JP2017019964A - Liquid detergent composition for hard surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition for hard surface where rich foaming and retentivity of foam are exhibited during cleaning and foam disappears immediately at rinsing and rinse is completed with a small amount of water.SOLUTION: There is provided a liquid detergent composition for hard surface containing (a) a nonionic surfactant where ethylene oxide of 1 mole or more and less than 6 mole as average is added to a secondary alcohol having 8 to 18 carbon atoms (hereafter called (a) component), (b) one or more surfactant selected from an anionic surfactant, a cationic surfactant, an ampholytic surfactant and a nonionic surfactant other than the (a) component (hereafter called (b) component) and water and having total content of the (a) component and the (b) component of 3 mass% to 10 mass% and a mass ratio of [content of the (a) component]/[total content of the (a) component and the (b) component] of 0.05 to 0.50.SELECTED DRAWING: None

Description

  The present invention relates to a hard surface liquid cleaning composition and a hard surface cleaning method.

Cleaning agents for hard surfaces such as bathroom cleaners require rich foaming and foam persistence during cleaning. This foaming property and foam persistence are very important physical properties that have a correlation with cleaning properties, and are factors that greatly affect the cleaning of an object having many vertical surfaces such as in a bathroom. Various surfactants are generally used to develop this foaming.
Patent Document 1 discloses an amidobetaine type amphoteric surfactant, a nonionic surfactant, a water-soluble solvent, and a neutral to basic detergent composition for hard surface, which contains water. It describes that it is excellent in strength and foaming power and is suitable as a cleaning agent for residential use, bathroom use, kitchen use, tableware and the like.
Patent Document 2 contains sulfosuccinic acid alkyl ester or a salt thereof, a specific anionic surfactant, and a specific polypropylene glycol, and shows abundant foaming at the time of washing and persistence of the foam at the time of washing, A dishwashing composition for hand-washing is described wherein the foam disappears instantaneously upon rinsing and is rinsed with a small amount of water.

Japanese Unexamined Patent Publication No. 7-3288 JP 2013-82847 A

On the other hand, after the hard surface is washed, an operation for removing bubbles is generally performed by rinsing with running water. In washing the bathroom, many methods of rinsing are performed by showering. However, since the operation is usually performed until the foam disappears, it takes time to use a large amount of water.
For the purpose of reducing the environmental load, effectively using water resources, and reducing the work load, it is desirable to reduce the rinse water after washing as much as possible. However, a cleaning agent that is generally excellent in foamability and foam persistence requires a large amount of water to complete rinsing. Accordingly, there is a strong demand for a cleaning agent that exhibits abundant foaming and persistence of foam during washing, but disappears instantly during rinsing and completes rinsing with a small amount of water.
In this regard, in Patent Document 1 and Patent Document 2, it is desired to further improve the disappearance of bubbles particularly for a cleaning agent that requires a large amount of water for rinsing, such as a bath cleaning agent.
The present invention provides a liquid detergent composition for a hard surface that exhibits abundant foaming and foam persistence during cleaning, but disappears instantly during rinsing and completes rinsing with a small amount of water.

The present invention relates to (a) a nonionic surfactant (hereinafter referred to as component (a)) in which ethylene oxide is added in an average of 1 mol or more and less than 6 mol to a secondary alcohol having 8 to 18 carbon atoms,
(B) One or more surfactants selected from anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants other than component (a) [hereinafter referred to as component (b) ], And
Contains water,
The total content of the component (a) and the component (b) is 3% by mass or more and 10% by mass or less,
The mass ratio of [content of (a) component] / [total content of (a) component and (b) component] is 0.05 or more and 0.50 or less,
The present invention relates to a liquid detergent composition for hard surfaces.

  Moreover, this invention relates to the liquid detergent product for hard surfaces formed by filling the liquid detergent composition for hard surfaces of the said invention into a spray-type container.

  The present invention also relates to a method for cleaning a hard surface, wherein a step of rinsing with water is performed after the step of applying the liquid detergent composition for hard surface of the present invention to a hard surface on which dirt has adhered.

According to the present invention, a hard surface that exhibits abundant foaming and long-lasting foaming during cleaning, but disappears instantly during rinsing, completes rinsing with a small amount of water, excellent cleaning power, and good blending stability. A liquid detergent composition is provided.
In the cleaning with the hard surface liquid cleaning composition of the present invention, it is possible to reduce rinsing water, which is effective for the purpose of reducing the environmental load and effectively using water resources, and from the viewpoint of reducing the work load. Time can be shortened and it is effective. In addition, it has excellent detergency such as sebum dirt adhering to the hard surface, and also has good blending stability.

  In addition, the hard surface liquid detergent composition of the present invention exhibits excellent detergency even without using a strong oxidizing agent or alkaline agent such as hypochlorite. Can be used for parts and tiles.

Schematic showing the evaluation method of foam extinction performed in the examples Schematic showing the perforated state of the hard water introduction means (water) used in the evaluation of foam extinction of the example

<(A) component>
The component (a) is a nonionic surfactant obtained by adding ethylene oxide in an average of 1 mol or more and less than 6 mol to a secondary alcohol having 8 to 18 carbon atoms.
The secondary alcohol preferably has 9 or more carbon atoms, more preferably 10 or more, further preferably 11 or more, and preferably 17 or less, more preferably 16 or less, further 15 or less, and further preferably 14 or less. The secondary alcohol is preferably a secondary alcohol having an alkyl group having 8 to 18 carbon atoms. The carbon number of the alkyl group is preferably in the same range as the carbon number of the secondary alcohol described above.
The average number of moles of ethylene oxide added is preferably 1.5 moles or more, more preferably 2 moles or more, still more preferably 3 moles or more, and preferably 5.8 moles or less, more preferably 5.5 or less. More preferably less than the mole.

  The component (b) is one or more surfactants selected from an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant other than the component (a).

  Examples of the anionic surfactant include an anionic surfactant having one or more hydrocarbon groups and one or more groups selected from the group consisting of sulfonic acid groups, sulfate ester groups, and carboxylic acid groups. .

  Examples of the anionic surfactant include alkyl or alkenyl benzene sulfonic acid or a salt thereof, polyoxyalkylene alkyl or alkenyl ether sulfate or a salt thereof, alkyl or alkenyl sulfate or a salt thereof, and a fatty acid or a salt thereof. From the viewpoint of detergency, foamability, and rinsing properties, the anionic surfactant is preferably at least one selected from the group consisting of polyoxyalkylene alkyl or alkenyl ether sulfates or salts thereof and fatty acids or salts thereof. . The oxyalkylene group of the polyoxyalkylene alkyl or alkenyl ether sulfate or a salt thereof is preferably an oxyethylene group. Moreover, the average addition mole number of the oxyalkylene group of polyoxyalkylene alkyl or alkenyl ether sulfate ester salt is preferably 1 or more and 10 or less. Examples of fatty acids or salts thereof include fatty acids having 10 to 18 carbon atoms and salts thereof. The alkyl group or alkenyl group of the anionic surfactant preferably has 10 to 18 carbon atoms. The salt is preferably an alkali metal salt such as sodium salt or potassium salt.

  Examples of the cationic surfactant include quaternary ammonium salt type cationic surfactants. As the quaternary ammonium salt type cationic surfactant, one or two of the groups bonded to the nitrogen atom is a hydrocarbon group having 6 to 18 carbon atoms, and the remainder is 1 to 3 carbon atoms. Examples thereof include quaternary ammonium salt type cationic surfactants, which are groups selected from the group consisting of the following alkyl groups, hydroxyalkyl groups having 1 to 3 carbon atoms, and arylalkyl groups (such as benzyl groups). Among these, a quaternary ammonium salt type cationic surfactant having a bactericidal performance is preferable, and a quaternary ammonium salt type cationic surfactant having a benzyl group is preferable from the viewpoint of bactericidal performance.

  As the cationic surfactant, a quaternary ammonium salt type cationic surfactant represented by the following general formula (1) is preferable.

[Wherein R ¹ represents a hydrocarbon group having 6 to 18 carbon atoms. R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ⁴ represents an alkylene group having 1 to 3 carbon atoms. Z ⁻ represents an anionic group. ]

The quaternary ammonium salt type cationic surfactant represented by the general formula (1) is a hydrocarbon having 6 to 18 carbon atoms in the general formula (1) from the viewpoint of improving detergency and foaming. It is a group. R ¹ preferably has 8 or more carbon atoms, 14 or less, and more preferably 10 or less. R ¹ is preferably an alkyl group.
In addition, from the viewpoint of improving detergency and low irritation, in the general formula (1), R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms, and having 1 to 2 carbon atoms. The alkyl group is preferably a methyl group.
Further, from the viewpoint of improving detergency and low irritation, in general formula (1), R ⁴ is an alkylene group having 1 to 3 carbon atoms, preferably an alkylene group having 1 to 2 carbon atoms, methylene Groups are more preferred.
Moreover, as Z < ^- > in General formula (1), halogen ions, such as a chloride ion, are preferable from the point of a detergency improvement. Z ⁻ is more preferably a chloride ion (Cl ⁻ ).

The amphoteric surfactant is preferably an amphoteric surfactant having an alkyl group having 8 or more and 22 or less carbon atoms from the viewpoint of improving detergency and foaming. Furthermore, in this amphoteric surfactant, the carbon number of the alkyl group is preferably 10 or more, more preferably 11 or more, and is preferably 18 or less, more preferably 13 or less.
As the amphoteric surfactant, at least one amphoteric surfactant selected from the group consisting of alkylbetaines, alkylamidobetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylamidohydroxysulfobetaines, and alkylamino fatty acid salts should be used. Is preferable from the viewpoint of detergency and foaming. Among them, amphoteric surfactants selected from the group consisting of alkyl (C8 or more and 22 or less) amidopropyl betaine and alkyl (C8 or more and 22 or less) hydroxysulfobetaine are preferable, and (3-lauramidopropyl is more preferable. ) An amphoteric surfactant selected from the group consisting of dimethylbetaine and lauryldimethylhydroxysulfobetaine is more preferred. Further, two or more amphoteric surfactants listed here may be mixed and used. As the amphoteric surfactant, one or more amphoteric surfactants selected from betaine-type amphoteric surfactants having an alkyl group having 8 or more, 10 or more, 11 or more, and 22 or less, 18 or less, and 13 or less carbon atoms are used. Agents are preferred.

  As the nonionic surfactant other than the component (a), a polyoxyalkylene alkyl ether having an alkyl group having 10 to 18 carbon atoms, a polyoxyalkylene alkenyl ether having an alkenyl group having 10 to 18 carbon atoms, Polyoxyalkylene sorbitan fatty acid ester having a fatty acid group of 10 to 18 carbon atoms, sucrose fatty acid ester having a fatty acid group of 8 to 18 carbon atoms, alkyl polyglyceryl ether having an alkyl group of 8 to 18 carbon atoms Etc.

  However, the amount of the alkylglycoside and the alkylpolyglycoside having an alkyl group having 8 or more and 18 or less carbon atoms and having a sugar condensation degree of 1 or more and 3 or less is limited from the viewpoint of foam control during rinsing. The content of the alkyl glycoside is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and further preferably 0.1% by mass or less in the composition.

<Composition, optional components, etc.>
In the liquid detergent composition for hard surface of the present invention, the total content of the component (a) and the component (b) is 3% by mass or more and 10% by mass or less from the viewpoint of cleaning performance and foam control. The total content of the component (a) and the component (b) is preferably 4% by mass or more, more preferably 5% by mass or more, still more preferably 6% by mass or more in the composition from the viewpoint of cleaning performance. From the viewpoint of foam extinction, it is preferably 9% by mass or less, more preferably 8% by mass or less, still more preferably 7% by mass or less, and still more preferably 6.5% by mass or less.

  From the viewpoint of cleaning performance and foam control, the hard surface liquid detergent composition of the present invention has a mass of [(a) component content] / [total content of (a) component and (b) component]. The ratio is 0.05 or more and 0.50 or less. The mass ratio of [(a) component content] / [total content of (a) component and (b) component] is preferably 0.08 or more, more preferably 0.8, from the viewpoint of foam extinction. 1 or more, more preferably 0.15 or more, and from the viewpoint of cleaning performance, it is preferably 0.45 or less, more preferably 0.35 or less, and still more preferably 0.25 or less.

  From the viewpoint of cleaning performance and foam control, the hard surface liquid detergent composition of the present invention has a mass ratio of [(a) component content] / [nonionic surfactant content] of 0.35 or more. It is preferable that The mass ratio of [content of (a) component] / [content of nonionic surfactant] is preferably 0.7 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and Most preferred is 1. The content of the nonionic surfactant is the total content of the nonionic surfactant other than the component (a) and the component (a).

  In the liquid detergent composition for hard surface of the present invention, the content of the amphoteric surfactant in the composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of foam control. Preferably it is 1.5 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 4 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2.5 mass% or less.

  The hard surface treating agent composition of the present invention is a liquid composition containing water. In order to ensure the uniformity of the liquid after long-term storage, the content of water is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and more preferably 80% by mass or more in the composition. Is even more preferable. And 95 mass% or less is preferable in a composition, as for content of water, 90 mass% or less is more preferable, and 85 mass% or less is still more preferable.

  Moreover, the liquid detergent composition for hard surfaces of this invention can contain a metal ion scavenger [henceforth (c) component].

Specific examples of the component (c) include one or more metal ion scavengers selected from the following (c1) to (c3).
(C1) Amino acids such as aspartic acid, glutamic acid and glycine, and alkali metal salts or alkanolamine salts thereof.
(C2) Aminocarboxylic acids such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, diencoric acid And alkali metal salts or alkanolamine salts thereof.
(C3) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid, and other organic acids Alkali metal salt or alkanolamine salt.

  Among these, hydroxycarboxylic acids such as citric acid and malic acid, aminocarboxylic acids such as ethylenediaminetetraacetic acid and hydroxyethylethylenediaminetriacetic acid, and salts thereof are preferable. Especially, it is preferable that it is 1 type, or 2 or more types chosen from a citric acid, ethylenediaminetetraacetic acid, and these salts. The salt form is preferably a sodium salt, potassium salt, ammonium salt or alkanolamine salt.

  The content of the component (c) in the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further 1% by mass or more, further 2% by mass or more, and further preferably 3% by mass or more, and 10 mass% or less, Furthermore 8 mass% or less, Furthermore 6 mass% or less, Furthermore 5 mass% or less are preferable.

  The hard surface liquid detergent composition of the present invention may contain an organic solvent (hereinafter referred to as component (d)).

  Examples of the organic solvent used as the component (d) include various mono-, di- or tri-alkylene glycol monoethers and mono-, di- or tri-alkylene glycol diethers. Specifically, mono-, di- or tri-ethylene glycol monoether, and mono-, di- or tri-ethylene glycol diether, and mono-, di- or tri-propylene glycol monoether, and mono-, Di- or tri-propylene glycol diether is suitable. Such glycol monoether and glycol diether preferably have an alkyl group, and the alkyl group can be selected from alkyl groups having various carbon numbers. For example, methyl, ethyl, propyl, butyl, hexyl and the like. These glycol ethers and glycol diethers preferably have a total carbon number of 4 or more, more preferably 6 or more, more preferably 8 or more, and preferably 14 or less, more preferably 12 or less, more preferably 10 or less. It is.

  As the component (d), from the viewpoint of imparting antifouling properties, ethylene glycol mono-butyl ether, diethylene glycol mono-butyl ether, ethylene glycol mono-isobutyl ether, diethylene glycol mono-isobutyl ether, ethylene glycol mono-hexyl ether, diethylene glycol mono-hexyl Ether, propylene glycol mono-butyl ether, dipropylene glycol mono-butyl ether, dipropylene glycol mono-methyl ether, tripropylene glycol mono-methyl ether, ethylene glycol mono-isopropyl ether, 2-propanol, ethylene glycol mono-2-ethylhexyl ether Propylene glycol mono-n-propyl ether and dipropylene glycol One or more organic solvent selected from -n- propyl ether. Among these, one or more organic solvents selected from ethylene glycol mono-butyl ether and diethylene glycol mono-butyl ether are preferable, and diethylene glycol mono-butyl ether is more preferable.

  The content of the component (d) is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 6% by mass or more, and more preferably 7% by mass or more in the composition. Preferably, 7.5 mass% or more is more preferable. And content of (d) component is 30 mass% or less in a composition, 20 mass% or less is more preferable, 15 mass% or less is more preferable, 9 mass% or less is more preferable.

  The liquid detergent composition for hard surface of the present invention can be blended with preservatives, hydrotropes, dyes, viscosity modifiers, antioxidants, fragrances and the like as long as they do not impair detergency and foaming. .

  The liquid detergent composition for hard surface of the present invention preferably has a pH at 20 ° C. of 5 or more, more preferably 6 or more, and 12 or less, further 10 or less, and further 9 from the viewpoint of safety during use. Hereinafter, it is further preferably 8 or less. A pH adjuster can be used to adjust the pH. As the pH adjusting agent, an inorganic acid such as hydrochloric acid or sulfuric acid, or an acid agent such as an organic acid can be used. Moreover, as an alkaline agent, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate can be used.

  The present invention has been found to be excellent in foam stability and foam disappearance by using the component (a) and the component (b) under specific conditions as a blending component of a composition containing water. The composition of the present invention has a very limited composition, and exhibits a rich foaming and foam persistence during washing, but the foam disappears instantly during rinsing and a cleaning agent that can be rinsed with a small amount of water is obtained. This is an unexpected effect that cannot be predicted from the common general technical knowledge of the industry.

  The liquid detergent composition for hard surfaces of the present invention is suitably used for cleaning hard surfaces such as bathrooms, bathtubs, washbasins, tiles, restrooms, washstands, mirrors, sinks around kitchens, countertops, and waterworks. It is done. It is suitably used for bathrooms. Here, the bathroom liquid detergent composition is intended not only for bathrooms but also for articles having other hard surfaces such as bathtubs and washbasins.

  Moreover, the liquid detergent composition for hard surfaces of the present invention is suitable for spraying. It is preferably used as a liquid detergent product for spray-type hard surfaces formed by filling a spray-type container. According to the present invention, there is provided a hard surface liquid detergent article obtained by filling a spray container with the hard surface liquid detergent composition of the present invention.

Examples of the spray container include a spray container equipped with a trigger sprayer (referred to as a trigger spray container).
Examples of the trigger type spray container include a container body containing a liquid composition, and a trigger type liquid ejector attached to the mouth part of the container body. Furthermore, a liquid is formed in the mouth part of the container body. A trigger sprayer for ejecting the composition is mounted, and a vertical pipe and a horizontal pipe are formed inside the trigger sprayer, and the vertical pipe and the horizontal pipe are communicated with each other in the vertical pipe. And a spray container (referred to as spray container (I)) in which a valve for shutting off is disposed.
The spray container (I) is provided with a cylinder at a position below the horizontal pipe, and a spin element is mounted at the tip of the horizontal pipe, and a nozzle having a nozzle hole is fitted at the tip of the spin element. It is fixed. The spray container (I) pulls the trigger to discharge the air in the cylinder to the outside, and when the trigger is returned, the liquid composition is sucked up through the vertical pipe immersed in the liquid composition of the container body, The liquid is filled in, and the trigger is pulled again to push out the liquid in the cylinder and guide it to the vertical pipe, and further spin the liquid flow through the horizontal pipe and the spin element, and finally eject from the nozzle. Is. The method of applying the liquid composition of the present invention to the hard surface can be selected according to the width (area) of the hard surface. For example, it can be carried out by spraying about 0.05 to 5 mL of the stock solution of the composition of the present invention as it is.

<Cleaning method of hard surface>
The present invention provides a method for cleaning a hard surface, wherein a step of rinsing with water is performed after the step of applying the liquid detergent composition for a hard surface of the present invention to a hard surface contaminated with dirt.
In the cleaning method of the present invention, a method in which the composition is filled in a spray container and sprayed in the form of foam and applied to dirt on a hard surface is preferable. In addition, a method of rinsing with a shower or the like after application to dirt is preferred, but a method of scrubbing with a sponge or the like and rinsing with a shower or the like is more preferred from the viewpoint of improving detergency. In order to obtain a sufficient detergency, the amount applied to the soil is preferably 0.3 g or more, more preferably 0.5 g or more, more preferably 5 g or less, and further 2 g or less per 20 cm ² . Even if the composition is applied and immediately washed with a sponge or the like, a good removal effect can be obtained, but after applying to the stain, it is 10 seconds or more, preferably 0.5 minutes or more, more preferably 1 minute or more, A method of scrubbing with a sponge or the like after standing for 5 minutes or less, preferably 3 minutes or less, more preferably 2 minutes or less is preferable from the viewpoint of increasing the cleaning power.

<Examples 1-3 and Comparative Examples 1-4>
The components listed in Table 1 were blended to prepare a hard surface liquid detergent composition. The pH (20 ° C.) of each composition was adjusted to 7 with hydrochloric acid or sodium hydroxide. These compositions were evaluated for foam stability and foam disappearance. The results are shown in Table 1. In addition, the liquid detergent composition for hard surfaces of the Example in Table 1 had favorable detergency for hard surfaces.

<Foam stability>
A container of a commercially available spray-type bathroom cleaner (Kao Corporation, Bath Magiclin) was used after cleaning. The container was filled with the liquid detergent composition for hard surface shown in the table. By pulling the trigger of the container 10 times, 10 g of foam was made in a 200 ml graduated cylinder. The pulling speed was 1 second per time. At this time, the volume was recorded from the scale of the graduated cylinder and used as the initial amount of foam. Thereafter, the mixture was allowed to stand, the volume of the foam after 3 minutes was measured, and the foam remaining rate after 3 minutes with respect to the initial amount of foam was determined from the following formula.
Foam remaining rate after 3 minutes (%) = (foam amount after 3 minutes / initial foam amount) × 100
If the foam remaining rate after 3 minutes is 50% or more, the foam stability is good, and this is “◯”, and if it is less than 50%, the foam stability is poor, and this is evaluated by “×”. .

<Bubble disappearance>
A container of a commercially available spray-type bathroom cleaner (Kao Corporation, Bath Magiclin) was used after cleaning. The container was filled with the liquid detergent composition for hard surface shown in the table. By pulling off the container trigger 5 times, 5 g of foam was made in a 500 ml graduated cylinder. The pulling speed was 1 second per time. At this time, the capacity was recorded from the scale of the graduated cylinder. This was defined as the initial amount of foam.
Next, the operation of adding 50 ml of 3.5 ° DH hard water to the foam through the means for introducing hard water (manufactured by hand) installed at the top of the graduated cylinder and adding 50 ml of hard water every 1 minute was performed a total of 9 times. (50 ml of hard water was added a total of 9 times, for a total addition amount of 450 ml). For each operation of adding 50 ml of hard water, the amount of foam 30 seconds after the addition of the entire amount of hard water was measured. This was taken as the amount of foam after the addition of hard water.
FIG. 1 shows the state when hard water is added to the graduated cylinder. In FIG. 1, 1 is a graduated cylinder, 2 is foam, 3 is a hard water introduction means (manufactured by hand), 4 is an opening of the introduction means, and FIG. 2 is a perforation of the opening 4 of the hard water introduction means 3. It is the schematic which shows a state. A method for producing a handmade water fountain as means for introducing hard water is as follows. First, from the bottom of a 250 ml polypropylene wide-mouthed bottle (manufactured by ASONE: I-boy wide-mouthed bottle) to the main body part having a height of about one third was excised. Next, as shown in FIG. 2, a polyethylene perforated plate having 13 holes with a diameter of 2 mm at 9 mm intervals was prepared for a thin circular polyethylene plate with a diameter of 4 cm. Finally, the polyethylene perforated plate was fixed as the opening 4 to the lid opening (diameter 4 cm) at the top of the excised wide-mouth bottle to produce hard water introducing means 3 (handmade watering device). The hard water introducing means 3 (manufactured by hand) thus produced was fitted into the opening of the graduated cylinder 1 while being kept in an inverted state as shown in FIG. Hard water was introduced from the excised side of the wide-mouth bottle.
From the initial amount of foam and the amount of foam after the addition of hard water, the rate of change in the amount of foam represented by the following formula was determined to evaluate the foam disappearance. The foam disappearance is better as the amount of hard water added is less than 50%, and in the above evaluation, the amount of hard water added is less than 250 ml (hard water addition operation). Is less than 5 times), it is evaluated as “○” as being able to achieve quick foam disappearance, and when the amount of hard water added is such that the rate of change in the amount of foam is 50% or less (hard water addition operation is 6 times), Evaluated as “△” as that the foam disappears to some extent quickly, and when the amount of hard water added at which the rate of change in the amount of foam is 50% or less is 350 ml or more (hard water addition operation is 7 times or more) It was evaluated as “x” because it could not be achieved.
Foam amount change rate (%) = [1- (foam amount after addition of hard water / initial foam amount)] × 100

In the table, the mass% of the blended components is described in terms of the effective amount.
In the table, (a) + (b) is the total content (% by mass) of the component (a) and the component (b).
In the table, (a) / [(a) + (b)] is a mass ratio of [content of (a) component] / [total content of (a) component and (b) component].
In the table, (a) / nonionic surfactant is a mass ratio of [content of (a) component] / [content of nonionic surfactant].

The components in the table are as follows.
<(A) component>
-Nonionic surfactant (a1): Softanol 33, polyoxyethylene alkyl (sec-12-14) ether, ethylene oxide average addition mole number 3, made by Nippon Shokubai Co., Ltd., the alkyl group has 12-14 carbon atoms Nonionic surfactant / nonionic surfactant (a2) having an average of 3 moles of ethylene oxide added to a secondary alcohol: Softanol 50, polyoxyethylene alkyl (sec-12-14) ether, average moles of ethylene oxide added A nonionic surfactant obtained by adding 5 moles of ethylene oxide on average to a secondary alcohol having an alkyl group of 12 to 14 and having an alkyl group of 12 to 14, manufactured by Nippon Shokubai Co., Ltd.

<(B) component>
Nonionic surfactant (b1): Softanol 70H, polyoxyethylene alkyl (sec-12-14) ether, ethylene oxide average added mole number 7, manufactured by Nippon Shokubai Co., Ltd., and the alkyl group has 12 to 14 carbon atoms Nonionic surfactant / nonionic surfactant (b2) obtained by adding 7 mol of ethylene oxide on average to a certain secondary alcohol: Emulgen 102, polyoxyethylene alkyl ether, alkyl group having 12 to 14 carbon atoms, ethylene oxide average Nonionic surfactant / nonionic surfactant in which 2 moles of ethylene oxide is added to an average of 2 moles of linear primary alcohol having an addition of 2 moles, Kao Corp., and an alkyl group having 12 to 14 carbon atoms ( b3): Emulgen 103, polyoxyethylene alkyl ether, alkyl group having 12 carbon atoms, ethylene Nonionic surfactant / nonion with an average addition of 2.9 moles of ethylene oxide and an average addition of 2.9 moles of ethylene oxide to a linear primary alcohol with an alkyl group of 12 carbon atoms, an alkoxide addition mole number of 2.9, manufactured by Kao Corporation Surfactant (b4): Emulgen 104, polyoxyethylene alkyl ether, alkyl group having 12 to 16 carbon atoms, ethylene oxide average addition mole number of 3.9, manufactured by Kao Corporation, alkyl group having 12 to 16 carbon atoms A non-ionic surfactant with an average of 3.9 mol of ethylene oxide added to a linear primary alcohol, sodium myristic acid: myristic acid (Lunac MY-98, manufactured by Kao Corporation), and then pH adjustment The mixture was neutralized with sodium hydroxide used in the above.
Sodium alkyl ether sulfate ester: polyoxyethylene (ethylene oxide average addition mole number 4.0) alkyl (carbon number 10-16) sodium ether sulfate ester (3-lauramidopropyl) dimethylbetaine: fatty acid (carbon number 12) amide Propyl-N, N-dimethyl-betaine acetate / octylbenzyldimethylammonium chloride: Sanizor 08, manufactured by Kao Corporation

<(C) component>
・ EDTA: Ethylenediaminetetraacetic acid tetrasodium salt ・ Citric acid

<(D) component>
・ Diethylene glycol monobutyl ether: BDG-NS, manufactured by Nippon Emulsifier Co., Ltd.

  From the results of Examples and Comparative Examples, it can be seen that the composition of the present invention using the component (a) and the component (b) under predetermined conditions is excellent in foam stability and foam disappearance.

Claims (6)

(A) a nonionic surfactant (hereinafter referred to as component (a)) in which ethylene oxide is added in an average of 1 mol or more and less than 6 mol to a secondary alcohol having 8 to 18 carbon atoms,
(B) One or more surfactants selected from anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants other than component (a) [hereinafter referred to as component (b) ], And
Contains water,
The total content of the component (a) and the component (b) is 3% by mass or more and 10% by mass or less,
The mass ratio of [content of (a) component] / [total content of (a) component and (b) component] is 0.05 or more and 0.50 or less,
Liquid detergent composition for hard surfaces.   The liquid detergent composition for hard surfaces according to claim 1, wherein a mass ratio of [content of component (a)] / [content of nonionic surfactant] is 0.35 or more.   The liquid detergent composition for hard surfaces according to claim 1 or 2, wherein the alkylglycoside content is 0.5 mass% or less.   The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein the pH at 20 ° C is 5 or more and 12 or less.   The liquid detergent product for hard surfaces formed by filling the liquid detergent composition for hard surfaces according to any one of claims 1 to 4 in a spray type container.   A method for cleaning a hard surface, comprising a step of rinsing with water after the step of applying the liquid detergent composition for hard surface according to any one of claims 1 to 4 to a hard surface on which dirt has adhered.

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