JP6584004B2 - Bathtub cleaning method using liquid detergent in foam discharge container for bathroom - Google Patents

Description

  The present invention relates to a container-containing cleaning agent for bathrooms and a bathtub cleaning method using the same.

The bathroom is usually washed by a sponge impregnated with a liquid detergent for the bathroom, and by scrubbing the bathroom wall surface, bathtub surface, and other bathroom accessories.
In scrubbing, the object to be cleaned is rubbed directly with a sponge.For example, when washing a bathtub, the entire surface of the bathtub must be rubbed with a sponge by bending forward, lying down, or squatting. And the physical burden is large.

  Conventionally, a cleaning agent for reducing the labor and physical burden of such bathroom cleaning has been proposed. 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 spraying the above-mentioned bathtub aerosol cleaner onto the remaining hot water surface of the bathtub and spreading it on the hot water surface, the bathtub is unplugged. A method of cleaning a bathtub is disclosed in which the remaining hot water is discharged and the cleaning component spread on the surface of the hot water is dropped to adhere to the side and bottom surfaces of the bathtub and then washed away by a shower or the like.

However, since the cleaning agent disclosed in Patent Document 1 is poorly water-soluble, it is difficult for bubbles to be discharged from the bathtub wall surface or the drainage port (that is, inferior in rinsing properties).
As a method for improving the rinsing property, it is conceivable to replace the poorly water-soluble solvent in the cleaning agent with a water-soluble solvent to increase the water solubility of the cleaning agent. However, in this case, the cleaning agent immediately diffuses in water, and the bubbles are likely to disappear (that is, the foam retention property is poor). If the foam retainability is not sufficient, the foam disappears before it reaches the entire bath wall surface, and the cleaning component cannot act on the dirt adhering to the bath wall surface, so that sufficient cleaning power cannot be obtained.

JP 2000-108991 A

  This invention is made | formed in view of the said situation, and it aims at the cleaning agent with the container for bathrooms which is excellent in the holding | maintenance and detergency of foam, and is excellent in a rinse property.

As a result of intensive studies, the present inventors have found that the following container-containing cleaning agents for bathrooms can solve the above problems.
That is, in the bathroom container cleaning agent of the present invention, the liquid cleaning agent is filled in a foam discharge container, and the liquid cleaning agent is (A) component: surfactant 0 containing non-soap anionic surfactant. 0.1 to 10% by mass, (B) component: water-soluble solvent, (C) component: aminocarboxylic acid type chelating agent, and (D) component: water-soluble polymer, and 25 ° C. The foam discharge container is capable of discharging the liquid cleaning agent as 100 mL / 20 g or more and 200 to 1000 mPa · s foam under the condition of 20 ° C.
In addition, the container-containing cleaning agent for the bathroom discharges the liquid cleaning agent as foam from the foam discharge container, and the foam adheres to the water line on the inner wall in the bathtub or the area above the water line. Then, it is preferably used in a bathtub washing method for discharging water from the bathtub.

  ADVANTAGE OF THE INVENTION According to this invention, the washing | cleaning agent with the container for bathrooms which is excellent in the retainability and detergency of foam, and excellent in the rinse property can be provided.

The bathroom cleaning agent for the bathroom of the present invention (hereinafter also simply referred to as “container cleaning agent”) is obtained by filling a foam discharge container with a liquid cleaning agent.
(Liquid cleaning agent)
The liquid cleaning agent filled in the container cleaning agent of the present invention is a composition containing the following components (A) to (D).

<(A) component>
The component (A) is a surfactant containing a non-soap anionic surfactant (a1) and is used for imparting detergency to the liquid detergent.
In the present invention, the non-soap anionic surfactant (a1) is an anionic surfactant excluding a 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 (a1), or may be composed of the component (a1) and a surfactant other than this.

Examples of the component (a1) 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 of: sulfate type anionic surfactants such as linear or branched alkyl sulfates (AS), alkyl ether sulfates or alkenyl ether sulfates (AES); alkyl ether carboxylates, Carboxylic acid type anionic surfactants such as polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, acylaminocarboxylates; alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate salts, poly Oxyalkylene alkylphenyl phosphate Ester salts, phosphoric acid ester type anionic surfactants such as glycerol fatty acid ester monophosphate ester salts.
Among these, a sulfonic acid type anionic surfactant, a sulfate ester type anionic surfactant, and a carboxylic acid type anionic surfactant are preferable, and a sulfonic acid type anionic surfactant is more preferable.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt, and ammonium salts. Among these, alkali metal salts are preferable.

Among these, the α-olefin sulfonate is preferably one having 10 to 20 carbon atoms, and more preferably one having 10 to 16 carbon atoms.
As the linear alkylbenzene sulfonate, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is more preferable.
As the alkanesulfonate, a secondary alkanesulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms is preferable.
The α-sulfo fatty acid ester salt is preferably an α-sulfo fatty acid ester salt having 10 to 20 carbon atoms, preferably 10 to 18 carbon atoms.
As the alkyl sulfate, those having 10 to 20 carbon atoms are preferable, and those having 10 to 16 carbon atoms are more preferable.
Examples of the alkyl ether sulfate or alkenyl ether sulfate include 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 moles of ethylene oxide added thereto. Or polyoxyethylene alkenyl ether sulfate is preferable.
As the polyoxyalkylene ether carboxylate, a polyoxyethylene alkyl ether carboxylate having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and added with an average of 1 to 10 moles of ethylene oxide or Polyoxyethylene alkenyl ether carboxylates are preferred.

  Of these, α-olefin sulfonates, linear alkylbenzene sulfonates, α-sulfo fatty acid ester salts, and alkyl sulfates are preferred because of their excellent foam retention and excellent detergency against sebum and protein stains. Α-olefin sulfonate is more preferable.

As the component (a1), any one type may be used alone, or two or more types may be used in combination.
The content of the component (a1) is preferably 0.1 to 10% by mass, more preferably 1.0 to 5.0% by mass, and 1.0 to 3.0% by mass with respect to the total mass of the liquid detergent. % Is more preferable. If the content of the component (a1) is less than 0.1% by mass, sufficient foam retention and detergency may not be obtained. When the content of the component (a1) exceeds 10% by mass, the rinsing property may be lowered.

(A) 50-100 mass% is preferable and, as for content of (a1) component in a component, 80-100 mass% is more preferable.
When the content of the component (a1) in the component (A) is in the above range, the foam retention and the cleaning power are more likely to be enhanced.

The component (A) may contain a surfactant other than the component (a1) (hereinafter also referred to as optional surfactant (a2)).
The optional surfactant (a2) is not particularly limited, and examples thereof include higher fatty acid salts, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
The component (A) preferably does not contain the component (a2) 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, stearate, or a mixture thereof, coconut oil fatty acid salt, hydrogenated 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, alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt, and ammonium salts.

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

  Examples of amphoteric surfactants include alkyl carboxy betaines, alkyl sulfo betaines, alkyl hydroxy sulfo betaines, alkyl amide betaines, imidazolinium betaines, and the like.

  Nonionic surfactants include higher alcohols, alkylphenols, polyoxyalkylene type nonionic surfactants obtained by adding alkylene oxide to higher fatty acids or higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamides, polyhydric alcohols. Fatty acid ester or its alkylene oxide adduct, fatty acid polyglycerin 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 Examples include polyglycosides and glyceryl ethers.

As the component (a2), any one type may be used alone, or two or more types may be used in combination.
When the component (a2) is contained in the component (A), the content of the component (a2) is preferably 0.1 to 5.0% by mass with respect to the total mass of the liquid detergent, and is 1.0 to 3 0.0 mass% is more preferable. When the content of the component (a1) is in the preferred range, a good balance between foam retention and rinsing properties can be easily maintained.

  The content of the component (A) is preferably 0.1 to 10% by mass, more preferably 1.0 to 5.0% by mass, and 1.0 to 3.0% by mass with respect to the total mass of the liquid detergent. % Is more preferable. When the content of the component (A) is less than 0.1% by mass, sufficient foam retention and detergency may not be obtained. When content of (A) component exceeds 10 mass%, there exists a possibility that rinse property may fall.

<(B) component>
(B) A component is a water-soluble solvent. In the present invention, the water-soluble solvent refers to a solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.

  Examples of the component (B) include ethylene glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, propylene glycol solvents such as propylene glycol, dipropylene glycol and tripropylene glycol, glycerin such as glycerin and diglycerin, or the like Derivatives, 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, diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, triethylene glycol Monochuchi Ethylene glycol ethers such as ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol ethers such as tripropylene glycol monomethyl ether, butylene glycol, and the like.

As the component (B), ethylene glycol solvents, propylene glycol solvents, ethylene glycol ethers, and propylene glycol ethers are preferable.
Among these, as the component (B), ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether are preferable, and diethylene glycol monobutyl ether is more preferable. .

As the component (B), any one type may be used alone, or two or more types may be used in combination.
(B) 1.0-18 mass% is preferable with respect to the total mass of a liquid detergent, and, as for content of a component, 7.0-15 mass% is more preferable. When the content of the component (B) is less than 1.0 mass, sufficient cleaning power may not be obtained. When the content of the component (B) is more than 18% by mass, sufficient foamability and foam retention may not be obtained.

<(C) component>
The component (C) is an aminocarboxylic acid type chelating agent.
In the present invention, by using the component (C) under alkaline conditions where the pH at 25 ° C. is more than 10 and less than 12, the detergency against fatty acid metal salts and sebum / protein stains adhering to the bathtub or the like can be enhanced.
As the component (C), methyl glycine diacetate (MGDA), aspartate diacetate (ASDA), isoserine diacetate (ISDA), β-alanine diacetate (ADAA), serine diacetate (SDA), glutamate diacetate (GLDA), Iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetrapropionic acid, N-lauroylethylenediaminetriacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetrimethyl Acetic acid (HEDTA), triethylenetetraamine hexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH), hydroxye Examples include leniminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), glycol ether diamine tetraacetic acid (GEDTA), dicarboxymethyl glutamic acid (CMGA), (S, S) -ethylenediamine disuccinic acid (EDDS), and salts thereof. It is done.
Among these, ethylenediaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, and ethylenediaminetetrapropionic acid are preferable, and ethylenediaminetetraacetic acid is more preferable.

As the component (C), any one type may be used alone, or two or more types may be used in combination.
The content of the component (C) is preferably 0.2 to 5.0% by mass with respect to the total mass of the liquid detergent.
When the content of the component (C) is in the above preferred range, the cleaning power and rinsing properties are more likely to be enhanced. When the content of the component (C) is less than 0.2% by mass, the detergency tends to decrease. When content of (C) component exceeds 5.0 mass%, there exists a tendency for rinse property to fall.

<(D) component>
The component (D) is a water-soluble polymer. In the present invention, the combined use of the component (D) and the above-described component (B) suppresses the foam discharged from the foam discharge container from diffusing into water, and improves the foam retention. .
In the present invention, the polymer means a polymer having a weight average molecular weight of 1000 or more. The weight average molecular weight is a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent based on a calibration curve in PEG (polyethylene glycol). Further, the water-soluble polymer is obtained by adding 10 g of a polymer to 1000 g of water at 40 ° C. in a 1 liter beaker and stirring (200 rpm) for 12 hours with a stirrer (thickness 8 mm, length 50 mm). What is dissolved.

As component (D), natural polysaccharide polymers represented by guar gum, gellan gum, xanthan gum, etc .; cellulose polymers such as hydroxyethyl cellulose and hydroxypropyl cellulose; pyrrolidone polymers such as polyvinylpyrrolidone and N-alkylpyrrolidone A polyalkylene glycol polymer such as polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol copolymer; and a polyvinyl polymer such as polyvinyl alcohol and polyvinyl acetate.
Moreover, a polymer electrolyte may be used as the component (D). Examples of polyelectrolytes include 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 these Amphoteric polymers; anionic, cationic, and amphoteric polysaccharide homopolymers, copolymers, and salts thereof; anionic, cationic, and amphoteric polysaccharide derivatives; anionic, cationic, and amphoteric polypeptide homopolymers; Copolymers and their salts; anionic, click , 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 derived proteins, gelatin, lignosulfonic acid homopolymers, copolymers, and salts thereof; ionene homopolymers, copolymers, and salts thereof; anionic, cationic, and amphoteric polyester homopolymers, copolymers Anionic, cationic, and amphoteric polyurethane homopolymers, copolymers, and salts thereof; combinations of listed homopolymers, copolymers, and copolymers of these salts; ionic and nonionic micelles Listed Polymers, copolymers, and combinations of stoichiometric and non-stoichiometric interpolymers of these salts; listed homopolymers, copolymers, and polymer matrices of these salts; listed homopolymers, copolymers, And the physical blends of these salts; the listed homopolymers, copolymers, and salts thereof, and combinations thereof, onto which anionic, cationic, and amphoteric components are grafted.

Among these, natural polysaccharide polymers are preferable from the viewpoint of rinsing properties. Among natural polysaccharide polymers, xanthan gum is preferable.
As the component (D), any one type may be used alone, or two or more types may be used in combination.
(D) 0.02-1.0 mass% is preferable with respect to the total mass of a liquid detergent, and, as for content of a component, 0.05-1.0 mass% is more preferable. When the content of the component (D) is less than 0.02% by mass, foamability and foam retention may be impaired. As a result, sufficient cleaning power may not be obtained. If the content of the component (D) is more than 1.0% by mass, the rinsing property may be lowered.

The mass ratio represented by (B) component / (D) component [the mass ratio of the content of (B) component to the content of (D) component, hereinafter also referred to as “B / D ratio”] is 20 to 20 350 is preferable and 100 to 200 is more preferable.
When the B / D ratio is in the above preferable range, the foaming property and the foam retention property are further improved. As a result, for example, when the foam is discharged from the foam discharge container of the container-containing cleaning agent of the present invention onto the remaining hot water surface of the bathtub to perform cleaning, a sufficient amount of foam can be spread on the inner wall of the bathtub. Good detergency can be obtained.
When the B / D ratio is less than 20 or more than 350, it is difficult to obtain sufficient foaming properties and foam retention.

The mass ratio represented by (C) component / (A) component [the mass ratio of the content of (C) component to the content of (A) component, hereinafter also referred to as “C / A ratio”] is 0. It is 6-6.0, 0.6-5.0 are preferable and 0.6-3.0 are more preferable.
In the present invention, by setting the C / A ratio within the above range, an excellent detergency against fatty acid metal salts, sebum and protein stains attached to a bathtub or the like can be obtained, and good rinsing properties can be easily obtained. . In particular, when the bathtub is washed without rubbing, the liquid detergent is applied to the entire surface of the bathtub, so that the amount of the detergent used increases. By setting the C / A ratio within the above range, good rinsing properties can be easily obtained even when the amount of cleaning agent used is increased.

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

<Optional component>
In addition to the above components, the liquid cleaning agent of the present invention can usually contain components that can be used in the cleaning agent as necessary. Examples of such optional components include bactericides, antiseptics, antifungal agents, dyes, antioxidants, thickeners (however, (D) component is not included), ultraviolet absorbers, solubilizers (however, (B) a component is not included), a fragrance | flavor, a pH adjuster, etc. are mentioned.

The pH adjuster is not particularly limited, but is selected from inorganic acids such as hydrochloric acid and sulfuric acid, 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 alkali agent selected from 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 sodium hydroxide and potassium hydroxide.
Any one of the pH adjusting agents may be used alone, or two or more may be used in combination.

The liquid detergent of the present invention has a pH at 25 ° C. of more than 10 and less than 12. When the pH is within the above range, good detergency can be obtained for fatty acid metal salts, sebum and protein stains adhering to a bathtub or the like. The pH of the liquid detergent of the present invention is preferably 10.1 to 11.4, more preferably pH 10.4 to 11.4.
In addition, pH of the liquid cleaning agent of this invention is the value measured in 25 degreeC by JISZ8802: 2011.

The liquid detergent of the present invention preferably has a viscosity at 25 ° C. of 1 to 100 mPa · s, and more preferably 1 to 50 mPa · s.
If the viscosity in 25 degreeC is more than the said lower limit, the adhesiveness of the liquid cleaning agent with respect to washing | cleaning objects, such as a bathtub, will improve more. If the viscosity at 25 ° C. is not more than the above upper limit value, the liquid detergent can be easily discharged from the foam discharge container, and the handleability becomes good.

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

(Foam discharge container)
The container-containing cleaning agent of the present invention is a foam discharge container filled with the above-described liquid cleaning agent.
The foam discharge container is a foam having a capacity of 100 mL / 20 g or more and a viscosity of 200 to 1000 mPa · s under the condition of 20 ° C. when the liquid cleaning agent is discharged from the foam discharge container. Although it will not specifically limit if it can discharge, For example, containers, such as a squeeze foamer type which presses and discharges the trunk | drum of a soft container, and a pump former type which discharges with a press pump, are mentioned.
The volume of foam (the volume of foam per unit mass) is 100 mL / 20 g or more, preferably 150 mL / 20 g or more, more preferably 250 mL / 20 g or more under the condition of 20 ° C. When the volume of the foam is not less than the above lower limit value, the discharged foam does not disappear over a long period of time, and the cleaning component can easily act on the dirt adhering to the object to be cleaned.
The foam has a viscosity of 200 to 1000 mPa · s, preferably 200 to 600 mPa · s, at 20 ° C. When the foam viscosity is less than 200 mPa · s, sufficient foam retention and foamability cannot be obtained. When the viscosity of the foam is more than 1000 mPa · s, sufficient foaming property, foam retention property and rinsing property cannot be obtained.
The foam volume and the foam viscosity are appropriately adjusted by adjusting the blending component and blending ratio of the liquid detergent or by adjusting the foaming mechanism in the foam discharge container.

Among the squeeze foamer type and pump foamer type containers, the foam discharge container of the present invention is preferably a container provided with a porous film body in a foaming mechanism. Examples of such a container include a container having a single layer or a plurality of layers of a porous film body having a thickness of about 0.1 to 2 mm, such as a sponge, a sintered body, or a net (for example, a single layer or a plurality of layers). No. 52-16567, No. 58-174272, No. 3-7963, No. 6-32346, No. 7-215352, No. 9-118352, etc. ). The mesh size of the porous membrane is preferably 50 to 500 mesh, particularly preferably 150 to 400 mesh. Moreover, as a material of the said porous membrane body, plastic materials, such as nylon, polyester, polyolefin, are preferable.
Moreover, as a foam discharge container, a pressure accumulation type discharge container and a pressurization type discharge container are preferable from the point of being convenient. By using these containers, the content liquid in the container body can be continuously discharged. The pressure-accumulation type discharge container includes, for example, a cylindrical cylinder body that is detachably attached to the bottom of the container body, a piston body that is provided in the cylinder body, and a piston body that is added according to sliding of the piston body in the cylinder body. There is a pressure accumulation type sprayer provided with a valve mechanism for introducing compressed air into the container body. As a pressurized discharge container, the content liquid stored in the container is pressurized with a pump, and the pressurized content liquid and air are introduced into the spray device main body from the introduction tube and bubbles are generated from the nozzle part. Examples thereof include a pressure spray device that ejects in a shape. Examples of the pressurizing spray device include a device in which a porous body made of an elastic material is provided in the nozzle portion so as to be expandable and contraction, and a pressure adjusting valve for keeping the pressure in the container constant is provided in the introduction pipe. In particular, it is preferable that a through hole for taking in the air in the container body is formed in the middle of the flow path of the content liquid.

As a method of using the container-containing cleaning agent of the present invention, for example, after foam is discharged from a foam discharge container and attached to a cleaning object such as a bathroom wall surface, a bathtub surface, or other bathroom accessory equipment, the foam How to scrub with a sponge, etc., after using a foam discharge container to attach the foam to the object to be cleaned, rinse it with a shower after a certain period of time, etc. Is mentioned.
In addition, as a method of adhering foam to the object to be cleaned, a method in which the foam discharged from the foam discharge container is directly attached to the object to be cleaned, and foam is discharged from the foam discharge container onto the surface of the remaining hot water in the bathtub. And a method of causing the bubbles to diffuse on the surface of the hot water and adhere to the inner wall of the bathtub to be cleaned.

Among them, the container-containing cleaning agent of the present invention discharges the liquid cleaning agent as bubbles from the foam discharge container, and directly attaches the bubbles to the water line on the inner wall of the bathtub in which water is put or the region above the water line. Then, it is preferably used for a washing method of a bathtub for discharging water from the inside of the bathtub. In this cleaning method, water is discharged from the bathtub and the water line is lowered, and bubbles attached to the water line or a region above the water line are also lowered. The container-containing cleaning agent of the present invention has excellent foam retention, so that the foam remains on the inner wall of the bathtub without disappearing for a long period of time (for example, until it is discharged from the drain of the bathtub) and is attached to the inner wall. The cleaning component of the liquid cleaning agent can act on the liquid. Thereby, a sufficient cleaning effect can be obtained. In the cleaning method, the foam or liquid cleaning agent remaining in the bathtub is then rinsed with a shower or the like and discharged from the drain outlet of the bathtub.
In such a cleaning method, the inner wall of the bathtub can be washed without rubbing, so that the labor of washing is not required and the physical burden is reduced. Furthermore, since the container-containing cleaning agent of the present invention has excellent detergency and excellent foam retention, bubbles are sufficiently adhered to the inner wall of the bathtub until all the water in the bathtub is discharged. And a better cleaning effect can be obtained. Furthermore, since the container-containing cleaning agent of the present invention is excellent in rinsing properties, rinsing properties when rinsing with a shower or the like are good, and the time required for rinsing is reduced.

As described above, the container-containing cleaning agent of the present invention is filled with a specific liquid cleaning agent, and since the liquid cleaning agent can be discharged as a specific bubble, the foam retention and cleaning power are improved, Moreover, it is excellent in rinsing properties.
In particular, since the container-containing cleaning agent of the present invention is excellent in foam retention and detergency and excellent in rinsing properties, it is suitably used for a method of “washing without rubbing”. Especially, it is used suitably for the washing | cleaning method which makes liquid cleaning agent adhere as a bubble on the waterline of the inner wall in a bathtub, or the area | region above a waterline, and discharges the water in the said bathtub.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In this example, “%” indicates “% by mass” unless otherwise specified.
The raw materials used in this example are as follows.

<(A) component>
A1-1: AOS, sodium α-olefin sulfonate (sodium α-olefin sulfonate having 14 carbon atoms), manufactured by Lion Corporation, trade name “Lipolane LJ441”.
A1-2: LAS, linear alkylbenzene sulfonate [alkyl group having 10 to 16 carbon atoms], manufactured by Lion Corporation, trade name “Lypon PS-230”.
A1-3: AES, polyoxyethylene alkyl ether sulfate [alkyl group having 12 to 14 carbon atoms, average addition mole number of ethylene oxide of 2]. New Nippon Rika Co., Ltd., trade name Sinoline SPE-1250.
A1-4: MES, α-sulfo fatty acid methyl ester salt (α-sulfo fatty acid methyl ester salt having a fatty acid residue of 16 to 18 carbon atoms), manufactured by Lion Corporation, trade name “MIZULAN FL-80”.
A1-5: SDS, lauryl sulfate, manufactured by Lion Corporation, trade name “SUNNOL LM-1130”.

<(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 Nippon Emulsifier Co., Ltd., trade name “benzyl diglycol”.
B-3: Diethylene glycol monomethyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name “methyl diglycol”.
B-4: Dipropylene glycol monomethyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name “methylpropylene diglycol”.
B-5: Diethylene glycol monoethyl ether, manufactured by Dow Chemical Japan Co., Ltd.
B-6: Propylene glycol monopropyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name “propylpropylene glycol”.
<(B ′) component, (B) component comparison component>
B′-1: Dipropylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name “butyl propylene diglycol”.

<(C) component>
C-1: Disodium ethylenediaminetetraacetate (EDTA2Na), manufactured by Akzo Nobel Co., Ltd., trade name “Disorbin NA2”.

<(D) component>
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 (CMC), manufactured by Lion Corporation, trade name “Leoguard GP”.
D-6: Cationized cellulose, manufactured by Lion Corporation, trade name “XE-511K”.
D-7: Polyvinyl alcohol (PVA), manufactured by Kuraray Co., Ltd., trade name “Kuraray Poval PVA-217”.
D-8: Polyethylene glycol (PEG), manufactured by Lion Corporation, trade name “PEG # 1000”.
<Other ingredients>
pH adjusting agent: 1N sodium hydroxide, 1N hydrochloric acid (manufactured by Kanto Chemical Co., Inc.).

(Liquid cleaning agent)
According to the composition shown in Tables 1 to 4, the components (A) to (D) were added to water and mixed, and then the pH was adjusted to the value in the table with a pH adjuster to produce a liquid detergent.
(Foam discharge container)
A foam discharge container was manufactured by attaching a pressurized spray head (manufactured by Maruhachi Sangyo) to a plastic container for carbonated beverages having a capacity of 500 mL.

<Examples 1-24, Comparative Examples 1-9>
The foam discharge container was filled with a liquid cleaning agent to produce a container-containing cleaning agent in each example.
The compositions (formulation components, content (mass%)) of the liquid detergent in the container-containing detergent of each example obtained are shown in Tables 1 to 4. In addition, unless otherwise indicated, mass% shows a pure part.
In the table, when there is a blank blending component, the blending 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 liquid cleaning agent of each example to the value in the table.
In the table, the water content “balance” means the remainder added so that the total amount (mass%) of all the ingredients contained in the liquid detergent is 100 mass%.
In the table, “B / D ratio” of Comparative Example 3 indicates a mass ratio of the component (B ′) to the component (D).

(Evaluation method for detergent in containers)
About the container-containing cleaning agent of each example, the viscosity of foam and the volume of foam were measured as follows. The measurement results are shown in Tables 1 to 4.
Moreover, about the cleaning agent in a container of each example, the foam retention property, the cleaning power, and the rinse property were evaluated as follows. The evaluation results are shown in Tables 1 to 4.

<Measurement method of foam viscosity>
A foam discharge container was filled with 20 g of the liquid cleaning agent of each example adjusted to 20 ° C. using a thermostatic bath. Next, about 100 mL of foam was discharged into a 200 mL beaker. The foam was allowed to stand for 1 minute, and then its viscosity was measured with a B-type viscometer (manufactured by TOKIMEC) (rotor No. 2, rotational speed 60 rpm, measured after 10 revolutions). The said measurement was performed 5 times and the average value was made into the viscosity of the foam discharged from the foam discharge container of the container-containing cleaning agent of each case.

<Method for measuring foam volume>
A foam discharge container was filled with 20 g of the liquid cleaning agent of each example adjusted to 20 ° C. using a thermostatic bath. After pressurizing the pressure cylinder of the foam discharge container 20 times, the foam was sprayed until no foam was discharged from the foam discharge container. The volume of the discharged foam was measured with a graduated cylinder. The said measurement was performed 5 times and the average value was made into the capacity | capacitance of a foam (volume of the foam per unit mass). The foam capacities measured in Tables 1 to 4 are shown according to the following criteria.
[Measurement result of foam volume]
A: 250 mL or more (250 mL / 20 g or more).
○: 150 mL or more and less than 250 mL (150 mL / 20 g or more and less than 250 mL / 20 g).
Δ: 100 mL or more and less than 150 mL (100 mL / 20 g or more and less than 150 mL / 20 g).
X: Less than 100 mL (less than 100 mL / 20 g).

<Evaluation method of foam retention>
A foam discharge container was filled with 20 g of the liquid cleaning agent of each example adjusted to 20 ° C. using a thermostatic bath. The pressure cylinder of the foam discharge container was pistoned 20 times and pressurized. Next, water at 40 ° C. is poured to about half of a cylindrical container having a diameter of 35 cm and a height of 60 cm. After the foam is discharged and adhered along the water line of the inner wall of the cylindrical container, the foam disappears completely. The time to do was measured. Note that the entire amount (20 g) of the liquid cleaning agent filled in the foam discharge container was discharged. The said measurement was performed 5 times, the average value was classified according to the following evaluation criteria, and the foam retention property was evaluated. ◎ and ○ were accepted.
[Evaluation criteria for foam retention]
A: More than 3 minutes.
○: 1 minute or more and less than 3 minutes.
Δ: 30 seconds or more and less than 1 minute.
X: Less than 30 seconds.

<Evaluation of cleaning power>
Three adult men bathe three times each on the inner wall surface of an ordinary household bath (repeat once a day for three days, replace only the bath water, and use the bathtub without washing). Dirt was attached to the surface. Without removing the hot water in the bathtub, bubbles were allowed to adhere to the entire inner wall surface of the bathtub so as to cover all the water lines on the inner wall surface of the bathtub with bubbles. The liquid cleaning agent discharged from the foam discharge container was 40 g. Thereafter, the hot water was immediately discharged, and left for 1 minute after all the hot water was discharged. Then, it was rinsed with tap water (15 ° C.). After sufficiently drying the inside of the bathtub, a residual protein detection solution (manufactured by Albose Co., Ltd.) was applied to the entire inner wall surface of the bathtub and left for 1 minute. Rinsing was performed with tap water (15 ° C.), and the colored state in the bathtub was visually observed. The said measurement was performed 5 times, the average value was classified according to the following evaluation criteria, and the cleaning power was evaluated. A score of 4 or more was accepted.
[Evaluation criteria for cleaning power]
5 points: Not colored (it is difficult to determine whether it is colored or not even if observed well).
4 points: When observed well, it can be seen that it is colored.
3 point: It turns out that it has colored lightly.
2 points: Slightly thinner than unwashed but clearly colored.
1 point: It is colored to the same extent as unwashed.

<Rinse evaluation>
After 40 g of liquid cleaning agent is discharged as foam from the foam discharge container onto the entire surface of the bathtub and adhered to the inner wall of the bathtub, it is rinsed with tap water using a shower (water temperature 15 ° C., flow rate 0.2 L) / Second), the time until the foam completely disappeared from the drain of the bathtub was measured. The said measurement was performed 5 times, the average value was classified according to the following evaluation criteria, and rinse property was evaluated. ◎ and ○ were accepted.
[Evaluation criteria for rinsability]
A: Less than 40 seconds.
○: 40 seconds or more and less than 50 seconds.
Δ: 50 seconds or more and less than 60 seconds.
X: 60 seconds or more.

From the results shown in Tables 1 to 4, it was confirmed that the container-containing cleaning agents of Examples 1 to 24 to which the present invention was applied were excellent in foam retention and cleaning power and excellent in rinsing properties.
On the other hand, a container-containing detergent not containing component (A) (Comparative Example 1), a container-containing detergent not containing component (B) (Comparative Example 2), and a container-containing detergent not containing (D) (Comparative Example 5) ), The container-containing cleaning agent (Comparative Example 8) in which the viscosity of the discharged foam was less than 200 mPa · s was insufficient in foam retention and cleaning power.
(B) In-container cleaning agent (Comparative Example 3) using the component (B ′) instead of the component, and in-container cleaning agent (Comparative Example 9) in which the viscosity of the discharged foam is more than 100 mPa · s The retention and cleaning power were not sufficient, and the rinsing properties were not sufficient.
The cleaning agent in a container not containing the component (C) (Comparative Example 4) and the cleaning agent in a container whose pH does not satisfy the range of the present invention (Comparative Examples 6 and 7) did not have sufficient cleaning power.
From the above results, it was confirmed that the container-containing cleaning agent to which the present invention was applied was excellent in foam retention and detergency and also had good rinsing properties.

Claims (3)

A cleaning method for a bathtub using a container-containing cleaning agent for a bathroom in which a liquid cleaning agent is filled in a foam discharge container ,
The liquid detergent is
(A) component: 0.1-10 mass% of surfactant containing non-soap anionic surfactant,
(B) component: water-soluble solvent,
(C) component: aminocarboxylic acid type chelating agent;
(D) component: water-soluble polymer,
And the pH at 25 ° C. is more than 10 and less than 12.
The foam discharge container is
A foam discharge container capable of discharging the liquid detergent as a foam of 100 mL / 20 g or more and 200 to 1000 mPa · s under a condition of 20 ° C .;
The liquid detergent is discharged as foam from the foam discharge container, and the foam is directly attached to the water line on the inner wall of the bathtub or the area above the water line, and then the water is discharged from the bathtub. How to wash the bathtub. (B) component of the liquid detergent is 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, diethylene glycol monobutyl ether, The bathtub according to claim 1, which is at least one water-soluble solvent selected from diethylene glycol monobenzyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. Cleaning method. The washing | cleaning method of the bathtub of Claim 1 or Claim 2 whose (D) component of the said liquid cleaning agent is a natural polysaccharide polymer.