JP5058579B2 - Liquid detergent article. - Google Patents

Description

  The present invention relates to a liquid detergent article suitable for a hard surface, which can discharge a liquid detergent composition in the form of foam.

A technique using a large amount of polyvalent carboxylic acid such as citric acid in a dishwashing liquid detergent composition is known, and Patent Document 1 can be referred to. Patent Documents 2 and 3 disclose a technique of a liquid detergent filled in a pump former container, and Patent Document 2 discloses a technique of an article filled with a dishwashing liquid detergent. .
JP 2006-160870 A JP-T-2006-513312, JP 2005-193972 A

  Since detergents such as dishwashing detergents require detergency for hard dirt such as oil stains, compositions containing a large amount of a surfactant are generally used. In addition, such a cleaning agent has a great demand for foaming and feel at the time of cleaning, and using a pump former container as disclosed in Patent Document 2, the cleaning agent is supplied in the form of foam to a sponge or the like for cleaning. A method has been proposed. And when utilizing a pump former container, it is desired that it is voluminous and can form aesthetically preferable bubbles (for example, fine bubbles) with excellent bubble persistence.

  When foam is formed using a porous membrane body such as a mesh as described in Patent Documents 2 and 3, when applied to a detergent containing a large amount of a surfactant such as a dishwashing detergent Because of the high viscosity of the composition, it is difficult to produce the desired foam described above.

  For this reason, Patent Document 2 discloses a technique for reducing the viscosity using a large amount of a hydrophobic solvent such as isoparaffin or a hydrophilic solvent such as ethanol. However, in such a technique using a large amount of a solvent, the persistence of foam is low (breaks bubbles immediately), and it is difficult to produce the above-mentioned desirable foam. In addition, it is uneconomical because it is necessary to use a large amount of a solvent that has little influence on the cleaning power. As other methods, a method of reducing the viscosity using a hydrotrope or the like can be considered, but the effect is limited in a composition having a large amount of surfactant.

  On the other hand, Patent Document 1 discloses a dishwashing detergent composition containing a large amount of citric acid. This technique was made for the purpose of improving the detergency of scale dirt adhering to the kitchen sink and the like. Regarding the formation of desirable foams when such a composition is applied to a pump former container. There is no disclosure.

  The problem to be solved by the present invention is that there is a voluminous feel and an excellent foam persistence despite filling a pump former container with a detergent composition containing a high concentration of surfactant. It is to provide a liquid detergent article capable of discharging a preferred foam.

The present invention provides the following solutions:
(A) 20-50 mass% of surfactant,
(B) 1 to 15% by mass of an organic solvent,
(C) containing 2.5 to 10% by mass of one or more selected from citric acid, tartaric acid, succinic acid, malic acid, lactic acid and derivatives thereof, and water,
A liquid detergent composition having a pH at 25 ° C. of 5 to 8 and a viscosity at 20 ° C. of 30 to 80 mPa · s,
Provided is a liquid detergent article filled in a container having a pump former having one or two porous membranes having a mesh size of 100 to 300 / inch as a foam discharge mechanism.

  The liquid detergent article of the present invention is a volumetric and aesthetically superior foam persistence comprising the above composition by combining a specific liquid detergent composition and a pump former container having a specific foam discharge mechanism. In particular, a preferable bubble can be formed and a high detergency can be exhibited.

<(A) component>
As the component (a) surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and a cationic surfactant can be used.

  In the present invention, in particular, an anionic surfactant (a1) and a nitrogen-containing surfactant (a2) selected from amine oxide type surfactants, betaine type surfactants, and alkanolamide type surfactants (a1) ) / (A2) = 1 to 20 mass ratio, preferably 1 to 10 mass ratio, particularly preferably 1 to 5 mass ratio. A detergent composition containing such a surfactant mixture has high detergency and excellent foaming properties.

  As the component (a1), an alkyl sulfate ester salt having 10 to 18 carbon atoms, preferably 10 to 14 carbon atoms, an alkyl group having 10 to 18 carbon atoms, preferably 10 to 14 carbon atoms, and an average addition mole number of 1 to 6, preferably A polyoxyalkylene alkyl ether sulfate ester having 1 to 4, particularly preferably 1.5 to 3 alkylene groups (the alkylene group has 2 or 3 carbon atoms) and an alkylbenzene sulfonate having 10 to 15 carbon atoms are preferred. As the salt, sodium salt, potassium salt, and magnesium salt are preferable.

  As the amine oxide type surfactant as the component (a2), a compound represented by the following general formula (1) is suitable.

[Wherein R ¹¹ is an alkyl group having 10 to 18 carbon atoms, preferably 10 to 14 carbon atoms, R ¹² is an alkylene group having 2 or 3 carbon atoms, and R ¹³ and R ¹⁴ are each having 1 to 3 carbon atoms. An alkyl group and / or a hydroxyalkyl group, preferably a methyl group and / or a hydroxyethyl group. A is a group selected from -COO- and -CONH-, and m is a number of 0 or 1. ]
As the betaine surfactant which is the component (a2), a compound represented by the following general formula (2) is suitable.

[Wherein R ²¹ is a hydrocarbon group having 10 to 16 carbon atoms, and preferably an alkyl group having 10 to 14 carbon atoms. R ²² is an alkylene group having 2 or 3 carbon atoms, and R ²³ and R ²⁴ are an alkyl group and / or hydroxyalkyl group having 1 to 3 carbon atoms, preferably a methyl group and / or a hydroxyethyl group. B is a group selected from -COO- and -CONH-, and n is a number of 0 or 1. D is _{^{-CH 2 COO -, -C 3 H}} 6 SO 3 -, or _{-CH 2 CH (OH) CH 2} SO 3 - a and, preferably _{-CH 2 CH (OH) CH 2} SO 3 - is . ]
As the alkanolamide-type surfactant that is the component (a2), a compound represented by the following general formula (3) is suitable.

[Wherein, R ³¹ is a hydrocarbon group having 10 to 16 carbon atoms, and preferably an alkyl group having 10 to 14 carbon atoms. R ³² is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or — (R ³⁴ —O) p—H (where R ³⁴ is an alkylene group having 2 or 3 carbon atoms, and p is an average addition mole) A number between 1 and 12.) R ³³ is an alkylene group having 2 or 3 carbon atoms, and o is 1 to 12, preferably 1 to 6].

  In the present invention, a surfactant other than the component (a1) and the component (a2) can be contained, and preferably an alkyl glyceryl ether having 8 to 12 carbon atoms (hereinafter referred to as component (a3)) is a detergency. From the viewpoint of foaming property, 2-ethylhexyl glyceryl ether is most preferable.

  As other surfactants (hereinafter referred to as (a4) component), an alkyl group having 10 to 18 carbon atoms, preferably 10 to 14 carbon atoms, and a polyoxyalkylene group having 2 to 30 and preferably 3 to 12 average added moles. A polyoxyalkylene alkyl ether type having 2 or 3 carbon atoms of the alkylene group, 8 to 16, preferably 8 to 14 carbon atoms of the alkyl group, and an average degree of condensation of glucose of 1 to 2, preferably 1 to 1. .5 alkylglycoside type nonionic surfactant, quaternary ammonium type having 1 to 2 alkyl groups having 8 to 12 carbon atoms and the remaining alkyl group having 1 to 3 carbon atoms, hydroxyalkyl group, or benzyl group Cationic surfactants can be used.

<(B) component>
The organic solvent of component (b) is a water-soluble solvent [hereinafter referred to as component (b1). Water-soluble is defined as a solvent that dissolves 10 g or more in 100 g of water at 20 ° C. ] And a water-insoluble solvent [hereinafter referred to as component (b2). It is preferable to use in combination with “water-insoluble” in which the amount dissolved in 100 g of water at 20 ° C. is defined as less than 10 g.

  Examples of the component (b1) include ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, particularly ethanol, Ethylene glycol and propylene glycol are preferred.

  Examples of the component (b2) include hydrocarbon solvents such as limonene and terpene, phenoxyethanol, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether.

  In the present invention, for the purpose of forming suitable bubbles, it is preferable to use the component (b1) and the component (b2) in combination, and the component (b1) / component (b2) is contained in a mass ratio of 0.05 to 20. Is preferable, more preferably 0.1 to 10, particularly preferably 0.2 to 8.

<(C) component>
Component (c) is a component that contributes to lowering the viscosity of the composition and can synergistically improve the effect of removing inorganic dirt. (C) component is citric acid, tartaric acid, succinic acid, malic acid, lactic acid, and their derivatives (including salts) in some cases (for example, carboxymethyloxysuccinic acid, ethylenediaminesuccinic acid, oxydisuccinic acid, carboxymethylsuccinic acid) 1 or more types selected from are used.

<Other ingredients>
Contains benzenesulfonate (hereinafter referred to as component (d)) which may be substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms for the purpose of forming bubbles suitable when using a pump former. Specifically, p-toluene sulfonate, meta-xylene sulfonate, and cumene sulfonate can be mentioned. As the salt, a sodium, potassium or magnesium salt is preferable, and sodium p-toluenesulfonate is particularly preferable.

  The cleaning agent of the present invention includes a polymer for preventing gelation, for example, a gelation-preventing polymer described in JP-A-11-513067 (hereinafter referred to as component (f)), particularly polyalkylene glycol. It is preferable from the viewpoint of viscosity control and storage stability. Specific examples of the polyalkylene glycol for preventing gelation include polypropylene glycol and polyethylene glycol having a weight average molecular weight of 200 to 3000 determined by gel permeation chromatography using polyethylene glycol as a standard. it can.

  In this invention, the component normally used for a liquid detergent can be contained, and a bactericidal agent, antiseptic | preservative, a fragrance | flavor, a pigment, and dye can be mentioned specifically.

<Liquid cleaning composition>
The content ratio of each component in the liquid detergent composition is as follows.

  (A) The content rate of a component is 20-50 mass% from the point of a detergency and foamability, Preferably it is 25-50 mass%, More preferably, it is 25-45 mass%.

  The total content when the component (a1) and the component (a2) are used in combination as the component (a) is preferably 10 to 40% by mass, more preferably 12 to 30% by mass. Further, when the component (a3) is used, the content ratio is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass from the viewpoints of detergency and foamability.

  The content rate of (b) component is 1-15 mass% from the objective of reducing the viscosity of a composition and forming a preferable foam. The viscosity of the liquid detergent tends to decrease substantially as the blending amount of the component (b) increases, but the blending amount of the component (b) is preferably from the viewpoint of foam volume feeling and foam persistence. It is 2-10 mass%, More preferably, it is 3-10 mass%.

  The content ratio of the component (c) is 2.5 to 10% by mass, preferably 3 to 8% by mass, more preferably 4 to 6% by mass, from the viewpoint of forming a preferable foam and the detergency.

  Although the component (d) is arbitrary, the content ratio is preferably 1 to 10% by mass, more preferably 1 to 8% by mass, and particularly preferably 2 to 6% by mass for the purpose of forming a preferable foam.

  The total content of the component (c) and the component (d) is preferably 3.5 to 20% by mass, more preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass. The mass ratio of component (c) / component (d) is preferably 0.4 to 20, more preferably 0.4 to 10, and particularly preferably 0.4 to 5.

  Component (f) is optional, but is a component capable of improving storage stability, and the content is 0.05 to 10% by mass, preferably 0.05 to 5% by mass, particularly preferably 0.1 to 3%. % By mass.

  The liquid detergent composition is in the form of an aqueous solution in which the above components are dissolved, emulsified and dispersed in water, and the pH at 25 ° C. is 5 to 8, preferably 5 to 7. The pH is adjusted using an inorganic acid such as hydrochloric acid or sulfuric acid, the component (c), and an alkali agent selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and alkanolamine. The pH was measured as follows.

  A pH measuring composite electrode (HORIBA glass sliding sleeve type) was connected to a pH meter (HORIBA pH / ion meter F-23), and the power was turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) was used as the pH electrode internal solution.

  Next, pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) were each filled in a 100 ml beaker. It was immersed in a constant temperature bath at 30 ° C. for 30 minutes. The pH measurement electrode was immersed in a standard solution adjusted to a constant temperature for 3 minutes, and calibration was performed in the order of pH 6.86 → pH 9.18 → pH 4.01.

  The sample was filled in a 100 ml beaker and adjusted to 25 ° C. in a constant temperature bath at 25 ° C. The pH measurement electrode was immersed in a sample adjusted to a constant temperature for 3 minutes, and the pH was measured.

  In the liquid detergent composition, inorganic cations are mixed from component (a), component (c), pH adjuster, etc., and these inorganic cations are composed of sodium ions, potassium ions, and magnesium ions. Is preferable, and potassium ion is more preferable. It is considered that the potassium ion may form a salt with an anion in the composition, but the potassium ion of the present invention includes all potassium in dissociation equilibrium.

  The mass ratio of (c) component citric acid or the like (preferably citric acid) and potassium ion [(c) component / potassium ion] is preferably 0.5 to 20, more preferably, for the purpose of forming a preferable foam. It is 0.7-10, Most preferably, it is 1-5.

  The viscosity of the liquid detergent composition at 20 ° C. is 30 to 80 mPa · s, preferably 30 to 70 mPa · s, particularly preferably 30 to 60 mPa · s. Such a viscosity range includes (b) component and ( The content of the component c) can be adjusted according to the content of the component (d) as necessary. As a preferable example when the components (b), (c), and (d) are contained, the total content in the composition is preferably 4.5 to 30% by mass, more preferably 10 to 20% by mass. It is preferable for the purpose of forming a preferable foam to contain (a) component / (b) component / (c) component by the mass ratio of 25-45 / 3-10 / 4-6.

  The viscosity as used in the present invention is measured as follows. First, TOKIMEC. The rotor type no. Prepare one equipped with 2 rotors. The sample is filled in a tall beaker and adjusted to 20 ° C. in a constant temperature bath at 20 ° C. A sample adjusted to a constant temperature is set in a viscometer. The rotational speed of the rotor is set to 60 r / m, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the present invention.

<Container with specific foam discharge mechanism>
An embodiment of a container (pump former container) having a specific foam discharge mechanism used in the present invention will be described with reference to the drawings. FIG. 1 is a longitudinal sectional view of a pump former container.

  In the pump former container 10, a foam dispenser 13 that can be foamed and discharged from the discharge port 26 by mixing the contained liquid (liquid cleaning composition) with air is attached to the neck 12 of the container body 11. ing. The discharge port 26 is preferably inclined upward, and the angle α formed with the horizontal plane is preferably 1 to 10 °. Furthermore, the interval β between the outer surface of the container body 11 and the discharge port 26 is preferably 3 to 20 mm.

  The foam discharger 13 has a cylindrical cap member 15 that sucks, pressurizes, and discharges the stored liquid, and aspirates, pressurizes, and discharges the air to the base cap portion 14 that is attached to the neck portion 12 of the container body 11. The air piston member 16 has a pump 18 composed of a single cylinder portion 17 incorporated in a concentric series.

  A foam member 20 is disposed in the height direction flow passage 21 in the pump head portion 19 protruding above the base cap portion 14. The foamed member 20 has a structure in which a porous film body having a mesh size of 100 to 300 / inch is fixed at least at one end opening of an independent cylindrical ring or inside the ring. It is arranged in the height direction flow path 21 so as to be perpendicular to the passing direction. The foam member 20 may be formed using one of the porous film bodies, or may be formed using two sheets having the same or different mesh sizes (double structure).

  The cylinder portion 17 includes a large-diameter air chamber 24 and a small-diameter liquid introduction chamber 28 having a lower end portion connected to the suction pipe 27 continuously in series downward from the large-diameter air chamber 24. Inside the small-diameter liquid introduction chamber 28, a spring member 29 that is compressively deformable in the axial direction is disposed. The spring member 29 urges the pump head portion 19 via the cylindrical piston member 15.

  The cylindrical piston member 15 includes a liquid chamber 30 and valve bodies 31a and 31b inside. The air piston member 16 is provided so as to project radially outward from the cylindrical piston member 15, and its peripheral portion is slidably in close contact with the inner peripheral surface of the large-diameter air chamber 24 so that the large-diameter air chamber 24 is moved up and down. It is divided into.

<Liquid detergent article>
In the liquid detergent product of the present invention, the above-described liquid detergent composition is filled in a pump former container having a specific foam discharge mechanism as shown in FIG. The method of using the liquid detergent article of the present invention is as follows.

  By pushing the pump head portion 19 against the urging force of the spring member 29 by a human hand, the cylindrical piston member 15 and the air piston member 16 of the pump 18 are simultaneously pushed down, and the valve body 31a is opened. The stored liquid (liquid detergent composition) that has flowed into the liquid chamber 30 is pressurized and discharged toward the height direction flow path 21 by opening the valve body 31a. In parallel with this, when an air flow path (not shown) formed along the fitting portion of the hollow pipe 22 and the cylindrical piston member 15 is opened, the height direction flow path 21 is extended from the large-diameter air chamber 24. Air is discharged under pressure. In this way, the accommodated liquid and the air are joined in the joining space 23 in the middle of being discharged toward the height direction flow path 21, and after being mixed under pressure, foaming disposed in the middle height direction flow path 21. It passes through the member 20 and is changed into a foam. The foamed stored liquid passes through the height direction flow path 21 and is discharged from the discharge port 26 to an object to be cleaned (hard surface such as tableware and cooking utensils), a sponge as a cleaning tool, and the like. In addition to the foam member 20, the foam quality is further improved by providing the mesh in the vicinity of the discharge port 26.

  The liquid detergent article of the present invention has a volume by combining a specific liquid detergent composition and a pump former container having a specific foam discharge mechanism, and has an aesthetically preferable foam having excellent foam persistence (for example, Fine bubbles) can be formed.

  The liquid detergent article of the present invention can be applied as a hard surface detergent, and is particularly suitable as a kitchen detergent.

  Each component shown in Table 1 was mixed to obtain a liquid detergent composition of each example. The liquid former composition of the present invention was obtained by filling 300 ml of these liquid detergent compositions into the pump former container shown in FIG.

  Using the obtained liquid detergent article, a discharge test was performed in which the pump head was pushed down at 20 ° C. at a constant speed of 20 mm / second, and the following evaluations were made. The results are shown in Table 1.

(1) Foam volume and uniformity After the pump head is pushed several times by hand and filled up to the discharge port, the foam is formed by discharging bubbles for one push on the black acrylic plate under the above conditions. Was visually observed.
○: There is volume and uniform foam. Δ: There is volume but there is no homogeneity. ×: There is no volume and there is no homogeneity. (2) Sustainability of foam. “(1) Foam volume and uniformity” In parallel with this test, the persistence of the foam was visually observed.
○: Persistence (maintains approximately the same state as during discharge for about 3 minutes or more)
Δ: Slightly non-persistent (coarse bubbles appeared due to coalescence of bubbles in about 3 minutes)
X: No persistence (coarse foams are predominant or disappeared in about 3 minutes)
The ease of pushing the pump head, which is an important factor in the usability of the product, is mainly determined by the viscosity of the filling liquid at the product use temperature and the mesh form of the porous membrane body provided in the pump former. . The lower the liquid viscosity is, the larger the pore size of the mesh is, and the smaller the number of installed sheets is, the easier it is for the user to press.

[Example of formulation]
Next, Table 2 shows formulation examples that can be used as kitchen detergents.

  The kitchen detergent in which the composition of the above blending example was filled in the pump former container of FIG. 1 was excellent in cleanability, the foam discharged from the container had a volume feeling, and the foam sustainability was also excellent.

(Used ingredients)
ES: Sodium polyoxyethylene alkyl ether sulfate [The raw material alcohol is an alcohol obtained by hydroformylation using 1-decene and 1-dodecene 50/50 (mass ratio) as raw materials. After adding 2 mol of EO to this alcohol on average, it was sulfated with sulfur trioxide and neutralized with sodium hydroxide (neutralized until the pH of 11 diluted with water was 11). The ratio of the total polyoxyethylene branched alkyl ether sulfate in the total sodium polyoxyethylene alkyl ether sulfate was 42% by mass. ]
AO: N-lauryl-N, N-dimethylamine oxide Sulfobetaine: Lauryl dimethyl sulfobetaine GE-2EH: 2-ethylhexyl monoglyceryl ether (monoglyceryl ether 98% by mass)
・ Alkenyl succinate: carbon number of alkenyl group 12
Alkyl glucoside: Alkyl glucoside having an alkyl group composition of C12 / C14 = 60/40 (mass ratio) and glucoside average condensation degree of 1.5. Polypropylene glycol: having an average molecular weight of 1000. Preservative: Proxel BDN ( Abyssia)

It is a longitudinal cross-sectional view of the container (pump former container) which comprises a foam discharge mechanism.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Pump former container 11 Container main body 13 Foam discharge device 14 Base cap part 15 Cylindrical piston member 16 Air piston member 17 Cylinder part 18 Pump 20 Foaming member 21 Height direction flow path 22 Hollow pipe 23 Merge space 26 Discharge port

Claims (4)

(A) 20-50 mass% of surfactant,
(B) 1 to 15% by mass of an organic solvent,
(C) 2.5 to 10% by mass of at least one selected from citric acid, tartaric acid, succinic acid, malic acid and lactic acid,
(D) 1 to 10% by mass of benzenesulfonate which may be substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms , and water,
The total content of the components (b), (c), and (d) in the composition is 4.5 to 20% by mass,
A liquid detergent composition having a pH at 25 ° C. of 5 to 8 and a viscosity at 20 ° C. of 30 to 80 mPa · s,
A liquid detergent article filled in a container having a pump former having one or two porous membranes having a mesh size of 100 to 300 / inch as a foam discharge mechanism. The liquid detergent article according to claim 1, wherein the component (b) contains (b1) a water-soluble solvent and (b2) a water-insoluble solvent in a mass ratio of 0.05 to 20 (b1) / (b2).   Furthermore, the liquid cleaning composition contains potassium ion, The liquid cleaning of Claim 1 or 2 which contains the said (c) component and potassium ion by the mass ratio of (c) component / potassium ion = 1-20. Agent articles.   Further, the liquid detergent composition comprises an anionic surfactant (a1) as component (a) and a nitrogen-containing surfactant selected from amine oxide surfactants, betaine surfactants, and alkanolamide surfactants. The liquid detergent article according to any one of claims 1 to 3, further comprising a surfactant mixture containing the agent (a2) at a mass ratio of (a1) / (a2) = 1 to 20.

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