JP6768282B2 - Liquid cleaning agent for bathroom - Google Patents

Description

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

Bathroom cleaning is usually performed by scrubbing the bathroom wall surface, bathtub surface, and other bathroom accessories with a sponge impregnated with a bathroom liquid cleaning agent.
In scrubbing, the object to be washed is rubbed directly with a sponge. For example, when cleaning a bathtub, the entire surface of the bathtub must be rubbed with a sponge by bending forward, leaning down, or crouching. Also, the physical burden is heavy.

Conventionally, cleaning agents have been proposed to reduce the labor and physical burden of cleaning the bathroom. For example, Patent Document 1 describes a sequestrant, a surfactant, an organic solvent having a solubility in water at 20 ° C. of 10% or less, and a propellant in specific weight ratios, respectively. Aerosol cleaning agents have been proposed. According to Patent Document 1, the air bath cleaning agent for bathtub is sprayed on the remaining hot water surface of the bathtub to diffuse it on the hot water surface and adhere to the side surface of the bathtub. After that, by unplugging the bathtub and discharging the remaining hot water, the cleaning component spread on the hot water surface together with the hot water surface is lowered and adhered to the side surface and the bottom surface of the bathtub, and then the cleaning method of the bathtub is disclosed. Has been done.
Patent Document 2 proposes a cleaning agent containing a specific aminocarboxylic acid salt and other carboxylic acids in a specific weight ratio. According to Patent Document 2, a method for cleaning a bathroom in which the cleaning agent is sprayed on light scale stains and then left for a while and then showered is disclosed.
Further, Patent Document 3 describes a cleaning method in a bathroom in which a cleaning liquid containing a surfactant and a chelating agent is sprayed on a bathtub or the like by a discharge means such as a shower device and then rinsed with tap water. ..

According to the cleaning agent or cleaning method disclosed in Patent Documents 1 to 3, the cleaning target such as a bathtub can be cleaned without scrubbing, so that the labor and physical burden of cleaning can be reduced. However, in the techniques of Patent Documents 1 to 3, the cleaning agent drips in a streak on the vertical surface of the bathtub, and the cleaning agent adheres and stays on the vertical surface (that is, the cleaning agent stays attached to the cleaning target). The nature) was not enough.

Patent Document 4 discloses a cleaning agent having an increased viscosity in order to improve the adhesion retention of the cleaning agent on a vertical surface. However, the spreadability of the cleaning agent (that is, the property that the cleaning agent spreads evenly and uniformly from the portion where the cleaning agent is sprayed to the periphery thereof) is insufficient.
Patent Document 5 discloses a cleaning agent that combines a specific solvent, a specific surfactant, and a specific thickener in order to achieve both adhesion retention and spreadability, and Patent Document 6 discloses a cleaning target. A cleaning agent having a controlled contact angle with the surface of the surface is disclosed. However, the cleaning target of each of these is a toilet bowl, and the cleaning power against fatty acid metal salts and sebum / protein stains adhering to bathtubs and the like has not been investigated.

Japanese Unexamined Patent Publication No. 2000-109891 JP-A-11-217600 Japanese Unexamined Patent Publication No. 2005-185352 Japanese Patent Application Laid-Open No. 1-221498 Japanese Unexamined Patent Publication No. 2011-225763 Japanese Unexamined Patent Publication No. 2004-210808

The present invention has been made in view of the above circumstances, and an object of the present invention is a liquid cleaning agent for a bathroom having excellent cleaning power even on a vertical surface of a bathtub.

The present inventors cannot obtain sufficient detergency on a vertical surface simply by increasing the viscosity of the cleaning agent to improve the adhesion retention property, and have both adhesion retention property and spreadability on a vertical surface. It was found that excellent detergency can be obtained.
Therefore, as a result of diligent studies, the present inventors have found that the following liquid cleaning agents for bathrooms can solve the above problems.
The liquid cleaning agent for bathroom of the present invention has the following aspects.
[1] Component (A): A surfactant containing a nonionic surfactant (a1), and
Component (B): Glycol solvent and
Component (C): Aminocarboxylic acid type chelating agent and
Component (D): Water-soluble polymer and
Contains,
A liquid cleaning agent for bathrooms having a kinematic viscosity of 1.5 to ²⁰ mm ² / s measured with a thin tube viscometer at 25 ° C.
[2] The liquid cleaning agent for a bathroom according to [1], wherein the pH at 25 ° C. is more than 10 and less than 12.
[3] The liquid cleaning agent for a bathroom according to [1] or [2], wherein the component (D) is a polysaccharide.

According to the present invention, it is possible to provide a liquid cleaning agent for a bathroom having excellent cleaning power even on a vertical surface of a bathtub.

The liquid cleaning agent for bathroom of the present invention is a composition containing the following components (A) to (D).

<Ingredient (A)>
The component (A) is a surfactant containing the nonionic surfactant (a1), and is used to impart detergency on the vertical surface of the bathtub to the liquid cleaning agent for bathrooms.

In the present invention, the nonionic surfactant (a1) is a polyoxyalkylene type nonionic surfactant obtained by adding an alkylene oxide to a higher alcohol, an alkylphenol, a higher fatty acid, a higher amine or the like, a polyoxyethylene polyoxypropylene block copolymer, and the like. Fatty acid alkanolamide, polyhydric alcohol fatty acid ester or its alkylene oxide adduct, fatty acid polyglycerin ester, sugar fatty acid ester, alkyl (or alkenyl) amine oxide, amidoamine oxide, hardened castor oil alkylene oxide adduct, N-alkylpolyhydroxy Examples thereof include fatty acid amides, alkyl glycosides, alkyl polyglycosides, and glyceryl ethers.
Among these, a polyoxyalkylene type nonionic surfactant obtained by adding an alkylene oxide to a higher alcohol is preferable.
Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide, with ethylene oxide and propylene oxide being preferable, and ethylene oxide being more preferable. The average number of moles of alkylene oxide added is preferably 3 to 50, more preferably 4 to 20, and particularly preferably 6 to 15.
The alkyl group of the higher alcohol preferably has 8 to 20 carbon atoms, more preferably 10 to 15 carbon atoms.
Among them, oxo alcohol ethoxylate, gelve alcohol ethoxylate, and polyoxyethylene alkyl ether are preferable.
The oxo alcohol ethoxylate preferably has an alkyl group having 10 to 15 carbon atoms and an ethylene oxide having an average added mole number of 6 to 15. Specifically, BASF's LutensolTO is preferable.
The gelber alcohol ethoxylate preferably has 10 carbon atoms of the alkyl group and 6 to 15 moles of ethylene oxide added. Specifically, BASF's Lutensol XP is preferable.
In the polyoxyethylene alkyl ether, the alkyl group preferably has 12 to 14 carbon atoms and the average number of moles of ethylene oxide added is 6 to 15. Specifically, LMAO-90 manufactured by Lion Chemical Co., Ltd. is preferable.

As the component (a1), any one of them may be used alone, or two or more of them may be used in combination.
The content of the component (a1) is preferably 0.04 to 5.0% by mass, more preferably 0.5 to 5.0% by mass, and even more preferably 1 with respect to the total mass of the bathroom liquid cleaning agent. It is 0 to 3.0% by mass. When the content of the component (a1) is within the above range, more excellent detergency can be easily obtained on the vertical surface of the bathtub.
The content of the component (a1) in the component (A) is preferably 0.1 to 100% by mass, more preferably 30 to 90% by mass, still more preferably 40 to 85% by mass.
When the content of the component (a1) in the component (A) is in the above range, it becomes easy to obtain better detergency on the vertical surface of the bathtub.

The component (A) preferably contains a non-soap-based anionic surfactant (hereinafter, also referred to as the component (a2)) as a surfactant other than the component (a1).
In the present invention, the non-soap-based anionic surfactant (a2) is an anionic surfactant excluding saturated or unsaturated fatty acid salts having 8 to 24 carbon atoms (so-called soap). The component (a2) is used to impart detergency to a liquid cleaning agent for bathrooms.

Examples of the component (a2) include α-olefin sulfonate (AOS), linear alkylbenzene sulfonate (LAS), alkane sulfonate having an alkyl group, α-sulfo fatty acid ester salt (α-SF) and the like. Sulfonic acid-type anionic surfactants; sulfate ester-type anionic surfactants such as linear or branched alkyl sulfates (AS), alkyl ether sulfates or alkenyl ether sulfates (AES); alkyl ether carboxylates, Caroic acid type anionic surfactants such as polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylate, acylaminocarboxylate; alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, Examples thereof include phosphoric acid ester-type anionic surfactants such as polyoxyalkylene alkylphenyl phosphate ester salt and glycerin fatty acid ester monophosphate ester salt.
Among these, sulfonic acid type, sulfate ester type, and carboxylic acid type anionic surfactants are preferable, and sulfonic acid type anionic surfactants are more preferable.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, monoethanolamine salts, diethanolamine salts, alkanolamine salts such as triethanolamine salts, and ammonium salts. Among these, alkali metal salts are preferable.

Among the above, as the α-olefin sulfonate, those having 10 to 20 carbon atoms are preferable, and those having 10 to 16 carbon atoms are more preferable.
As the linear alkylbenzene sulfonate, those having a linear alkyl group having 8 to 16 carbon atoms are preferable, and those having 10 to 14 carbon atoms are more preferable.
As the alkane sulfonate, a secondary alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms is preferable.
As the α-sulfofatty acid ester salt, an α-sulfofatty acid ester salt having 10 to 20 carbon atoms, preferably 10 to 18 carbon atoms is preferable.
The alkyl sulfate preferably has 10 to 20 carbon atoms, and more preferably 10 to 16 carbon atoms.
The alkyl ether sulfate or alkenyl ether sulfate is a polyoxyethylene alkyl ether sulfate having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average of 1 to 10 mol of ethylene oxide added. Alternatively, polyoxyethylene alkenyl ether sulfate is preferable.
The polyoxyalkylene ether carboxylate is a polyoxyethylene alkyl ether carboxylate having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average of 1 to 10 mol of ethylene oxide added. Polyoxyethylene alkenyl ether carboxylate is preferred.

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

As the component (a2), any one of them may be used alone, or two or more of them may be used in combination.
The content of the component (a2) is preferably 0.1 to 3.0% by mass, more preferably 0.5 to 2.0% by mass, based on the total mass of the liquid cleaning agent for bathroom. When the content of the component (a2) is within the above numerical range, it becomes easy to obtain better detergency on the vertical surface of the bathtub.

The component (A) may contain a surfactant other than the component (a1) and the component (a2) (hereinafter, also referred to as an optional surfactant (a3)).
The optional surfactant (a3) is not particularly limited, and examples thereof include higher fatty acid salts, cationic surfactants, and amphoteric surfactants.
The component (A) is preferably one that does not contain the component (a3) from the viewpoint of obtaining better detergency.

Examples of the higher fatty acid salt include saturated or unsaturated fatty acid salts having 8 to 24 carbon atoms such as laurate, myristate, and stearate, or coconut oil fatty acid salts and cured coconut oil fatty acid salts which are mixtures thereof. Examples thereof include palm oil fatty acid salt, hardened palm oil fatty acid salt, beef fat fatty acid salt, and hardened beef fat fatty acid salt. Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, monoethanolamine salts, diethanolamine salts, alkanolamine salts such as triethanolamine salts, and ammonium salts.

Examples of the cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzalkonium salt, benzethonium salt, pyridinium salt, imidazolium salt and the like. Examples of the counter ion of these salts include halogen ions and the like.

Examples of the amphoteric surfactant include alkylcarboxybetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamide betaine, and imidazolinium betaine.

As the component (a3), any one of them may be used alone, or two or more of them may be used in combination.

The content of the component (A) is preferably 0.1 to 6.0% by mass, more preferably 1.0 to 3.0% by mass, based on the total mass of the liquid cleaning agent for bathroom.
When the content of the component (A) is within the above numerical range, it becomes easy to obtain better detergency on the vertical surface of the bathtub.

<Ingredient (B)>
The component (B) is a glycol solvent.
As the glycol solvent of the present invention, those selected from the compounds represented by the following general formula (I) are 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 group or an alkenyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group. x is a number representing the average number of repetitions of the oxyethylene group, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. y is a number representing the average number of repetitions of the oxypropylene group, preferably 1 to 5, more preferably 1 to 2. However, x and y do not become 0 at the same time.

Examples of the component (B) include ethylene glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol, propylene glycol-based solvents such as propylene glycol, dipropylene glycol, tripropylene glycol, and isoprene glycol, ethylene glycol monomethyl ether, and ethylene. Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether Ethylene glycol-based ethers such as, propylene glycol 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 ether, etc. Examples thereof include propylene glycol-based ethers such as dipropylene glycol monobutyl ether, dialkyl glycol ether-based solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ethyl ether, and dipropylene glycol methyl ethyl ether.

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

As the component (B), any one of them may be used alone, or two or more of them may be used in combination.
The content of the component (B) is preferably 0.1 to 5.0% by mass, more preferably 1.0 to 3.0% by mass, based on the total mass of the liquid cleaning agent for bathroom. When the content of the component (B) is within the above range, better detergency can be easily obtained.

<Component (C)>
The component (C) is an aminocarboxylic acid type chelating agent.
In the present invention, by using the component (C), the detergency against fatty acid metal salts, sebum and protein stains adhering to bathtubs and the like can be enhanced.
As the component (C), methylglycine diacetic acid (MGDA), aspartate diacetic acid (ASDA), isoserine diacetic acid (ISDA), β-alanine diacetic acid (ADAA), serine diacetic acid (SDA), glutamate diacetic acid (GLDA), Imminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), ethylenediaminetetraacetic acid (EDTA), N-lauroylethylenediaminetriacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), Triethylenetetraaminehexacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH), hydroxyethyleneiminodiacetic acid (HIDA), dihydroxy Examples thereof include ethylglycine (DHEG), glycol etherdiaminetetraacetic acid (GEDTA), dicarbokimethylglutamic acid (CMGA), (S, S) -ethylenediaminediaminedic acid (EDDS), and salts thereof.

As the component (C), ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), dihydroxyethylglycine (DHEG), hydroxyethyleneiminodiacetic acid (HIDA), diethylenetriaminetetraacetic acid (DTPA) are preferable, and ethylenediaminetetraacetic acid is preferable. (EDTA) is particularly preferred.

As the component (C), any one of them may be used alone, or two or more of them may be used in combination.
The content of the component (C) is preferably 0.2 to 8.0% by mass, more preferably 1.5 to 7.0% by mass, based on the total mass of the liquid cleaning agent for bathroom. When the content of the component (C) is within the above range, more excellent detergency can be easily obtained.

The mass ratio represented by the component (C) / component (a1) [the mass ratio of the content of the component (C) to the content of the component (a1), hereinafter also referred to as “C / a1 ratio”] is 0. 1 to 5.0 is preferable, 0.4 to 4.0 is more preferable, and 0.6 to 3 is particularly preferable.
In the present invention, by setting the C / a1 ratio in the above range, it becomes easy to obtain better detergency against fatty acid metal salts, sebum and protein stains adhering to bathtubs and the like.

The mass ratio represented by the component (C) / component (a2) [the mass ratio of the content of the component (C) to the content of the component (a2), hereinafter also referred to as “C / a2 ratio”] is 0. It is preferably 6 to 6.0, more preferably 0.6 to 5.0, and particularly preferably 0.6 to 3.0.
In the present invention, by setting the C / a2 ratio in the above range, it becomes easy to obtain better detergency against fatty acid metal salts, sebum and protein stains adhering to bathtubs and the like.

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

<Ingredient (D)>
The component (D) is a water-soluble polymer. The component (D) is used to impart adhesion retention and spreadability on the vertical surface of the bathtub.
In addition, in this specification, a polymer means a polymer having a weight average molecular weight of 1000 or more. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent and converted based on a calibration curve in PEG (polyethylene glycol). The water-soluble polymer is obtained by adding 10 g of the polymer to 1000 g of water under the condition of 40 ° C. in a 1 liter beaker, and stirring (200 rpm) with a stirrer (thickness 8 mm, length 50 mm) for 12 hours. It means something that is dissolved.
As the component (D), polysaccharides typified by xanthan gum, gellan gum, caraginan, guar gum and the like; cellulose-based polymers such as cationized cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose (CMC); polyvinylpyrrolidone, N- Pyrrolidone-based polymers such as alkylpyrrolidone; polyalkylene glycol-based polymers such as polyethylene glycol (PEG), polypropylene glycol, polyethylene glycol / polypropylene glycol copolymer; polyvinyl-based polymers such as polyvinyl alcohol (PVA) and polyvinyl acetate And so on.
Of these, polysaccharides are preferable.
Further, the component (D) includes the following. For example, alkali-soluble / swellable emulsion (ASE) polymers, hydrophobically modified alkali-soluble / swellable emulsion (HASE) polymers, acid-soluble / swellable emulsion polymers, hydrophobically modified acid-soluble. / Swellable emulsion polymers, acidic homopolymers, copolymers, and salts thereof; basic homopolymers, copolymers, and salts thereof; poly (quaternized amine) homopolymers, copolymers, and salts thereof; amphoteric polymers; anions. Sexual, cationic, and amphoteric polysaccharide homopolymers, copolymers, and salts thereof; anionic, cationic, and amphoteric polysaccharide derivatives; anionic, cationic, and amphoteric polypeptide homopolymers, copolymers, and salts thereof. Anionic, cationic, and amphoteric polypeptide derivatives; chemically modified polypeptide homopolymers, copolymers, and salts thereof; nucleic acid homopolymers, copolymers, and salts thereof; chemically modified nucleic acids, Naturally occurring nucleic acids, enzymes, synthetic and naturally occurring proteins, gelatin, lignosulfonic acid homopolymers, copolymers, and salts thereof; ionen homopolymers, copolymers, and salts thereof; anionic, cationic, and amphoteric polyesters. Homopolymers, copolymers, and salts thereof; anionic, cationic, and amphoteric polyurethane homopolymers, copolymers, and salts thereof; combinations of homopolymers, copolymers, and copolymers of these salts listed; ionic. And nonionic micelles; a combination of the chemopolymers, copolymers, and biopolymeric and non-chemical interpolymers of these salts; of the listed homopolymers, copolymers, and salts thereof. Polymer Matrix; Physical blends of listed homopolymers, copolymers, and salts thereof; listed homopolymers, copolymers, and salts thereof on which anionic, cationic, and amphoteric components are grafted. , And a combination of these.
As the component (D), xanthan gum, gellan gum, carrageenan, guar gum, CMC, cationized cellulose, PVA, and PEG are particularly preferable.

The component (D) may be used alone or in combination of two or more.
The content of the component (D) is preferably 0.005 to 0.15% by mass, more preferably 0.01 to 0.10% by mass, based on the total mass of the liquid cleaning agent for bathroom.
When the content of the component (D) is at least the above lower limit value, the adhesion retention property on the vertical surface of the bathtub is likely to be enhanced, and better cleaning power on the vertical surface of the bathtub is likely to be obtained. When the content of the component (D) is not more than the above upper limit value, the spreadability on the vertical surface of the bathtub is likely to be enhanced, and better cleaning power on the vertical surface of the bathtub is likely to be obtained.

As a preferable combination of the components (A) to (D), the component (a1) is at least one selected from the group consisting of oxoalcohol ethoxylate, gelvealcohol ethoxylate, and polyoxyethylene alkyl ether, and (a2). The component is α-olefin sulfonate, and the component (B) is selected from the group consisting of diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monopropyl ether, and ethylene glycol monohexyl ether. It is at least one kind, and the component (C) consists of ethylenediamine tetraacetic acid (EDTA), hydroxyethylenediamine triacetic acid (HEDTA), dihydroxyethylglycine (DHEG), hydroxyethyleneiminodiacetic acid (HIDA), and diethylenetriamine pentaacetic acid (DTPA). It is at least one selected from the group, and it is preferable that the component (D) is at least one selected from the group consisting of xanthan gum, gellan gum, caraginan, guar gum, CMC, cationized cellulose, PVA, and PEG.

<Solvent>
The bathroom liquid cleaning agent of the present invention usually contains water as a solvent because it is easy to prepare the bathroom liquid cleaning agent and is easily dissolved in water during rinsing.
The amount of water to be blended in the bathroom liquid cleaning agent is not particularly limited, but is preferably 50 to 99.5% by mass, more preferably 70 to 99% by mass, and further preferably 75 to 98% by mass in the bathroom liquid cleaning agent. preferable.

<Arbitrary ingredient>
If necessary, the liquid cleaning agent for bathrooms of the present invention may contain components that can be usually used in cleaning agents in addition to the above components. Such optional components include, for example, bactericides, preservatives, antifungal agents, pigments, antioxidants, thickeners, UV absorbers, solubilizers (however, component (B) is not included), and fragrances. , PH adjuster and the like.

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 the following acid agents, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and its derivatives, monoethanolamine, diethanolamine, triethanolamine and the like, and hydrochloric acid, sulfuric acid and citric acid. It is more preferable to use an acid agent selected from the above, an alkali agent selected from sodium hydroxide and potassium hydroxide.
As the pH adjuster, any one of them may be used alone, or two or more of them may be used in combination.

The bathroom liquid cleaning agent of the present invention preferably has a pH of more than 10 and less than 12 at 25 ° C., more preferably pH 10.1 to 11.4, and even more preferably pH 10.4 to 11.4.
When the pH of the liquid cleaning agent for bathrooms of the present invention is in the above range, it becomes easy to obtain better cleaning power against fatty acid metal salts, sebum and protein stains adhering to bathtubs and the like.
The pH of the liquid cleaning agent for bathroom of the present invention is a value measured at 25 ° C. according to JIS Z8802: 2011.

<Viscosity>
The bathroom liquid cleaning agent of the present invention has a kinematic viscosity of 1.5 to ²⁰ mm ² / s measured with a thin tube viscometer at 25 ° C. More preferably, it is 1.8 to 15 mm ² / s.
If the kinematic viscosity measured with a thin tube at 25 ° C. is less than the above lower limit, the adhesion retention property on the vertical surface of the bathtub cannot be obtained, and the cleaning agent drips in a streak pattern, which is sufficient on the vertical surface of the bathtub. Detergency cannot be obtained. If the kinematic viscosity measured with a thin tube at 25 ° C. exceeds the above upper limit value, the spreadability on the vertical surface of the bathtub deteriorates, and sufficient cleaning power on the vertical surface of the bathtub cannot be obtained.
The kinematic viscosity using a thin tube can be measured by the procedure of the viscosity measuring method using a JIS Z8803 (2011) thin tube viscometer.

The liquid cleaning agent for bathroom of the present invention is produced by a conventionally known production method. For example, a method of adding the above-mentioned components (A) to (D) to water as a solvent, adding an arbitrary component as necessary, and mixing them can be mentioned.

As a method of using the bathroom liquid cleaning agent of the present invention, for example, the bathroom liquid cleaning agent is impregnated into a cleaning tool such as a sponge, and the cleaning target of the bathroom wall surface, bathtub surface, other bathroom ancillary equipment, etc. How to use by scrubbing with, or put the bathroom liquid cleaning agent in the discharge container, apply an appropriate amount of bathroom liquid cleaning agent to the cleaning target from this discharge container, and rinse with a shower etc. after a certain period of time. , How to use for "washing without rubbing".

The bathroom liquid cleaning agent of the present invention has a high cleaning power against fatty acid metal salts, sebum and protein stains adhering to the bathtub, and when the bathroom liquid cleaning agent is applied to the entire surface of the bathtub, the vertical surface of the bathtub. However, since it has excellent detergency, it is suitably used for a usage method of "washing without rubbing".

Examples of the discharge container for accommodating the liquid cleaning agent for bathroom of the present invention include a spray container and a squeeze container, but a spray container is preferable 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-9-268473, JP-A-10-76196, and the like.
Examples of the dispenser spray container include those described in JP-A-9-256272.
Examples of the pressure-accumulation type trigger spray container include those described in Japanese Patent Application Laid-Open No. 2013-154276.
Among these, a pressure-accumulation type trigger spray container is preferable because the spray properties and the spray pattern are good and good coatability can be obtained.

As described above, the bathroom liquid cleaning agent of the present invention contains the components (A) to (D), and the kinematic viscosity measured by the thin tube viscometer at 25 ° C. is within a specific range. Excellent detergency on the surface.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In this embodiment, "%" indicates "mass%" unless otherwise specified.
The composition of the liquid cleaning agent for bathroom in each example is shown in Tables 1 to 3.
The raw materials used in this example are as follows.

<(A1) component>
a1-1: Polyoxyethylene alkyl (C13, 100% branched) ether [average number of moles of ethylene oxide added 7], manufactured by BASF, trade name "Lutensol TO-7". The "C" in the "C13" means the number of carbon atoms of the alkyl group (hydrocarbon group), and the same applies hereinafter.
a1-2: Polyoxyethylene mono (2-propylheptyl) ether [average number of moles of ethylene oxide added 8], manufactured by BASF, trade name "Lutensol XP80".
a1-3: Polyoxyethylene mono (2-propylheptyl) ether [average number of moles of ethylene oxide added 10], manufactured by BASF, trade name "Lutensol XP100".
a1-4: Polyoxyethylene alkyl (C12-14, linear 100%) ether [average number of moles of ethylene oxide added 15], manufactured by Lion Corporation, trade name "LMAO-90".

<(A2) component>
a2-1: AOS, sodium C14-α-olefin sulfonate, manufactured by Lion Corporation, trade name "Liporan LJ441".
a2-2: LAS, long-chain alkyl (C10-16) sodium benzenesulfonate, manufactured by Lion Corporation, trade name "Rypon PS-230".

<Ingredient (B)>
B-1: Diethylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name "butyl diglycol".

<Component (C)>
C-1: Disodium ethylenediaminetetraacetate (EDTA2Na), manufactured by AkzoNobel, trade name "Disorbin NA2".

D-1: Xanthan gum, manufactured by Sansho Co., Ltd., trade name "KELZAN".
D-2: Gellan gum, manufactured by DSP Gokyo Food & Chemical Co., Ltd., trade name "Kelcogel".
D-3: Carrageenan, manufactured by Saneigen FFI Co., Ltd., trade name "Carrageenin CS-558".
D-4: Guar gum, manufactured by Sansho Co., Ltd., trade name "GRINDSTED GUAR175".
D-5: Carboxymethyl cellulose, manufactured by Lion Corporation, trade name "Leoguard GP".
D-6: Catified cellulose, manufactured by Lion Corporation, trade name "XE-511K".
D-7: Polyvinyl alcohol, manufactured by Kuraray Co., Ltd., trade name "Kuraray Poval PVA-217".
D-8: Polyethylene glycol, manufactured by Lion Corporation, trade name "PEG # 1000".

<Other ingredients>
pH adjuster: 1N sodium hydroxide, 1N hydrochloric acid, (manufactured by Kanto Chemical Co., Inc.).

<Examples 1 to 20, Comparative Examples 1 to 7>
According to the composition shown in Tables 1 to 3, the components (A) to (D) are added to water and mixed, and then the pH is adjusted to the value in the table with a pH adjuster to adjust the pH to the value in the table, and the liquid cleaning agent for bathroom of each example. Got
In addition, Examples 13 , 18, and 20 are reference examples.
Tables 1 to 3 show the compositions (blending components, content (mass%)) of the obtained liquid cleaning agents for bathrooms of each example. Unless otherwise specified, mass% indicates 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 cleaning agent of 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 (mass%) of all the blended components contained in the bathroom liquid cleaning agent is 100% by mass.

<Viscosity measurement method>
For the bathroom liquid cleaning agents of each example, the kinematic viscosity when using a thin tube viscometer and the viscosity when using a B-type viscometer were measured as follows.
[Kinematic viscosity measured with a thin tube viscometer]
The sample was adjusted to 25 ° C, and the kinematic viscosity was measured with an automatic kinematic viscosity measuring device (manufactured by Tanaka Kagaku Kikai Seisakusho Co., Ltd.) as a thin tube viscometer (JISZ8803 (2011: Viscosity measurement method using a thin tube viscometer) Compliant with).
The measurement results are shown in Tables 1 to 3.

<Evaluation method of liquid cleaning agent for bathroom>
For the bathroom liquid cleaning agents of each example, the cleaning power on a vertical surface and the cleaning power on a horizontal surface were evaluated as follows.
The evaluation results are shown in Tables 1 to 3.

[Evaluation of detergency on vertical surfaces]
After fixing a glass fiber reinforced plastic (FRP) test piece (10 cm x 10 cm) on the inner wall of the bathtub in a general household, three adult men each take a bath three times (one bath per day is repeated for three days). During that time, only the bath water was replaced, and the bathtub was used without washing), and dirt was attached to 10 places on the surface of the test piece.
After the dirty test piece is sufficiently dried, the bathroom detergent of each example is applied linearly to the upper part of the test piece, tilted to 90 ° C and left for 1 minute, and then rinsed with tap water (15 ° C). did. The test piece was sufficiently dried. The state of removal of dirt from 10 places on the surface of the dried test piece was evaluated visually and by touch according to the following evaluation criteria for detergency. In the following evaluation criteria, ◎ and ○ were accepted. As the 10 locations on the surface of the test piece, 10 locations located on the entire surface of the test piece at substantially even intervals were selected.
[Evaluation criteria for detergency]
⊚: Very good stain removal [Cleaning agent spreads evenly over the entire surface of the test piece, 8 or more of the 10 test piece surfaces, no visual stains are observed, and 8 or more on the entire surface of the test piece. You can get a smooth touch].
◯: Good stain removal [Cleaning agent spreads almost all over the surface of the test piece, 5 or more of the 10 parts on the surface of the test piece are not visually observed, and the entire surface of the test piece is smooth to the touch. However, at least 3 of the 10 test piece surfaces feel a rough touch on the test piece].
Δ: Almost no stains are removed [The cleaning agent spreads on about half of the surface of the test piece, and 6 or more of the 10 parts on the surface of the test piece are visually stained, and a rough touch is felt. The visual stains and rough touch are reduced compared to before cleaning].
×: Dirt does not come off at all [The cleaning agent does not spread evenly on the surface of the test piece, and out of 10 parts on the surface of the test piece, stains are visually observed at 10 places, and a rough touch is felt. The visual stains and rough touch are the same as before cleaning]
The evaluation results are shown in the column of detergency on the vertical surface in Tables 1 to 3.
Further, among the 10 places on the surface of the test piece, the number of places where dirt removal was confirmed is shown in the column of dirt removal points in Tables 1 to 3.

[Evaluation of detergency on a horizontal surface]
After fixing a glass fiber reinforced plastic (FRP) test piece (2 cm x 10 cm) on the inner wall of the bathtub in a general household, three adult men each take a bath three times (one bath per day is repeated for three 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 was sufficiently dried, the test piece was placed horizontally. Then, the bathroom liquid cleaning agent of each example was dropped onto the test piece so that the entire surface was wet, left for 5 minutes, and then rinsed with tap water (15 ° C.). The test pieces were sufficiently dried, and the state of removal of dirt on the surfaces of the five test pieces was evaluated visually and by touch according to the following evaluation criteria for detergency. In the following evaluation criteria, ◎ and ○ were accepted.
[Evaluation criteria for detergency]
⊚: 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].
◯: 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. At least one feels a rough touch on the test piece].
Δ: Almost no stains were removed [Of the five test pieces, three were visually observed to have a rough touch, but the visual stains and the rough touch were not found. It is less than before cleaning].
X: Dirt does not come off at all [Of the five test pieces, visual stains were observed on all five pieces, and all five pieces felt a rough touch, and the visual stains and the rough touch were washed. Same as before].
The evaluation results are shown in the columns of detergency (5 minutes) on the horizontal surface in Tables 1 to 3.

Further, in the evaluation of the detergency on the horizontal surface, the detergency was evaluated in the same manner as described above by changing the leaving time after dropping the liquid cleaning agent for bathroom on the test piece from 5 minutes to 10 minutes. ..
The evaluation results are shown in the columns of detergency (10 minutes) on the horizontal surface in Tables 1 to 3.

From the results shown in Tables 1 to 3, it can be confirmed that the bathroom liquid cleaning agents of Examples 1 to 20 to which the present invention is applied have excellent cleaning power on a vertical surface and also good cleaning power on a horizontal surface. It was. The reason why the cleaning power is excellent on the vertical surface is that the cleaning agent has excellent adhesion retention and spreadability, so that the cleaning agent spreads evenly on the vertical surface without dripping, and thus the cleaning power on the vertical surface. It is presumed that it was because it demonstrated.
On the other hand, the bathroom liquid cleaning agent (Comparative Example 1) containing no component (D) did not provide sufficient cleaning power on a vertical surface.
The bathroom liquid cleaning agents (Comparative Examples 2 and 3) whose kinematic viscosities do not meet the scope of the present invention did not have sufficient cleaning power on a vertical surface.
The bathroom liquid cleaning agent (Comparative Example 4) containing no component (a1) did not provide sufficient cleaning power on a vertical surface.
The bathroom liquid cleaning agent (Comparative Example 5), which does not contain the component (D) and whose kinematic viscosity does not meet the range of the present invention, did not provide sufficient cleaning power on a vertical surface.
The bathroom liquid cleaning agent (Comparative Example 6) containing no component (C) did not provide sufficient cleaning power on a vertical surface and a horizontal surface.
The bathroom liquid cleaning agent (Comparative Example 7) containing no component (B) did not provide sufficient cleaning power on a vertical surface and a horizontal surface.
From the above results, it was confirmed that the liquid cleaning agent for bathroom to which the present invention was applied has excellent cleaning power even on the vertical surface of the bathtub.

Claims (3)

Component (A): A surfactant containing a polyoxyalkylene type nonionic surfactant (a1), and
Component (B): Glycol solvent and
Component (C): Aminocarboxylic acid type chelating agent and
Ingredient (D): At least one water-soluble polymer selected from the group consisting of xanthan gum, gellan gum, carrageenan, guar gum, carboxymethyl cellulose, cationized cellulose, polyvinyl alcohol, and polyethylene glycol.
Contains,
The mass ratio represented by the component (C) / component (a1) is 0.6 to 3.
The kinematic viscosity measured with a thin tube viscometer at 25 ° C. is 1.5 to ²⁰ mm ² / s.
The content of the component (A) is 0.1 to 6.0% by mass.
The content of the component (a1) in the component (A) is 40 to 85% by mass.
The content of the component (B) is 0.1 to 5.0% by mass.
The content of the component (C) is 0.2 to 8.0% by mass.
The content of component (D) is 0.01 to 0.10% by mass is,
PH at 25 ° C. is Ru der less than 12 greater than 10, bathroom liquid cleaning agent. The liquid cleaning agent for a bathroom according to claim 1, wherein the component (B) is diethylene glycol monobutyl ether. The liquid cleaning agent for a bathroom according to claim 1 or 2, wherein the component (A) further contains a non-soap-based anionic surfactant (a2).