JP6516353B2 - Liquid cleaning agent for bathroom - Google Patents

Description

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

Cleaning of the bathroom is usually carried out by rubbing with a sponge impregnated with a liquid cleaning agent for the bathroom with respect to the wall of the bathroom, the bath surface, other facilities attached to the bathroom, and the like.
In the case of scrubbing, for example, when the tub is cleaned, the entire surface of the tub must be rubbed with a sponge, because the scrub target is scrubbed directly with a sponge. In addition, physical burden is big.

Heretofore, cleaning agents have been proposed to reduce the time and effort required to wash the bathroom. For example, Patent Document 1 discloses a sequestering agent, a surfactant, an organic solvent having a solubility in water at 20 ° C. of 10% or less, and a propellant, each for a specific weight ratio. Aerosol cleaners have been proposed. According to Patent Document 1, after the bathtub cleaning agent is sprayed onto the remaining hot water surface of the bathtub to diffuse it onto the hot water surface and adhere to the side surface of the bathtub, the stopper of the bathtub is removed. There is disclosed a method of cleaning a bath which causes the side and bottom of the bath to adhere to the side and bottom of the bath while lowering the cleaning component spread on the hot water side together with the hot water side by draining the remaining hot water.
Patent Document 2 proposes a cleaning agent containing a specific aminocarboxylic acid salt and a carboxylic acid other than this in a specific weight ratio. According to Patent Document 2, there is disclosed a method of cleaning a bathroom which is allowed to stand for a while and then flowed with a shower after the cleaning agent is sprayed to light boil stains.
In addition, Patent Document 3 describes a cleaning method in a bathroom in which a cleaning liquid containing a surfactant and a chelating agent is sprayed onto a bath tub or the like by a discharge device such as a shower device and then rinsed with tap water. .

According to the cleaning agent or the cleaning method disclosed in Patent Documents 1 to 3, the cleaning target such as a bath can be cleaned without scrubbing, so that the time and effort for physical cleaning can be reduced.
However, in the method of washing without scrubbing such a bath (washing without rubbing), it is necessary to make the liquid detergent for a bathroom adhere to the entire surface of the object to be washed such as the bath. Usage increases. When the amount of use of the liquid cleaning agent for a bathroom increases, there is a problem that foaming originating from components such as a surfactant in the cleaning agent occurs and the rinse property is deteriorated.

With respect to this problem, Patent Document 4 describes a liquid cleaning agent for a bath containing a fatty acid or a salt thereof, and discloses that the cleaning agent is excellent in rinseability. However, when the amount of the detergent used increases, as in "washing without rubbing", sufficient rinse performance can not be obtained only by incorporating a fatty acid or a salt thereof into the detergent.
In addition, in order to improve the rinse performance of the detergent, it is conceivable to reduce the content of surfactant in the detergent. However, the surfactant is the main cleaning component of the detergent, and if its content is simply reduced, sufficient detergency against fatty acid metal salts such as fatty acid calcium salts adhering to the bath etc., sebum and protein stains etc. It can not be obtained.

JP, 2000-109891, A JP-A-11-217600 JP 2005-185352 A Japanese Patent Application Laid-Open No. 7-34091

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid cleaning agent for a bathroom which has a superior cleaning power and which is also excellent in rinseability.

As a result of intensive studies, the present inventors have found that the following bath liquid cleaner can solve the above-mentioned problems.
That is, the present invention comprises: (A) component: 0.1 to 5.0% by mass of a surfactant containing a non-soap anionic surfactant; (B) component: a glycol based solvent; An acid type chelating agent, and the mass ratio represented by the component (C) / component (A) is 0.6 to 6.0, and the pH at 25 ° C. is more than 10 and 12 It is a liquid cleaning agent for a bathroom characterized by being less than.

  According to the present invention, it is possible to provide a bath liquid cleaner having superior detergency and good rinse performance.

  The liquid cleaning agent for a bathroom of the present invention contains the following components (A) to (C).

<(A) component>
The component (A) is a surfactant containing a non-soap anionic surfactant (A-1), and is used to impart a detergency to a bathroom liquid detergent.
In the present invention, the non-soap anionic surfactant (A-1) is an anionic surfactant other than saturated or unsaturated fatty acid salt having 8 to 24 carbon atoms (so-called soap).

  The component (A) may be composed only of the component (A-1), or may be composed of the component (A-1) and a surfactant other than this.

As the component (A-1), for example, linear alkyl benzene sulfonate (LAS); linear or branched alkyl sulfate (AS); alkyl ether sulfate or alkenyl ether sulfate (AES); α-olefin Sulfonate (AOS); alkanesulfonate having alkyl group; α-sulfo fatty acid ester salt (α-SF); alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylic Acid, anionic surfactant of carboxylic acid type such as acylamino carboxylate; alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkyl phenyl phosphate ester salt, glycerin fatty acid ester monophosphate ester Phosphoric acid such as salt Anionic surfactants such as the ester-type and the like.
Examples of these salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; monoethanolamine salts; alkanolamine salts such as diethanolamine salts and triethanolamine salts; and ammonium salts. Among these, alkali metal salts are preferable.

Among the above, as the linear alkyl benzene sulfonate, one having a linear alkyl group having 8 to 16 carbon atoms is preferable, and one having 10 to 14 carbon atoms is more preferable.
As an alkyl sulfate, a C10-C20 thing is preferable and a C10-C16 thing is more preferable.
As alkyl ether sulfates or alkenyl ether sulfates, polyoxyethylene alkyl ether sulfates having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added thereto Or polyoxyethylene alkenyl ether sulfate is preferable.
As an alpha-olefin sulfonate, a C10-C20 thing is preferable and a C10-C16 thing is more preferable.
The alkane sulfonate is preferably a secondary alkane sulfonate having an alkyl group having 10 to 20, preferably 14 to 17 carbon atoms.
As the α-sulfo fatty acid ester salt, an α-sulfo fatty acid ester salt having 10 to 20 carbon atoms, preferably 10 to 18 carbon atoms is preferable.
As a polyoxyalkylene ether carboxylate, a polyoxyethylene alkyl ether carboxylate having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added thereto or Polyoxyethylene alkenyl ether carboxylate is preferred.

  Among these, α-olefin sulfonate is particularly preferable because of its excellent detergency against sebum and protein stains.

As the component (A-1), one type may be used alone, or two or more types may be used in combination.
0.1-5.0 mass% is preferable with respect to the total mass of the liquid cleaning agent for bathrooms, and, as for content of (A-1) component, 1.0-3.0 mass% is more preferable. When the content of the component (A-1) is less than 0.1% by mass, sufficient detergency may not be obtained. When the content of the component (A-1) exceeds 5.0% by mass, the rinse property is reduced.

50-100 mass% is preferable, and, as for content of the (A-1) component in (A) component, 80-100 mass% is more preferable.
When the content of the component (A-1) in the component (A) is in the above range, good detergency can be easily obtained.

The component (A) may contain a surfactant other than the component (A-1) (hereinafter, also referred to as an optional surfactant (A-2)).
Although it does not specifically limit as arbitrary surfactant (A-2), For example, a higher fatty acid salt, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant etc. are mentioned.
From the viewpoint of obtaining better detergency, the component (A) preferably does not contain the component (A-2).

  As higher fatty acid salts, saturated or unsaturated fatty acid salts having 8 to 24 carbon atoms, such as laurate, myristate, stearate, etc., or coconut oil fatty acid salt which is a mixture thereof, hardened coconut oil fatty acid salt, Palm oil fatty acid salt, hardened palm oil fatty acid salt, beef tallow fatty acid salt, hardened beef tallow fatty acid salt and the like can be mentioned. Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, monoethanolamine salts, alkanolamine salts such as diethanolamine salts and triethanolamine salts, and ammonium salts.

  Examples of cationic surfactants include alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, benzalkonium salts, benzethonium salts, pyridinium salts, imidazolium salts and the like. Examples of counter ions of these salts include halogen ions.

  Amphoteric surfactants include alkyl carboxy betaines, alkyl sulfo betaines, alkyl hydroxy sulfo betaines, alkylamido betaines, imidazolinium betaines and the like.

  Nonionic surfactants include polyoxyalkylene type nonionic surfactants obtained by adding an alkylene oxide to higher alcohol, alkylphenol, higher fatty acid or higher amine, etc., polyoxyethylene polyoxypropylene block copolymer, fatty acid alkanolamide, polyhydric alcohol Fatty acid ester or its alkylene oxide adduct, fatty acid polyglycerol ester, sugar fatty acid ester, alkyl (or alkenyl) amine oxide, amidoamine oxide, alkylene oxide adduct of hydrogenated castor oil, N-alkyl polyhydroxy fatty acid amide, alkyl glycoside, alkyl Polyglycosides, glyceryl ethers and the like can be mentioned.

  As the component (A-2), any one type may be used alone, or two or more types may be used in combination.

The content of the component (A) is 0.1 to 5.0% by mass, more preferably 1.0 to 3.0% by mass, with respect to the total mass of the liquid cleaning agent for a bathroom.
If the content of the component (A) is less than 0.1% by mass, sufficient detergency can not be obtained. When the content of the component (A) exceeds 5.0% by mass, good rinse properties can not be obtained.

<(B) component>
The component (B) is a glycol solvent.
As the glycol solvent of the present invention, a solvent selected from compounds represented by the following general formula (I) is preferable.

R ¹ -O- (C ₂ H ₄ O) _x- (C ₃ H ₆ O) _y -R ² (I)

In the above formula (I), R ¹ and R ² 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 repetition of the oxyethylene group, preferably 0 to 5, more preferably 1 to 3, and still more preferably 1 or 2. y is a number representing the average number of repetition of the oxypropylene group, preferably 0-5, more preferably 0-2. However, x and y do not simultaneously become 0.

  As component (B), for example, ethylene glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, propylene glycol solvents such as propylene glycol, dipropylene glycol, tripropylene glycol and isoprene glycol, ethylene glycol monomethyl ether, 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 monobutyl ether Ethylene glycol-based ethers such as benzyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl Propylene glycol ethers such as ether and 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 It is.

  As the component (B), diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monopropyl ether, ethylene glycol monohexyl ether are preferable, and diethylene glycol monobutyl ether is particularly preferable.

As the component (B), any one type may be used alone, or two or more types may be used in combination.
0.1-5.0 mass% is preferable with respect to the total mass of the liquid cleaning agent for bathrooms, and, as for content of (B) component, 1.0-3.0 mass% is more preferable. If content of (B) component is more than the said lower limit, favorable cleaning power will be easy to be obtained. If content of (B) component is below the said upper limit, favorable rinse property will be easy to be acquired.

<(C) component>
The component (C) is an aminocarboxylic acid type chelating agent.
In the present invention, the range in which the content of the component (A) is suppressed by using the component (C) under alkaline conditions where the pH at 25 ° C. is more than 10 and less than 12 (0.1 to 5.0) Even in the case of% by mass, the detergency against fatty acid metal salts, sebum and protein stains attached to a bath or the like can be enhanced.
As component (C), methylglycine diacetic acid (MGDA), aspartic acid diacetic acid (ASDA), isoserine diacetic acid (ISDA), β-alanine diacetic acid (ADAA), serine diacetic acid (SDA), glutamic acid diacetic acid (GLDA), Iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), ethylenediaminetetraacetic acid (EDTA), N-lauroylethylenediaminetriacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), Triethylene tetraamine hexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropane tetraacetic acid (DPTA-OH), hydroxyethylene iminodiacetic acid (HIDA), dihydric acid B carboxyethyl glycine (DHEG), glycol ether diaminetetraacetic acid (GEDTA), dicarboxylate methyl glutamate (CMGA), (S, S) - ethylenediamine disuccinic acid (EDDS) or the salts thereof.

  As component (C), ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), dihydroxyethylglycine (DHEG), hydroxyethylene iminodiacetic acid (HIDA) and diethylenetriaminepentaacetic acid (DTPA) are preferable, and ethylenediaminetetraacetic acid is preferable. (EDTA) is particularly preferred.

As the component (C), any one type may be used alone, or two or more types may be used in combination.
0.2-5.0 mass% is preferable with respect to the total mass of the liquid cleaning agent for bathrooms, and, as for content of (C) component, 1.5-4.0 mass% is more preferable. If the content of the component (C) is equal to or more than the above lower limit, the detergency is further enhanced. If content of (C) component is below the said upper limit, rinse property will improve more.

The mass ratio represented by (C) component / (A) component [the mass ratio of the content of the (C) component to the content of the (A) component, hereinafter also referred to as “C / A ratio”] is 0. 6 to 6.0, preferably 0.6 to 5.0, and more preferably 0.6 to 3.0.
In the present invention, by setting the C / A ratio in the above range, even when the content of the component (A) is suppressed (0.1 to 5.0% by mass), it adheres to a bath etc. Excellent detergency against fatty acid metal salts, sebum and protein stains can be obtained, and good rinse properties can be obtained. In particular, when the bath is cleaned without rubbing, the liquid cleaning agent for a bathroom is applied to the entire surface of the bath, so the amount of cleaning agent used increases. By setting the C / A ratio in the above range, good rinse performance can be obtained even when the amount of detergent used is increased.
If the C / A ratio is less than 0.6, sufficient rinse performance can not be obtained. In addition, if the C / A ratio exceeds 6.0, sufficient detergency can not be obtained.

  The total content of the components (A) and (B) [hereinafter referred to as "the total content of A and B"] is preferably 0.5 to 8.0% by mass with respect to the total mass of the liquid cleaning agent for a bathroom . If the total content of the component (A) and the component (B) is equal to or more than the above lower limit, the detergency can be further enhanced. If total content of (A) component and (B) component is below the said upper limit, rinse property will be improved more.

  The mass ratio represented by (B) component / (C) component [the mass ratio of the content of the (B) component to the content of the (C) component, hereinafter also referred to as “B / C ratio”] is 0. 01-4.0 are preferable and 0.4-3.0 are more preferable. If the B / C ratio is in the above-mentioned preferable range, the detergency can be further enhanced.

<Solvent>
The liquid cleaning agent for a bathroom of the present invention usually contains water as a solvent because it is easy to prepare for a liquid cleaning agent for a bathroom and easily dissolved in water at the time of rinsing.
Although the compounding quantity of water in the liquid detergent for bathroom is not specifically limited, 50-99.5 mass% is preferable in the liquid detergent for bathroom, 70-99 mass% is more preferable, and 75-98 mass% is further more preferable. preferable.

<Optional component>
The liquid cleaning agent for a bathroom of the present invention can contain, in addition to the above-mentioned components, components which can usually be used for the cleaning agent, if necessary. As such optional components, for example, bactericidal agents, preservatives, antifungal agents, dyes, antioxidants, thickeners, UV absorbers, solubilizers (but not including the component (B)), perfumes And pH adjusters.

The pH adjuster is not particularly limited, but is selected from inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and p-toluenesulfonic acid. It is preferable to use an alkaline agent selected from an acid agent, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and derivatives thereof, monoethanolamine, diethanolamine, triethanolamine etc., hydrochloric acid, sulfuric acid, citric acid It is more preferable to use an alkali agent selected from an acid agent selected from among sodium hydroxide and potassium hydroxide.
The pH adjuster may be used singly or in combination of two or more.

The liquid cleaning agent for a bathroom of the present invention has a pH of more than 10 and less than 12 at 25 ° C., preferably pH 10.1 to 11.4, more preferably pH 10.4 to 11.4.
The liquid cleaning agent for a bathroom of the present invention is a range in which the content of the component (A) is suppressed by using the components (A) to (C) at a specific C / A ratio within the above range of pH Even in the case of 0.1 to 5.0% by mass), good detergency can be obtained against fatty acid metal salts, sebum and protein stains attached to a bath or the like.
The pH of the liquid cleaning agent for a bathroom of the present invention is a value measured at 25 ° C. according to JIS Z8802: 2011.

The liquid cleaning agent for a bathroom of the present invention preferably has a viscosity of 1 to 100 mPa · s at 25 ° C., and more preferably 1 to 50 mPa · s.
If the viscosity at 25 ° C. is equal to or more than the above lower limit value, the adhesion of the bathroom liquid cleaning agent to the cleaning target such as a bath is further improved. When the viscosity at 25 ° C. is equal to or less than the upper limit value, the liquid cleaning agent for a bathroom is easily discharged from a discharge container such as a spray container, and the handling property is improved.

  The liquid cleaning agent for a bathroom of the present invention is produced by a conventionally known production method. For example, the method of adding the said (A)-(C) component to the water which is a solvent, adding an arbitrary component as needed, and mixing this etc. is mentioned.

  As a method of using the liquid cleaning agent for a bathroom according to the present invention, for example, a liquid cleaning agent for a bathroom is impregnated into a cleaning tool such as a sponge, and a cleaning object such as a wall surface of a bathroom, a bathtub surface, or other bathroom accessories How to use to wash with, or store the liquid cleaning agent for the bathroom in the discharge container, apply an appropriate amount of the liquid cleaning agent for the bathroom from the discharge container to the object to be cleaned, and after a certain time, rinse with a shower etc. , And a method of using "wash without rubbing".

  The liquid cleaning agent for a bathroom of the present invention has high detergency against fatty acid metal salt, sebum and protein stain attached to a bath, and the liquid cleaning agent for a bathroom is applied to the entire surface of the bath to use the cleaning agent Since it has excellent rinse properties even when the amount is increased, it is suitably used for the method of use "washing without rubbing".

Although a spray container, a squeeze container, etc. are mentioned as a discharge container which accommodates the liquid cleaning agent for a bathroom of this invention, A spray container is preferable from having excellent coating property with respect to washing | cleaning object.
As a spray container, an aerosol spray container, a trigger spray container (direct pressure type or pressure accumulation type), a dispenser spray container, etc. are mentioned. 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 a propellant. These propellants may be used alone or in combination of two or more.
As an example of a trigger spray container, the thing as described in Unexamined-Japanese-Patent No. 9-268473, 10-76196 etc. is mentioned, for example.
As an example of a dispenser spray container, the thing as described in Unexamined-Japanese-Patent No. 9-256272 etc. is mentioned, for example.
As a pressure-accumulation type trigger spray container, the thing as described in Unexamined-Japanese-Patent No. 2013-154276 etc. is mentioned, for example.
Among these, a pressure-accumulated trigger spray container is preferable because the spray property and the spray pattern are good and the good coatability is obtained.

  As described above, the liquid cleaning agent for a bathroom of the present invention contains the components (A) to (C), and the mass ratio of the component (C) to the component (A) is in a specific range, and as described above, Since the pH at 25 ° C. is within the specific range, the detergency is further enhanced and the rinse performance is also excellent.

EXAMPLES The present invention will be described in more detail using the following examples, but the present invention is not limited to these examples. In the present example, “%” indicates “% by mass” unless otherwise noted.
The composition of the liquid cleaning agent for a bathroom of each example is shown in Tables 1-6.
The raw materials used in this example are as follows.

<(A-1) component, non-soap based anionic surfactant>
A-1-1: AOS, sodium C14-α olefin sulfonate, manufactured by Lion Corporation, trade name "Lipolan LJ441". In addition, "C" of said "C14" means carbon number, and so on.
A-1-2: LAS, sodium long chain alkyl (C10-16) alkyl benzene sulfonate, manufactured by Lion Corporation, trade name "Lipon PS-230".
A-1-3: AES, polyoxyethylene alkyl (C12-14) ether sulfate [average added mole number 2 of ethylene oxide]. Shin-Nippon Rika Co., Ltd., brand name Sinoline SPE-1250.
A-1-4: MES, C16-18 alpha sulfo fatty acid methyl ester salt, manufactured by Lion Corporation, trade name "MIZULAN FL-80".
A-1-5: SDS, lauryl sulfate, manufactured by Lion Corporation, trade name "Sannol LM-1130".
<(A-2) Component, Optional Surfactant>
A-2-1: C10-18 fatty acid potassium, manufactured by Lion Corporation, trade name "30% aqueous solution of potassium fatty acid potassium".
A-2-2: Fatty acid amidopropyl betaine, manufactured by Lion Corporation, trade name "Enazicol L-30B".
A-2-3: alkylamine oxide (AX), manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Kadenax DM 12 D-W (C)".
A-2-4: polyoxyethylene alkyl ether (AE), C ₁₃ H ₂₇ O (CH ₂ CH ₂ O) ₇ H (average ethylene oxide 7-mole adduct of branched C 13 alcohol), manufactured by BASF, trade name “ Lutensol TO-7 ".
A-2-5: alkyl polyglycoside, manufactured by BASF Japan Ltd., trade name "Glucopon 215 UP".
A-2-6: polyoxyethylene nonylphenyl ether (average ethylene oxide 8 mol adduct of nonylphenol), manufactured by Lion Corporation, trade name "Laol XA-60-50".
A-2-7: Glyceryl ether (CH ₃ (CH ₂ ) ₅ OCH ₂ CH (OH) CH ₂ OH), synthetic product (n-hexanol and 1-chloro-2,3-epoxypropane, Lewis acid catalyst) Prepared by a method of condensation by an etherification reaction in the presence of and opening the epoxy ring by hydrolysis).

<(B) component>
B-1: Diethylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name "butyl diglycol".
B-2: Diethylene glycol monobenzyl ether, manufactured by Japan Emulsifier Co., Ltd., trade name "phenyl diglycol".
B-3: Ethylene glycol monophenyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name "phenyl glycol".
B-4: Propylene glycol monopropyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name "propyl propylene glycol".
B-5: ethylene glycol monohexyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name "Hexyl glycol".
B-6: Diethylene glycol monoethyl ether, manufactured by Dow Chemical Japan Ltd.
B-7: (CH ₃ ) ₂ CH-O- (C ₂ H ₄ O)-(C ₃ H ₆ O) -H, synthetic product (addition of 1 mol of propylene oxide and 1 mol of ethylene oxide to i-propanol Manufactured).
B-8: Dipropylene glycol monomethyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name "methyl propylene diglycol".
B-9: C ₄ H ₉ -O- (C ₂ H ₄ O) _2- (C ₃ H ₆ O) ₂ -H, manufactured by Sanyo Kasei Co., Ltd., New Pole 50 HB-55.

<(C) component>
C-1: Ethylenediaminetetraacetic acid disodium (EDTA2Na), manufactured by Akzo Nobel, trade name "Dissolvin NA2".
C-2: Hydroxyethylenediaminetriacetic acid, manufactured by Chelest Co., Ltd., trade name "HEDTA".
C-3: Dihydroxyethyl glycine, Chelest Co., Ltd., trade name "DHEG".
C-4: hydroxyethylene iminodiacetic acid, manufactured by Chelest Co., Ltd., trade name "HIDA".
C-5: Diethylenetriaminepentaacetic acid, Chelest Co., Ltd., trade name "DTPA".
<Other ingredients>
pH adjuster: 1 N sodium hydroxide, 1 N hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.).

<Examples 1 to 35, Comparative Examples 1 to 19>
The components (A) to (C) are added to water according to the compositions shown in Tables 1 to 6 and mixed, and then the pH is adjusted to a value in the table with a pH adjuster, and the liquid detergent for bathroom of each example I got
The composition (compounding component, content (% by mass)) of the obtained liquid detergent for a bathroom is shown in Tables 1 to 6. In addition, mass% shows pure content unless there is particular notice.
In the table, when there is a blank combination component, the combination component is not blended.
In the table, the content "appropriate amount" of the pH adjusting agent is an amount required to bring the pH of the bathroom liquid cleaner in each example to the value in the table.
In the table, the water content "balance" means the balance added so that the total blending amount (% by mass) of all the blending components contained in the liquid cleaning agent for a bathroom is 100% by mass.
However, Examples 20-23 are reference examples.

<Evaluation method of liquid cleaning agent for bathroom>
For each of the bathroom liquid cleaners, the detergency and the rinse performance were evaluated as follows.
The evaluation results are shown in Tables 1 to 6.

[Evaluation of detergency]
After fixing a test piece (2 cm × 10 cm) made of glass fiber reinforced plastic (FRP) on the inner wall surface of a general household bathtub, three adult men take baths three times each (one bathing per day for three days, During that time, only bath water was replaced, and the bath was not washed, and the test piece was stained.
After thoroughly drying the test piece to which this stain adheres, the liquid cleaning agent for a bathroom of each example is dropped onto the test piece so that the entire surface thereof becomes wet, and left for 30 seconds, tap water (15 ° C.) ) It was washed away. The test pieces were sufficiently dried, and the removal of stains on the surfaces of the five test pieces was visually evaluated and evaluated by finger touch according to the following evaluation criteria for detergency. In the following evaluation criteria, ◎ and を were accepted.
[Evaluation criteria for detergency]
:: very good stain removal [of five test pieces, no visual stain was observed on all five test pieces, and all five test pieces were slippery on the entire surface of the test piece].
:: Good stain removal [with 5 or more test pieces, no visual stains are observed, and a finger touch smooth on the entire surface of the test piece is obtained, and out of 5 test pieces, At least one feels rough finger touch on the test piece].
:: Almost no stains removed [Among five test pieces, five of the test pieces were observed visually, and all five felt rough to the touch, but the visual stains and rough to the touch were: It is alleviated than before cleaning].
X: No stains were observed [All five of the five test pieces were visually observed, and all five felt rough finger touch, and the visual stain and rough finger touch were not good. It is the same as before.]
The evaluation results are shown in the column of cleaning power (30 seconds) in Tables 1 to 6.

Furthermore, in the evaluation of the cleaning power, the cleaning time was evaluated in the same manner as described above, changing the standing time after dropping the liquid cleaning agent for a bathroom onto the test piece from 30 seconds to 60 seconds, and 120 seconds. .
The evaluation results are shown in the columns of cleaning power (60 seconds) and cleaning power (120 seconds) in Tables 1 to 6, respectively.

[Evaluation of rinseability]
After spraying 40 g of the liquid cleaner for bathroom in each case on the entire surface of the bath, it is rinsed with tap water using a shower (water temperature 15 ° C., flow rate 0.2 L / sec). The time until the foam completely disappeared from the drainage port was measured, and the rinse property of the bathroom liquid detergent was evaluated according to the following evaluation criteria. In the following evaluation criteria, ◎ and を were accepted.
[Evaluation criteria for rinseability]
◎: less than 40 seconds ○: 40 seconds or more and less than 50 seconds Δ: 50 seconds or more and less than 60 seconds ×: 60 seconds or more The evaluation results are shown in the column of rinse properties (15 ° C.) in Tables 1-6.

Furthermore, in the above evaluation of the rinse property, the water temperature when performing rinsing with tap water using a shower is changed from 15 ° C. to 40 ° C., and the rinse property is evaluated in the same manner as described above. , ○ and を were accepted.
The evaluation results are shown in the column of rinseability (40 ° C.) in Tables 1 to 6.

From the results shown in Tables 1 to 6, it can be confirmed that the liquid cleaning agent for a bathroom of Examples 1 to 35 to which the present invention is applied is excellent in cleaning power and good in rinse property.
On the other hand, bathroom liquid cleaners (comparative examples 1, 2 and 8) whose C / A ratio does not satisfy the range of the present invention (comparative examples 1, 2 and 8) and (A) to (C) components In Comparative Examples 6, 7, 10, 11, 13, 16 to 19), sufficient detergency was not obtained. Moreover, the liquid cleaning agent for baths (comparative examples 8, 9, 12) whose content of (A) component exceeds the upper limit of this invention did not obtain sufficient rinse property. Furthermore, bathroom liquid detergents whose pH values do not satisfy the range of the present invention (Comparative Examples 3-5, 13-15, 17-19) do not have sufficient detergency or sufficient rinse performance. It was not obtained.
From the above results, it can be confirmed that the liquid cleaning agent for a bathroom to which the present invention is applied is excellent in cleaning power and good in rinseability.

Claims (4)

Component (A): 0.1 to 5.0% by mass of a surfactant containing an α-olefin sulfonate having 10 to 20 carbon atoms ,
Component (B): a glycol solvent represented by the following general formula (I) ,
R ¹ -O- (C ₂ H ₄ O) _x- (C ₃ H ₆ O) _y -R ² (I)
[In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a C1-C6 alkyl group or alkenyl group, a phenyl group, or a benzyl group. x is a number representing the average number of repetition of the oxyethylene group, and is 0 to 5; y is a number representing the average number of repetition of the oxypropylene group, and is 0 to 5; However, x and y do not simultaneously become 0. ]
(C) Component: aminocarboxylic acid type chelating agent,
A bath liquid detergent you containing,
The content of the α-olefin sulfonate is 0.1 to 5.0% by mass with respect to the total mass of the liquid cleaning agent for a bathroom,
The mass ratio represented by the component (C) / the component (A) is 0.6 to 6.0, and the pH at 25 ° C. is more than 10 and less than 12 Liquid detergent. The liquid cleaning agent for a bathroom according to claim 1, wherein the content of the component (B) is 0.1 to 5.0% by mass with respect to the total mass of the liquid cleaning agent for a bathroom. The liquid cleaning agent for a bathroom according to claim 1 or 2, wherein the content of the component (C) is 0.2 to 5.0% by mass with respect to the total mass of the liquid cleaning agent for a bathroom. The total amount of the said (A) component and the said (B) component is 0.5-8.0 mass% with respect to the total mass of the said liquid cleaning agent for baths, The any one of Claims 1-3 Liquid cleaner for bathroom as described in.