JP2022078812A - Liquid detergent for bathrooms - Google Patents

Abstract

To provide a liquid detergent for bathrooms that can well remove sebum stains on a hydrophobic face and can be rinsed out well.SOLUTION: A liquid detergent for bathrooms contains component (A): a non-soap anionic surfactant, component (B): an ethylene oxide-added acetylene glycol represented by the following formula (b), and component (C): a glycol ether solvent. The content of the component (A) is 0.5 mass% or more relative to the total mass of the liquid detergent for bathrooms, and the mass ratio represented by the component (B)/the component (C) is 0.25-1.5, wherein, EO is an oxyethylene group, m and n independently represent an average number of repetitions of EO, ranging from 0 to 8, and the sum total of m and n is 1-8.SELECTED DRAWING: None

Description

The present invention relates to a liquid cleaning agent for bathrooms.

Conventionally, various liquid cleaning agents for bathrooms have been proposed for removing stains in the bathroom.
Patent Document 1 discloses a liquid detergent for bathrooms containing a surfactant containing a non-soap-based anionic surfactant, a glycol-based solvent, and an aminocarboxylic acid-type chelating agent, and having a pH of more than 10 and less than 12. ing.
Patent Document 2 discloses a liquid detergent for a bathroom containing a surfactant containing a non-soap-based anionic surfactant and an amine-type surfactant, a chelating agent, and a glycol-based solvent.

Japanese Unexamined Patent Publication No. 2016-124965 Japanese Unexamined Patent Publication No. 2020-105322

However, the liquid cleaning agent for bathroom of Patent Document 1 does not have sufficient sebum cleaning power.
In Patent Document 2, the detergency against sebum adhering to the glass surface is enhanced by containing the glycol-based solvent and the amine-type surfactant. However, sebum stains adhere more firmly to the hydrophobic surface such as PP (polypropylene) resin than to the hydrophilic surface such as the glass surface. The bathroom liquid detergent of Patent Document 2 does not have sufficient detergency against sebum stains adhering to the hydrophobic surface.
If an attempt is made to increase the detergency by simply increasing the amount of the anionic surfactant or the like (for example, making it more than 5% by mass with respect to the total mass of the liquid cleaning agent for bathroom), there arises a problem that the rinsing property is lowered.

One aspect of the present invention is to provide a liquid cleaning agent for a bathroom having excellent detergency and rinsing property against sebum stains adhering to a hydrophobic surface.

The present invention has the following aspects.
[1] Ingredient (A): Non-soap-based anionic surfactant and
Component (B): Ethylene oxide adduct of acetylene glycol represented by the following formula (b) and
(C) Component: Glycol ether type solvent and
Is a liquid cleaning agent for bathrooms containing
The content of the component (A) is 0.5% by mass or more with respect to the total mass of the liquid cleaning agent for bathroom.
A liquid cleaning agent for a bathroom, characterized in that the mass ratio represented by the component (B) / the component (C) is 0.25 to 1.5.

However, EO is an oxyethylene group, m and n are independently numbers of 0 to 8 indicating the average number of repetitions of EO, and the sum of m and n is 1 to 8.
[2] The component (C) is
Component (C1): Glycol ether type solvent represented by the following formula (c1) and
Component (C2): Glycol ether type solvent represented by the following formula (c2) and
Contains,
The bathroom liquid detergent according to the above [1], wherein the mass ratio represented by the component (C1) / the component (C2) is 0.1 to 10.
R ¹ O- (A ¹ O) _r -R ² ... (c1)
Ph-X- (A ² O) _s -R ³ ... (c2)
However, R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms, and R ² is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an acetyl group, and A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, and r is a number of 0.1 to 20 representing the average number of repetitions of A ¹ O.
Ph is a phenyl group, X is an oxygen atom or a CH ₂ O group, A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and s is 1 to 6 representing the average number of repetitions of A ² O. It is a number, and R3 is a hydrogen atom or an alkyl group having 1 to ³ carbon atoms.
[3] The bathroom liquid detergent according to the above [1] or [2], wherein the mass ratio represented by the component (A) / the component (C) is 0.1 to 1.5.
[4] The above [1] to [3], wherein the total content of the component (B) and the component (C) is 1 to 8% by mass with respect to the total mass of the bathroom liquid detergent. One of the bathroom liquid cleaners.

According to one aspect of the present invention, it is possible to provide a liquid cleaning agent for a bathroom having excellent detergency and rinsing property against sebum stains adhering to a hydrophobic surface.

The bathroom liquid detergent according to one aspect of the present invention contains the following component (A), the following component (B), and the following component (C).
The bathroom liquid detergent may further contain the following component (D), if necessary.
The bathroom liquid detergent may further contain components other than the components (A) to (D) (hereinafter, also referred to as "arbitrary components"), if necessary.

<Ingredient (A)>
The component (A) is a non-soap-based anionic surfactant.
The component (A) is used to exert effective detergency against sebum stains, protein stains, etc. adhering to the bathroom.

The components (A) include a sulfonate-type anionic surfactant, a sulfate ester-type anionic surfactant, an ether carboxylate-type anionic surfactant, an alkyl phosphate salt-type anionic surfactant, and an alkylpolyoxyethylene phosphate. Examples thereof include a salt-type anionic surfactant, an alkenyl succinate-type anionic surfactant, an N-acylamino acid salt-type anionic surfactant, and an N-acylmethyl taurine salt-type anionic surfactant.

Examples of the sulfonate type anionic surfactant include an olefin sulfonic acid type, an alkylbenzene sulfonic acid type, a sulfosuccinic acid dialkyl ester type, an alkyl sulfosuccinate type, an alkane sulfonic acid type, an alkylphenoxyphenyldisulfonic acid type, and an α-sulfo fatty acid type. Can be mentioned.
As the olefin sulfonic acid type anionic surfactant, α-olefin sulfonic acid or a salt thereof (AOS) in which the carbon-carbon double bond position is at the 1-position (α-position), and the carbon-carbon double bond is at the 2-position or higher. Examples thereof include internal olefin sulfonic acid or a salt thereof (IOS) in (inside).

The α-olefin sulfonic acid has preferably 8 to 24 carbon atoms, more preferably 10 to 20 carbon atoms.
Examples of the salt of α-olefin sulfonic acid include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
As the α-olefin sulfonate, an α-olefin sulfonate having 10 to 20 carbon atoms is preferable.
The α-olefin sulfonate is obtained by sulfonated an olefin having a carbon-carbon double bond position at the 1-position (α-position), neutralizing it with an alkali such as sodium hydroxide, and hydrolyzing it.
As the α-olefin sulfonate, a commercially available product can be used, and examples thereof include “Liporan LB440” manufactured by Lion Specialty Chemicals Co., Ltd.

The number of carbon atoms of the internal olefin sulfonic acid is preferably 8 to 24, more preferably 10 to 20.
Examples of the salt of the internal olefin sulfonic acid include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
As the internal olefin sulfonate, an internal olefin sulfonate having 8 to 24 carbon atoms is preferable, and examples thereof include the internal olefin sulfonate described in JP-A-2003-81935.
The internal olefin sulfonate is obtained by sulfonated an olefin having a carbon-carbon double bond position at the 2-position or higher (inside), neutralizing it with an alkali such as sodium hydroxide, and hydrolyzing it.

Examples of the sulfate ester type anionic surfactant include an alkyl ether sulfate ester type such as an alkyl ether sulfate ester or a salt thereof, and a polyoxyalkylene alkyl ether sulfate ester type such as a polyoxyalkylene alkyl ether sulfate ester or a salt thereof.

As the component (A), one type may be used alone, or two or more types may be used in combination as appropriate.
Among the above, as the component (A), a sulfonate-type anionic surfactant is preferable, and an olefin sulfonic acid type or an alkylbenzene sulfonic acid type anionic surfactant is more preferable, from the viewpoint of the detergency of soil stains and the detergency of sebum. An olefin sulfonic acid type anionic surfactant is more preferable.
As the olefin sulfonic acid type, α-olefin sulfonate is preferable from the viewpoint of sebum detergency. As the alkylbenzene sulfonic acid type anionic surfactant, an alkylbenzene sulfonate is preferable from the viewpoint of sebum detergency. Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine. Of these, alkali metal salts such as sodium salt and potassium salt are preferable.

<Ingredient (B)>
The component (B) is an ethylene oxide adduct of acetylene glycol represented by the following formula (b). The component (B) has a function of improving sebum detergency when used in combination with the component (C), and further has an effect of suppressing a decrease in rinsability due to the component (A).

ただし、ＥＯはオキシエチレン基であり、ｍ及びｎはそれぞれ独立に、ＥＯの平均繰り返し数を示す０～８の数であり、ｍとｎとの総和は１～８である。

However, EO is an oxyethylene group, m and n are independently numbers of 0 to 8 indicating the average number of repetitions of EO, and the sum of m and n is 1 to 8.

The sum of m and n is represented by m + n. When m + n is 1 to 8, it is easy to obtain good sebum detergency, and it is easy to suppress deterioration of rinsing property due to the component (A). m + n is preferably 2 to 8, more preferably 3.5 to 6, and particularly preferably 3.5 to 4.

The HLB (Hydrophilic-Lipopicular Balance) value of the component (B) is preferably 8 to 12, more preferably 8 to 11, and particularly preferably 8 to 9 from the viewpoint of detergency and rinsability.
The HLB value of the component (B) is a value calculated by the Griffin method, specifically, a value calculated by the following formula (1). The HLB value of the nonionic surfactant other than the component (B) is also calculated in the same manner.
HLB value = 20 x proportion of hydrophilic groups (% by mass) ... (1)
In the formula, the ratio of the hydrophilic group is the ratio of the total mass of the oxyethylene group (EO) to 100% by mass of the molecular weight of the component (B). The total mass of the oxyethylene group (EO) is calculated by multiplying the molecular weight of the oxyethylene group by (m + n).
The HLB value by the Griffin method is a value for evaluating the hydrophilicity of the compound proposed by Griffin, and shows a value in the range of 0 to 20. The higher the number, the more hydrophilic the compound.

Commercially available products can be used as the component (B), for example, acetylenol E13T (m + n = 1.3, HLB value: 4) and acetylenol E40 (m + n = 4, HLB value: 9) manufactured by Kawaken Fine Chemicals Co., Ltd.). , Acetylenol E60 (m + n = 6, HLB value: 11), Surfinol 420 (m + n = 1.3, HLB value: 4) manufactured by Nissin Chemical Industry Co., Ltd., Surfinol 440 (m + n = 3.5, HLB value) : 8) and the like.
As the component (B), one type may be used alone, or two or more types may be used in combination as appropriate.

<Ingredient (C)>
The component (C) is a glycol ether type solvent.
From the viewpoint of sebum detergency, the component (C) preferably contains at least one selected from the group consisting of the following (C1) component and the following (C2) component, and the (C1) component and the (C2) component. Is more preferable.

The component (C1) is a glycol ether type solvent represented by the following formula (c1).
R ¹ O- (A ¹ O) _r -R ² ... (c1)
However, R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms, and R ² is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an acetyl group, and A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, and r is a number of 0.1 to 20 representing the average number of repetitions of A ¹ O.

Specific examples of the component (C1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether. Ethylene glycol-based ether compounds such as triethylene glycol monobutyl ether; propylene glycol-based ether compounds such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether can be mentioned. Of these, ethylene glycol-based ether compounds are preferable, and diethylene glycol monobutyl ether is more preferable. One of these solvents may be used alone, or two or more of them may be used in combination as appropriate.

The component (C2) is a glycol ether type solvent represented by the following formula (c2).
Ph-X- (A ² O) _s -R ³ ... (c2)
However, Ph is a phenyl group, X is an oxygen atom or a CH ₂ O group, A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and s is 1 to 1 representing the average number of repetitions of A ² O. It is a number of 6, and R3 is a hydrogen atom or an alkyl group having 1 to ³ carbon atoms.

Specific examples of the component (C2) include ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monophenyl ether, and dipropylene glycol monophenyl ether. Of these, ethylene glycol monophenyl ether and diethylene glycol monophenyl ether are preferable from the viewpoint of sebum detergency. One of these solvents may be used alone, or two or more of them may be used in combination as appropriate.

<(D) component>
The component (D) is an aminocarboxylic acid type chelating agent.
The component (D) exhibits excellent detergency against fatty acid metal salts, sebum and protein stains adhering to bathtubs and the like.
The component (D) is not particularly limited as long as it is normally used. Specifically, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionacetic acid, triethylenetetrahexacetic acid, ethyleneglycoldietherdietherdiaminetetraacetic acid, hydroxyethyliminodi. Examples thereof include acetic acid, cyclohexane-1,2-diaminetetraacetic acid and the like. Of these, ethylenediaminetetraacetic acid is preferable from the viewpoint of detergency. These compounds can also be used in the form of acids and are salts with basic substances such as salts with alkali metals such as potassium and sodium, salts with alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. It can also be used in the form of.
As the component (D), one type may be used alone, or two or more types may be used in combination as appropriate.

<Arbitrary ingredient>
As the optional component, a component that can be usually used as a cleaning agent can be appropriately contained. Such optional components include, for example, soap-based anionic surfactants, cationic surfactants, amphoteric surfactants, bactericides, preservatives, antifungal agents, pigments, antioxidants, thickeners, and UV absorbers. , Metal sequestering agents, solubilizers, emulsifiers, fragrances, pH adjusters, water and the like.
The pH adjusting agent is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid and sulfuric acid, and alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and derivatives thereof. Among these, at least one acid agent selected from the group consisting of hydrochloric acid and sulfuric acid, or at least one alkaline agent selected from the group consisting of sodium hydroxide and potassium hydroxide are preferable. As the pH adjuster, any one of them may be used alone, or two or more of them may be used in combination.

<Contents of each component>
The content of the component (A) is 0.5% by mass or more, preferably 0.5 to 5.0% by mass, and 0.5 to 1.5% by mass with respect to the total mass of the liquid cleaning agent for bathroom. % Is more preferable. When the content of the component (A) is not less than the lower limit value, good sebum detergency can be obtained, and when it is not more than the upper limit value, good rinsing property can be obtained.

The total content of the component (B) and the component (C) (hereinafter, also referred to as “B + C”) is preferably 1 to 8% by mass, preferably 2 to 5% by mass, based on the total mass of the bathroom liquid detergent. Is more preferable. When B + C is within the above range, better sebum detergency and rinsing property can be obtained.

The content of the component (B) is preferably 0.1 to 3.0% by mass, more preferably 0.5 to 3.0% by mass, and 1.1 to 1.1% by mass with respect to the total mass of the liquid cleaning agent for bathrooms. 2.0% by mass is particularly preferable. When the content of the component (B) is within the above range, better sebum detergency (to rinse property) can be obtained when used in combination with the component (C).

The content of the component (C) is preferably 0.1 to 5.0% by mass, more preferably 1.0 to 2.5% by mass, based on the total mass of the bathroom liquid detergent. When the content of the component (C) is not less than the lower limit value, better sebum detergency can be obtained, and when it is not more than the upper limit value, better rinsing property can be obtained.

The content of the component (D) is preferably 0.1 to 5.0% by mass, more preferably 1.5 to 3.0% by mass, based on the total mass of the bathroom liquid detergent. When the content of the component (D) is within the above range, better descaling power can be obtained.

Bathroom liquid cleaners typically contain water.
The water content is, for example, 75 to 98% by mass with respect to the total mass of the bathroom liquid detergent.

<Mass ratio of (B) component / (C) component>
The mass ratio represented by the component (B) / component (C) (hereinafter, also referred to as “B / C”) is 0.25 to 1.5, preferably 0.5 to 0.7. When B / C is not less than the lower limit value, good sebum detergency can be obtained, and when it is not more than the upper limit value, good sebum detergency and rinsing ability can be obtained.

<Mass ratio of (C1) component / (C2) component>
The mass ratio represented by the component (C1) / component (C2) (hereinafter, also referred to as “C1 / C2”) is preferably 0.1 to 10, more preferably 0.5 to 5, and 1.0 to 3. 5 is particularly preferable. When C1 / C2 is within the above range, better sebum detergency can be obtained.

<Mass ratio of (A) component / (C) component>
The mass ratio represented by the component (A) / the component (C) (hereinafter, also referred to as “A / C”) is preferably 0.1 to 1.5, more preferably 0.3 to 0.75. When the A / C is within the above range, better sebum detergency and rinsing property can be obtained.

<Mass ratio of (A) component / (B) component>
The mass ratio represented by the component (A) / the component (B) (hereinafter, also referred to as “A / B”) is preferably 0.25 to 3.0, more preferably 0.5 to 1.5. When A / B is within the above range, better sebum detergency and rinsing property can be obtained.

<pH of liquid cleaning agent for bathroom>
The pH of the bathroom liquid detergent at 25 ° C. is preferably 6 or more, more preferably 9 or more, still more preferably 9.5 to 12, and particularly preferably 10 to 11. When the pH is within the above range, better descaling power can be obtained.

<Manufacturing method of liquid cleaning agent for bathroom>
The bathroom liquid detergent can be produced according to a conventionally known method for producing a liquid detergent. For example, each component excluding a pH adjuster is added to a part of water and mixed, and if necessary, a pH adjuster is added to adjust the pH, and then the rest of the water is added to make the total amount 100% by mass. By doing so, a liquid cleaning agent for bathroom can be manufactured. Further, the obtained liquid cleaning agent for bathroom can be stored in a container (for example, a discharge container described later) to obtain a liquid cleaning agent product for bathroom in a container.

<How to use liquid cleaning agent for bathroom>
As a method of using the bathroom liquid cleaning agent, for example, the bathroom liquid cleaning agent is impregnated into a cleaning tool such as a sponge, and the cleaning target such as the bathroom wall surface, the bathtub surface, and other bathroom accessories is scrubbed with a sponge or the like. A method of storing the bathroom liquid cleaning agent in a discharge container, applying an appropriate amount of the bathroom liquid cleaning agent to the cleaning target from this discharge container, and after a certain period of time, rinse with a shower or the like, "wash without rubbing". , Etc. can be mentioned.
Examples of the discharge container for accommodating the liquid cleaning agent for the bathroom include a spray container and a squeeze container. Among them, a spray container is preferable as a discharge container for accommodating a liquid cleaning agent for a bathroom because it is excellent in applicability to a cleaning target.

Examples of the spray container include an aerosol spray container, a trigger spray container (direct pressure type or accumulator type), a dispenser spray container and the like. These containers may be manual or electric. Examples of the aerosol spray container include those described in JP-A-9-3441, JP-A-9-58765, and the like. When filling the aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, nitrous oxide gas and the like can be used as the propellant. These propellants may be used alone or in combination of two or more. Examples of the trigger spray container include those described in JP-A-9-268473A, JP-A-10-76196, and the like. Examples of the pressure-accumulation type trigger spray container include those described in Japanese Patent Application Laid-Open No. 2013-154276. Examples of the dispenser spray container include those described in JP-A-9-256272. Among these, a trigger spray container is preferable because the spray properties and the spray pattern are good and good coatability can be obtained.

The bathroom liquid detergent described above contains the component (A), the component (B), and the component (C), and the content of the component (A) is 0.5% by mass or more, and the B / C is When it is 0.25 to 1.5, it is possible to achieve both detergency and rinsability for sebum stains adhering to a hydrophobic surface such as PP resin.
In particular, when the alkyl-based (C1) component and the phenyl-based (C2) component are used in combination as the (C) component, the detergency is improved.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The raw materials used in this example are as follows.

(Ingredients used)
<Ingredient (A)>
A-1: AOS, α-olefin (C14) sodium sulfonate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Liporan LJ441". In addition, "C" of the said "C14" means a carbon number, and the same applies hereinafter.
A-2: LAS, linear alkyl (C12-14) sodium benzenesulfonate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Rypon PS-230".

<Ingredient (B)>
B-1: Acetylene glycol EO adduct (m + n = 4, HLB value: 9), manufactured by Kawaken Fine Chemical Co., Ltd., trade name "Acetyleneol E40".
B-2: Acetylene glycol EO adduct (m + n = 6, HLB value: 11), manufactured by Kawaken Fine Chemical Co., Ltd., trade name "Acetyleneol E60".
B-3: Acetylene glycol EO adduct (m + n = 3.5, HLB value: 8), manufactured by Nisshin Kagaku Kogyo Co., Ltd., trade name "Surfinol 440".

<Comparison product of (B) component>
B'-1 (Comparative product): Polyoxyethylene alkyl ether (EO average number of moles added: 7, HLB value: 13), manufactured by BASF Japan Ltd., trade name "Lutenzal TO7".
B'-2 (Comparative product): Acetylene glycol EO adduct (m + n = 10, HLB value: 13), manufactured by Kawaken Fine Chemicals Co., Ltd., trade name "Acetyleneol E100".

<Ingredient (C)>
C1-1: Diethylene glycol monobutyl ether, manufactured by Nippon Embroidery Co., Ltd., trade name "butyl diglycol".
C1-2: Dipropylene glycol monomethyl ether, manufactured by Dow Chemical Japan Co., Ltd., trade name "DOWNOL DPM Glycol Ether".
C2-1: Ethylene glycol monophenyl ether, manufactured by Nippon Embroidery Co., Ltd., trade name "Phenyl glycol".
C2-2: Diethylene glycol monophenyl ether, manufactured by Nippon Embroidery Co., Ltd., trade name "Phenyldiglycol".
C2-3: Ethylene glycol monobenzyl ether, manufactured by Nippon Embroidery Co., Ltd., trade name "benzyl glycol".

<(D) component>
D-1: Ethylenediamine tetraacetic acid, manufactured by Nourion Japan Co., Ltd., trade name "Dizorbin".

<Other optional ingredients>
Potassium coconut oil: Made by Lion Specialty Chemicals Co., Ltd., trade name "Potassium coconut oil fatty acid".
pH regulator: 1N aqueous sodium hydroxide solution, manufactured by Kanto Chemical Co., Inc.
Water: Ion-exchanged water.

(Examples 1 to 25, Comparative Examples 1 to 6)
According to the composition shown in Tables 1 to 4, components (A) to (D) and potassium coconut oil fatty acid are added and mixed with a part of water, and the pH is adjusted to the value in the table with a pH adjuster. The remainder of the water was added to give each example a liquid cleaning agent for the bathroom. The composition (blending component, content (%)) of the obtained liquid cleaning agent for bathroom of each example is shown in the table. Unless otherwise specified, "%" indicates "mass%" of pure content. If there is a blank compounding ingredient in the table, that compounding ingredient is not blended. In the table, the content "appropriate amount" of the pH adjuster is the amount required to bring the pH of the bathroom liquid detergent of each example to the value in the table. In the table, the water content "balance" means the amount added so that the total amount (% by mass) of all the components contained in the bathroom liquid detergent is 100% by mass.
The bathroom liquid detergents of each example were evaluated for descaling power, sebum detergency, and rinsing property as follows. The results are shown in Tables 1 to 4.

<Evaluation of descaling power>
After fixing a glass fiber reinforced plastic (FRP) test piece (2 cm x 10 cm) to the inner wall of the bathtub in a general household, three adult men each take a bath five times (one bath per day is repeated for five days). During that time, only the bath water was replaced, and the bathtub was used without washing) to make the test piece dirty.
After the test piece with the stain is sufficiently dried, the bathroom cleaner of each example is dropped onto the test piece so that the entire surface is wet, and the test piece is left for 30 seconds, and then tap water (15 ° C.) is applied. I rinsed it off. The test pieces were sufficiently dried, and the state of removing stains on the surfaces of the five test pieces was visually and touched, and evaluated according to the following evaluation criteria. In the following evaluation criteria, if it is ◎ or ○, the descaling power is practically good.
[Evaluation criteria]
⊚: Very good stain removal [Of the 5 test pieces, no visual stains were observed on any of the 5 test pieces, and a smooth touch was obtained on the entire surface of the test pieces].
〇: Good stain removal [Of the 5 test pieces, 1 or more of the 5 test pieces were not visually observed and a smooth touch was obtained on the entire surface of the test piece. One or more pieces feel a rough touch on the test piece].
Δ: Almost no stains were removed [Of the 5 test pieces, 5 of the 5 test pieces were observed to have visual stains, and all 5 had a rough touch, but the visual stains and rough fingers were not present. It is less than before cleaning].
X: Dirt does not come off at all [Of the 5 test pieces, 5 of the 5 test pieces were observed to have visual stains, and all 5 had a rough finger touch, and the visual stain and rough finger touch were washed. Same as before].

<Evaluation of sebum stain cleaning power>
30 g of beef tallow (manufactured by Kanto Chemical Co., Inc.), 20 g of soybean oil (manufactured by Kanto Chemical Co., Inc.), and 0.05 g of Zudan IV (manufactured by Kanto Chemical Co., Inc.) are mixed with 50 mL of chloroform (manufactured by Kanto Chemical Co., Inc., special grade) to stain. A sap was prepared. 50 mL of this stain liquid was placed in a glass bottle, a 1 × 5 cm PP plate (manufactured by Testpiece Co., Ltd.) was immersed and pulled up, and the one dried for 1 hour or more was used as a stain plate.
50 mL of the bathroom liquid cleaner is put in a 100 mL glass bottle, the stain plate is immersed in this bathroom liquid cleaner for 3 minutes, then the stain plate is taken out, and the state of stain removal is visually observed, and the following evaluation criteria are used. Evaluated according to. In the following evaluation criteria, if it is ⊚ or ◯, the practical detergency for sebum stains is good.
[Evaluation criteria]
◎: Very good dirt removal.
〇: Good dirt removal.
Δ: There is unevenness in removing dirt.
×: Almost no dirt is removed.

<Evaluation of rinsing property>
The trigger container of the commercially available bathroom detergent "Ofuro Look" (manufactured by Lion Co., Ltd.) is filled with a liquid bathroom cleaner, and the inside of the FRP bathtub (100 x 75 x 65 cm) is filled with 10 at equal intervals. Sprayed once. After that, using a urethane sponge, rub the entire inside of the bathtub in a circular motion while applying a load of about 10 g / cm ² , and then rinse with tap water using a shower (water temperature 15 ° C, flow rate 0). .2 L / sec), the time until the bubbles completely disappeared from the drain of the bathtub was measured, and the rinse property of the liquid cleaning agent for bathroom was evaluated according to the following evaluation criteria. In the following evaluation criteria, ◎ and ○ were accepted.
[Evaluation criteria]
⊚: 19 seconds or less.
◯: 20 seconds or more and less than 23 seconds.
Δ: 23 seconds or more and less than 30 seconds.
×: 31 seconds or more.

The bathroom liquid detergents of Examples 1 to 25 had good descaling power, sebum detergency, and rinsing property.
On the other hand, the bathroom liquid detergent of Comparative Example 1 was inferior in descaling power and sebum detergency because the content of the component (A) was less than 0.5% by mass.
The bathroom liquid detergent of Comparative Example 2 containing no component (B) was inferior in sebum detergency.
The bathroom liquid detergents of Comparative Examples 3 to 4 in which a comparative product was used instead of the component (B) were inferior in sebum detergency.
The bathroom liquid detergent of Comparative Example 5 having a B / C of less than 0.25 was inferior in sebum detergency.
The bathroom liquid detergent of Comparative Example 6 having a B / C of more than 1.5 was inferior in descaling power.

Claims (4)

(A) Ingredients: Non-soap-based anionic surfactant,
Component (B): Ethylene oxide adduct of acetylene glycol represented by the following formula (b) and
(C) Component: Glycol ether type solvent and
Is a liquid cleaning agent for bathrooms containing
The content of the component (A) is 0.5% by mass or more with respect to the total mass of the liquid cleaning agent for bathroom.
A liquid cleaning agent for a bathroom, characterized in that the mass ratio represented by the component (B) / the component (C) is 0.25 to 1.5.

However, EO is an oxyethylene group, m and n are independently numbers of 0 to 8 indicating the average number of repetitions of EO, and the sum of m and n is 1 to 8. The component (C) is
Component (C1): Glycol ether type solvent represented by the following formula (c1) and
Component (C2): Glycol ether type solvent represented by the following formula (c2) and
Contains,
The liquid cleaning agent for a bathroom according to claim 1, wherein the mass ratio represented by the component (C1) / the component (C2) is 0.1 to 10.
R ¹ O- (A ¹ O) _r -R ² ... (c1)
Ph-X- (A ² O) _s -R ³ ... (c2)
However, R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms, and R ² is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an acetyl group, and A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, and r is a number of 0.1 to 20 representing the average number of repetitions of A ¹ O.
Ph is a phenyl group, X is an oxygen atom or a CH ₂ O group, A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and s is 1 to 6 representing the average number of repetitions of A ² O. It is a number, and R3 is a hydrogen atom or an alkyl group having 1 to ³ carbon atoms. The liquid cleaning agent for a bathroom according to claim 1 or 2, wherein the mass ratio represented by the component (A) / the component (C) is 0.1 to 1.5. The invention according to any one of claims 1 to 3, wherein the total content of the component (B) and the component (C) is 1 to 8% by mass with respect to the total mass of the bathroom liquid detergent. Liquid cleaning agent for bathrooms.