No. 1. This value is measured 60 seconds after the rotor starts rotating at a rotor rotation speed of 60 rpm.

(Production method)
The liquid cleaning composition of the present invention is manufactured by a conventionally known manufacturing method.
A method for producing a liquid cleaning composition includes, for example, adding components (A) to (C) and optional components as necessary to a portion of water, mixing, adjusting the pH, and then adding the remainder of the water. There are several methods.

The obtained liquid cleaning composition may be filled into a container to form a container-filled article. Examples of containers include trigger spray containers, squeeze containers, and the like, with trigger spray containers being preferred.

(how to use)
Examples of how to use the liquid cleaning composition include applying the liquid cleaning composition to the object to be cleaned, leaving it for an arbitrary period of time (for example, 10 seconds to 10 minutes), and then rinsing it off with water. .
Another method includes applying a liquid detergent composition to an object to be cleaned and rubbing it with a cleaning tool such as a sponge.

Examples of objects to be cleaned include bathroom components and accessories such as the bathroom floor, walls, ceiling, bathtub, mirror, chair, and bucket. Examples of objects to be cleaned include a bathroom mirror, floor, washstand, and the like.
Examples of the material of the object to be cleaned include plastic, fiber-reinforced plastic, glass, ceramics, and metal.

(effect)
By containing a specific amount of component (A), the liquid detergent composition of the present invention can increase its detergency against sebum stains.
The liquid cleaning composition of the present invention can suppress the formation of complex stains by containing a specific amount of component (B).
By containing a specific amount of component (C), the liquid cleaning composition of the present invention improves sprayability, allows the components (A) and (B) to be applied over a wide range, and improves the workability of cleaning work. It will be done.
The liquid cleaning composition of the present invention is particularly suitable for use in bathrooms.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the following description.

(Raw materials used)
<(A) component>
- A-1: AOS, sodium α-olefin sulfonate having 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Liporan LJ441").
- A-2: LAS, linear (C10-16) sodium alkylbenzene sulfonate, (manufactured by Lion Corporation, trade name "Lipon LH-200CJ").
- A-3: SAS, sodium secondary alkanesulfonate having 14 to 17 carbon atoms, "HOSTAPUR (registered trademark) SAS30A" manufactured by Clariant Japan Co., Ltd.

<(A') component> Comparison product of component (A)・A'-1: SDS, lauryl sulfate, manufactured by Lion Corporation, product name "Sunol LM-1130".

<(B) component>
・B-1: Dimethyldiallylammonium/acrylamide copolymer, weight average molecular weight 120,000, contains repeating unit (b1-1) and repeating unit (b2-2), b2-2/b1 ratio = 3.2 (Lubrizol company, product name ``Marquat 740'').
・B-2: Methacrylamide propyltrimethylammonium acrylic acid methyl acrylate copolymer), weight average molecular weight 1.3 million, repeating unit (b1-2), repeating unit (b2-1), repeating unit (b2-3) b2-1/b1 ratio = 1, b2-3/b1 ratio = 0.2 (manufactured by Lubrizol, trade name "Marquat 2001").
・B-3: Dimethyldiallylammonium/acrylic acid/acrylamide copolymer, weight average molecular weight 1.5 million, containing repeating unit (b1-1), repeating unit (b2-1), and repeating unit (b2-2) b2-1 /b1 ratio = 1.1, b2-2/b1 ratio = 1.1 (manufactured by Lubrizol, trade name "Marquat 3330PR").

<Component (B')> Comparison product of component (B) - B'-1: CC, cationized cellulose (manufactured by Dow Chemical Company, trade name "Supracare 212").
- B'-2: DADMAC, diallyldimethylammonium chloride (manufactured by Lubrizol, trade name "Marquat 100").

<(C) component>
- C-1: C1214 (15EO), polyoxyethylene alkyl (C12-14, long chain 100%) ether (average number of added moles of ethylene oxide 15) (manufactured by Lion Corporation, product name "LMAO-90"). Note that "C" in "C12-14" means the number of carbon atoms in an alkyl group (hydrocarbon group) (the same applies hereinafter).
- C-2: C13 (7EO), polyoxyethylene alkyl (C13, 100% branched) ether (average number of added moles of ethylene oxide 7) (manufactured by BASF, trade name "Lutensol TO7").

<Optional ingredients>
・Water: Ion exchange water.
- Coconut oil fatty acid K: Coconut oil fatty acid potassium (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Coconut oil fatty acid potassium", soap-based anionic surfactant).
- Potassium myristate: Potassium myristate (manufactured by NOF Corporation, trade 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 Akzo Nobel Co., Ltd., trade name "Disolvin Z", chelating agent).
- pH adjuster: 1N sodium hydroxide (manufactured by Kanto Chemical Industry Co., Ltd.).

(Evaluation method)
<Evaluation of compound stain suppression effect>
A commercially available Look Plus Bathtub Cleansing trigger spray container was filled with the liquid cleaning composition of each example. The liquid cleaning composition of each example was sprayed onto the surface of a 50 cm x 50 cm mirror and left in a vertical position for 1 minute. Thereafter, a 15° C. soap solution was discharged from the washing bottle and the surface of the mirror was rinsed for 10 seconds. As the soap liquid, a 1% by mass aqueous solution of Hadkara (manufactured by Lion Corporation) was used.
The mirror surface after rinsing was visually observed, and the composite stain suppression effect was evaluated based on the following evaluation criteria. The above evaluation test was conducted three times, and the average score was determined. If the average score was 3 or more points, it was evaluated that the compound stain suppression effect was high.
Note that the blanks are those in which the above evaluation test was conducted using tap water instead of the liquid cleaning composition of each example.

≪Evaluation criteria≫
5 points: Complex stains were reduced by 70% or more compared to the blank.
4 points: Complex stains were reduced by 50 to 60% compared to the blank.
3 points: Complex stains were reduced by 30 to 40% compared to the blank.
2 points: Complex stains were reduced by 10 to 20% compared to the blank.
1 point: The amount of composite stains generated was the same as that of the blank.

<Evaluation of mirror visibility during bathing>
The liquid cleaning composition of each example was filled into a Look Plus Bathtub Cleansing trigger spray container. I sprayed it on my bathroom mirror (50cm x 80cm) and then rinsed it in the shower. Thereafter, three adult men took a bath one after another and evaluated the visibility of the mirror using the following evaluation criteria. The average score of the three people was calculated, and if the average score was 3 or more, it was determined that the visibility was good.

≪Evaluation criteria≫
4 points: While taking a bath, there are almost no water droplets or cloudy water, and you can see the mirror.
3 points: While taking a bath, there are no water droplets or fog on the mirror, and you can see the mirror.
Point 2: While taking a bath, most of the mirror cannot be seen due to water droplets and cloudiness.
1 point: While taking a bath, the entire mirror cannot be seen due to water droplets and cloudiness.

<Evaluation of sprayability>
The liquid cleaning composition of each example was filled into a Look Plus Bathtub Cleansing trigger spray container. The liquid cleaning composition of each example was sprayed in one operation (1 push spray atomization) from a trigger spray container toward a flat plate. The spray appearance (degree of spread) on a flat plate was evaluated based on the following evaluation criteria. If it was ◎ or ○, it was judged that the sprayability was good.

≪Evaluation criteria≫
◎: Cleaning agent can be applied over a wider area.
○: Cleaning agent can be applied over a wide area.
△: Cleaning agent comes out in a narrow area.
×: Cleaning agent comes out in a narrower area.

<Evaluation of sebum cleaning power>
A 2 cm x 10 cm test piece made of glass fiber reinforced plastic (FRP) (manufactured by Nitto Shinko Co., Ltd.) was immersed in model sebum for 5 seconds and dried to obtain a dirt piece.
0.5 mL of the liquid cleaning composition of each example was dropped onto the soiled piece so that the entire surface was wetted, and the piece was left in a horizontal position for 1 minute. After standing for 1 minute, the liquid cleaning composition on the stain piece was rinsed with tap water at 15° C. for 10 seconds at 120 mL/s. Thereafter, the test piece was dried, and the state of removal of dirt from the surface of the test piece was visually confirmed, and the sebum cleaning power was evaluated based on the following evaluation criteria. In the following evaluation criteria, if it received a score of 3 or more, it was judged that the detergency against sebum stains was high.

≪Evaluation criteria≫
5 points: All dirt has been removed from the entire piece.
4 points: Most of the dirt on the entire piece has been removed.
Point 3: Dirt from about half of the entire piece has been removed.
2 points: Dirt on the entire piece is slightly removed.
1 point: Dirt on the entire piece cannot be removed at all.

(Examples 1 to 29, Comparative Examples 1 to 12)
According to the compositions shown in Tables 1 to 5, each component was added to water and mixed to prepare a liquid cleaning composition for each example.
The blending amounts in the table are pure equivalent values. Components whose blending amounts are not listed in the table are not blended. In the table, the water content "balance" is the amount required to make the liquid cleaning composition 100% by mass.
The liquid cleaning agent of each example was evaluated for drainage and sliminess, and the results are shown in the table.

As shown in Tables 1 to 4, in Examples 1 to 29 to which the present invention was applied, the composite stain suppression effect was 3.7 points or more, the mirror visibility was 3 points or more, and the sprayability was ``〇'' or ``. ◎", and the sebum cleaning power was "3 points or more.
In Comparative Examples 1 and 2 containing component (B') instead of component (B), the mirror visibility was 2.7 points or less.
Comparative Example 3, which contained component (A') in place of component (A), received 2 points for mirror visibility and sebum cleansing ability, and △ for sprayability.
Comparative Example 4, which lacks component (B), and Comparative Example 9, in which the content of component (B) is 0.01% by mass, received 2 points in composite stain suppression effect, mirror visibility, and sebum cleaning power. .
Comparative Example 5 lacking component (A) and Comparative Example 7 having a content of component (A) of 0.01% by mass had sebum detergency of 2 points or less.
Comparative Example 6 lacking component (C) and Comparative Example 11 in which the content of component (C) was 0.01% by mass had a composite stain suppression effect and mirror visibility of 2.3 points or less, and the spray The gender was △.
Comparative Example 7, in which the content of component (A) was 0.01% by mass, was rated 2.7 points for compound stain suppression effect and mirror visibility, and 2 points for sebum detergency.
Comparative Example 8 where the content of component (A) is 10% by mass, Comparative Example 10 where the content of component (B) is 5% by mass, Comparative Example 12 where the content of component (C) is 10% by mass The sprayability was rated as x.
From the above results, it was confirmed that by applying the present invention, the workability of cleaning work can be improved, the formation of complex stains can be suppressed, and the cleaning power for sebum stains can be increased.

Claims (6)

(A) Component: an anionic surfactant containing at least one selected from α-olefin sulfonic acid or its salt, linear alkylbenzenesulfonic acid or its salt, secondary alkanesulfonic acid or its salt,
Component (B): a copolymer containing a repeating unit (b1) derived from a monomer having a quaternary ammonium group,
(C) Component: Contains a nonionic surfactant,
The content of the component (A) is 0.1 to 5.0% by mass based on the total mass of the liquid cleaning composition for hard surfaces,
The content of the component (B) is 0.01 to 2.0% by mass based on the total mass of the liquid cleaning composition for hard surfaces,
A liquid cleaning composition for hard surfaces, wherein the content of component (C) is 0.1 to 5.0% by mass based on the total mass of the liquid cleaning composition for hard surfaces. The liquid cleaning composition for hard surfaces according to claim 1, wherein the mass ratio represented by the component (A)/the component (B) is 0.1 to 24. The liquid cleaning composition for hard surfaces according to claim 1 or 2, wherein the mass ratio represented by (the (A) component + the (B) component)/the (C) component is 0.1 to 24. thing. The component (B) has the repeating unit (b1) and the repeating unit (b2),
The repeating unit (b1) is at least one type selected from a repeating unit (b1-1) derived from a dimethyldiallylammonium salt and a repeating unit (b1-2) derived from a methacrylamide propyl trialkylammonium salt. ,
The repeating unit (b2) includes a repeating unit (b2-1) derived from acrylic acid, a repeating unit (b2-2) derived from acrylamide, and a repeating unit (b2-3) derived from methyl acrylate. ) The liquid cleaning composition for hard surfaces according to claim 1 or 2, wherein the composition is one or more repeating units selected from the following. The liquid cleaning composition for hard surfaces according to claim 1 or 2, wherein the weight average molecular weight of the component (B) is 10,000 to 2,000,000. The liquid cleaning composition for hard surfaces according to claim 1 or 2, which is for bathroom use.