JP2005187741A - Method for improving foam property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method which allows improvement in foam property of an aqueous solution containing a surfactant at a low concentration. <P>SOLUTION: The method comprises using one or more kinds of water-soluble organic solvents selected from formula (I-1) and formula (I-2) in order to improve the foam property of an aqueous composition having a surfactant concentration of 2% by mass or less. Formula (I-1): R'O(C<SB>2</SB>H<SB>4</SB>O)<SB>m</SB>(C<SB>3</SB>H<SB>6</SB>O)<SB>n</SB>R", wherein R' and R" are H, a 1-5C alkyl group, phenyl, or benzyl, and at least one of R' and R" is H; m is 0-5, n is 0-3, and when both m and n are 0, R' is a 3-5C alkyl group. In formula (I-2), R is a 1-8C alkyl group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for imparting sufficient foamability to an aqueous solution having a low surfactant concentration.

  Dirt on hard surfaces in the house can be dust, sebum dirt, dirt, relatively light dirt in the dining room such as cigarette crabs, kitchen table, table, ventilator, range, wall around range, glass, refrigerator Various types of dirt such as oily smoke, food spills, blown spills, and other stubborn oil stains and burnt dirt are generated. It is cleaned and removed using a dedicated cleaning agent.

Patent Document 1 describes a residential cleaner containing propylene glycol monomethyl ether, and Patent Document 2 describes a weakly acidic bathroom cleaner containing a surfactant, soap and a water-soluble organic solvent. Patent Documents 3 to 5 describe hard cleaners containing alkylglycoside surfactants, and Patent Documents 6 and 7 include bathroom cleaners or hard surface cleaners containing alkylamidopropylbetaine and organic solvents. Agents are described.
Japanese Unexamined Patent Publication No. 63-20400 JP-A 63-245499 JP-A-5-51600 JP-A-5-279698 JP-A-5-279696 JP 7-34092 A Japanese Unexamined Patent Publication No. 7-3288

  Conventionally, for dirt adhered on a hard surface, there is a case where a cleaning agent is foamed and sprayed onto the dirt and wiped off with a cloth, but if the surfactant concentration is low, sufficient foaming properties are obtained. It becomes difficult to obtain. In the case of insufficient foaming, the cleaning liquid will flow to areas other than dirt, especially on hard surfaces with inclined surfaces, so that the cleaning liquid will reach the areas that the user does not want to contact with the cleaning liquid. In addition to being very inconvenient in terms of convenience, there is a problem that it is difficult to attach a sufficient amount of application to dirt. On the other hand, when the concentration of the surfactant is increased in order to improve the foaming property, the resistance at the time of wiping is increased, or the residual amount of the surfactant is increased. In some cases, there is a problem that the wiping is required after wiping.

  An object of the present invention is to provide a technique capable of obtaining excellent foaming properties even at a low surfactant concentration. Such a technique is considered useful for obtaining an aqueous composition or a foam-like composition suitable for foam application cleaning.

In the present invention, the foamability of a surfactant aqueous solution having a surfactant concentration of 2% by mass or less is represented by a water-soluble organic solvent represented by the following general formula (I-1) and the following general formula (I-2). The present invention relates to a method for improving the foamability of an aqueous surfactant solution, which is improved by using one or more water-soluble organic solvents selected from water-soluble organic solvents.
R′O (C ₂ H ₄ O) _m (C ₃ H ₆ O) _n R ″ (I-1)
[Wherein, R ′ and R ″ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group, and at least one of R ′ and R ″ is a hydrogen atom. It is. m represents a number from 0 to 5, and n represents a number from 0 to 3. When both m and n are 0, R ′ is an alkyl group having 3 to 5 carbon atoms. ]

  Regarding the water-soluble organic solvent, the term “water-soluble” as used in the present invention refers to a property that dissolves in water at a concentration of 5% by mass or more in water at 20 ° C. without separation or clouding.

  Further, in the present invention, the foaming property means that foaming occurs when the aqueous composition that is the basis of foaming is foamed using a foaming device, and the foaming property is improved. It means that the apparent volume (or bulkiness) of bubbles is improved. Moreover, foam stability shall mean the grade by which the apparent volume of the produced | generated foam is maintained.

  According to the present invention, a method for improving the foamability of a low surfactant concentration aqueous solution is provided. The method of the present invention is expected to be applied to aqueous compositions and foam compositions suitable for foam coating and cleaning.

  In the present invention, a part of water in a low surfactant concentration aqueous solution having a surfactant concentration of 2% by mass or less is mixed with a water-soluble organic solvent represented by the following general formula (I-1) and the following general formula (I-2). The foaming property is found to be improved by substituting one or more water-soluble organic solvents selected from water-soluble organic solvents represented by the formula (1). Hereinafter, the surfactant will be described as the component (a), and the water-soluble organic solvents of the general formulas (I-1) and (I-2) as the component (b).

Regarding the component (b), in the present invention, in the general formula (I), a compound in which one of R ′ or R ″ is a hydrogen atom is more foamable by blending than a compound in which both are hydrogen atoms. Specifically, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, polyoxyethylene (average number of added moles of 1 to 5) ) Monophenyl ether.
Moreover, the compound of general formula (II) is monoalkyl glyceryl ether, and R is preferably an alkyl group having 3 to 5 carbon atoms.

  In general, water-soluble organic solvents are strongly recognized as foam breakers, and it is surprising that water-soluble organic solvents act as foaming improvers for low-concentration surfactants. The reason why the blending of the water-soluble organic solvent has an effect on the foaming property is that we originally added a suitable amount of the water-soluble organic solvent to the surfactant that preferentially forms micelles in the aqueous composition. The degree of micelle formation in the composition is reduced, and it is speculated that the surfactant may be easily arranged at the gas-liquid interface when a foaming operation such as foaming device is performed by gas-liquid mixing. .

  The present invention relates to a method for further improving the foaming property of a low-concentration surfactant. Therefore, the surfactant or the combination of surfactants referred to in the present invention foams in a maximum of 2% by mass aqueous solution. In particular, surfactants or combinations of surfactants that are capable of producing foams with an apparent volume of at least 2.0 ml / g are preferred.

  The component (b) used in the present invention improves the foaming property of the component (a), but the amount of the component (b) to be replaced with water is sufficient to obtain a sufficient foaming property. Except for compounds in which R ′ and R ″ in general formula (I) are both hydrogen atoms, the content is 4% by mass or more, preferably 5% by mass or more in an aqueous solution. Further, the upper limit is 15% by mass in order to obtain a sufficient effect, and particularly 10% by mass is sufficient. In the case of ethylene glycol, dipropylene glycol, and propylene glycol in which both R ′ and R ″ in the general formula (I) are hydrogen atoms, the effect increases as the blending concentration increases. It is 10 mass% or more, preferably 15 mass% or more. Moreover, an upper limit is 20 mass% or less.

[(A) component]
The component (a) of the present invention is a surfactant or a combination of surfactants. When foaming operation is performed using a foaming device, foaming occurs in a maximum of 2% by mass of an aqueous composition (aqueous solution). It is limited to what you do. Even if a surfactant that does not foam at a surfactant concentration of 2% by mass is used, this effect can be obtained depending on the substance. Is not obtained. Accordingly, an antifoaming surfactant is not preferable as the component (a) used in the present invention.

  As the surfactant to be used, an anionic surfactant capable of foaming at a low concentration, an amphoteric surfactant, a nonionic surfactant, and a combination thereof can be used. More specifically, an amine oxide compound having one hydrocarbon group having 8 to 18 carbon atoms and two hydrocarbon groups having 1 to 3 carbon atoms, an alkyl group having 8 to 16 carbon atoms, and an average condensation degree. 1-10 alkylglycoside type nonionic surfactant, alkylbenzene sulfonate having an alkyl group having 8-15 carbon atoms, alkyl sulfate ester salt having 8-16 carbon atoms, average addition mole number of 1-4, alkyl group A polyoxyethylene alkyl ether sulfate having 8 to 16 carbon atoms, an alkyl diphenyl ether disulfonate having 8 to 16 carbon atoms, an alkenyl succinate having 8 to 16 carbon atoms, and carbon An anionic surfactant and an amphoteric surfactant selected from fatty acid salts having a number of 8 to 16.

  Among these surfactants, amphoteric surfactants represented by the following general formula (II) are preferable from the viewpoint of foaming property and general soil removal performance.

[Wherein, R ²⁰ represents an alkyl group or alkenyl group having 9 to 23 carbon atoms, and R ²¹ represents an alkylene group having 1 to 6 carbon atoms. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and p is a number of 0 or 1. R ²² and R ²³ are an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ²⁴ is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. D is a group selected from —SO ₃ ⁻ , —OSO ₃ ⁻ and —COO ⁻ . ]

  Of the surfactants represented by the general formula (II), an alkylamidopropyl acetate betaine type is more preferable.

  An amine oxide compound (i) is also suitable, and an amine oxide compound having one hydrocarbon group having 8 to 18 carbon atoms and two hydrocarbon groups having 1 to 3 carbon atoms [hereinafter referred to as component (i)] is used. preferable. As the component (i), the compound of the general formula (1) is suitable.

[Wherein, R ¹ is an alkyl group or alkenyl group having 8 to 18 carbon atoms, preferably 9 to 12 carbon atoms, R ² is an alkylene group having 1 to 3 carbon atoms, and A is —COO—, —CONH— , -OCO-, -NHCO-. a is a number of 0 or 1, and R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. ]

In the general formula (1), the carbon number of R ¹ is particularly preferably 11 or 12. A is preferably —COO— or —CONH—, and most preferably —CONH—. R ² preferably has 2 or 3 carbon atoms, and R ³ and R ⁴ are preferably methyl groups. a is preferably 0. The most preferred compound as component (i) according to the present invention is decyldimethylamine oxide, lauryldimethylamine oxide, amidopropyldimethylamine oxide caprate, or amidopropyldimethylamine oxide laurate.

Further, as the component (ii) in terms of foam stability, an alkyl glycoside type nonionic surfactant having an alkyl group having 8 to 16 carbon atoms and an average degree of condensation of 1 to 3 can be mentioned. Include those represented by the following general formula (2).
R ⁵ − (OR ⁶ ) _x G _y (2)
[Wherein, R ⁵ represents a linear alkyl group having 8 to 16, preferably 10 to 16, and particularly preferably 10 to 14 carbon atoms, R ⁶ represents an alkylene group having 2 to 4 carbon atoms, and G represents Residues derived from reducing sugars, x is an average value of 0-6, y is an average value of 1-3, preferably 1-2. ]

  In the compound of the general formula (2), G is a residue derived from a reducing sugar, and the starting reducing sugar may be either aldose or ketose, and a triose having 3 to 6 carbon atoms. , Tetrose, pentose, hexose. Specific examples of aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, galose, aldose, idose, talose, and xylose. Examples of ketose include fructose. In the present invention, among these, aldopentose or aldohexose having 5 or 6 carbon atoms is particularly preferred, and glucose is most preferred.

  In the method for improving foamability of the present invention, the component (a) is a combination of the component (i) and the component (ii), or the component (i) and a fatty acid salt having 8 to 16 carbon atoms (iii) [hereinafter, ( It is preferable to target a system that is a combination of [iii) component]. These combinations not only improve foaming and foam stability, but also improve foam adhesion to hard surfaces (for example, foam is less likely to sag on an inclined surface), improve foam stability, and wipe the wipes after wiping. There is a tendency for (wiping performance) to become inconspicuous. When using together, since the tendency for foam adhesion to fall is seen when the mass ratio of (i) component / (ii) component is 50/50 or less, preferably 99/1 to 50/50, more preferably 95 / 5-60 / 40. The mass ratio of component (i) / component (iii) is preferably 99/1 to 20/80, more preferably 95/5 to 30/70. In addition, you may use three components of (i) component, (ii) component, and (iii) component together. In the present invention, the component (a) is composed of an amphoteric surfactant represented by the general formula (II), or a combination of the component (i) and the component (ii) or the component (iii). Most preferably.

  In addition, since the polyoxyethylene (and / or polyoxypropylene) alkyl ether type nonionic surfactant having an average added mole number of 4 to 20 and an alkyl group having 8 to 14 carbon atoms has a defoaming property, It is difficult to obtain this effect alone as the component (a).

  Based on the above-mentioned knowledge about improvement of foamability, the present invention provides an aqueous composition suitable for foam coating and cleaning, which is improved in foamability, and further a foam composition formed from the composition. Is done.

  Here, the concentration of the component (a) is preferably 0.1 to 1.5% by mass in the aqueous composition from the viewpoint of resistance when wiping with a towel or a waste cloth or generation of wiping traces after wiping. More preferably, it is 0.1-1.0 mass%, Most preferably, 0.1-0.5 mass% is contained.

  In such an aqueous composition, from the viewpoint of foam adhesion as well as foaming property and foam stability, (i) component and (ii) are used in combination as component (a), or (i) component and (iii) ) Component is preferably used in combination, and the combination ratio is also as described for the aqueous solution.

  Moreover, the density | concentration of (b) component in this aqueous composition is also as the density | concentration in the said aqueous solution.

  A foam-like composition is produced | generated by foaming operation by a foaming device, for example from the aqueous composition containing the said (a) component and (b) component. Hereinafter, the optional components that can be blended in the aqueous composition for obtaining the foam composition will be described in detail.

  When applying the foam composition of the present invention to a cleaning agent for oil stains such as around the kitchen, it is desirable to add an inorganic alkaline agent [hereinafter referred to as component (c)] ( As the component c), one or more selected from sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate are preferred. In particular, the aqueous composition preferably contains 0.1 to 2% by mass of sodium carbonate, more preferably 0.2 to 1.5% by mass, and particularly preferably 0.5 to 1.5% by mass. As other alkaline agents, alkanolamine [hereinafter referred to as component (d)] is suitably used because it exhibits excellent detergency and is volatile so that there is no need for wiping twice. In this case, the ratio is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 4.0% by mass, and particularly preferably 0.5 to 3.5% by mass in the aqueous composition.

  In addition, when the technology of the present invention is applied to a sterilization cleaning agent, it can contain various antibacterial agents. For example, “Technical Information Association, Inc.” The antibacterial agent [hereinafter referred to as “component (e)”] described in “Evaluation” chapters I and II may be added within a range that does not hinder foaming ability. Among these antibacterial agents, preferred examples include quaternary ammonium compounds having one or more hydrocarbon groups having 6 to 16 carbon atoms and the remainder being a hydrocarbon group or benzyl group having 1 to 3 carbon atoms. Specific preferred compounds of the quaternary ammonium compound include compounds of the following general formula (3) to general formula (5).

[Wherein R ⁷ and R ¹² are each an alkyl group or an alkenyl group having 6 to 16 carbon atoms, preferably 8 to 16 carbon atoms, preferably an alkyl group, and R ⁹ and R ¹⁰ are each an alkyl group having 1 to 3 carbon atoms. An alkyl group or a hydroxyalkyl group; W is an aromatic ring or an ester group or an amide group selected from —COO—, OCO—, —CONH—, and —NHCO—. R ⁸ is an alkylene group of 2 to 4 when W is an aromatic ring, or — (O—R ¹⁷ ) _p —, and an alkylene group of 2 to 4 when W is an ester group or an amide group. It is a group. Here, R ¹⁷ is an ethylene group or a propylene group, preferably an ethylene group, and p is an average of 1 to 10, preferably 1 to 5. R ¹¹ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, particularly preferably a methylene group. Q is a number of 0 or 1. Two or more (preferably two) of R ^{13 to} R ¹⁶ are alkyl groups having 8 to 14 carbon atoms, preferably 8 to 12 carbon atoms, and the rest are alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms. It is. Z ⁻ is an anion group, preferably a halogen ion, a sulfate ion, an alkyl sulfate ion having 1 to 3 carbon atoms, or an aromatic sulfonate ion optionally substituted with an alkyl group having 1 to 3 carbon atoms. ]
As the most preferred component (e), compounds of the following general formula can be mentioned.

  These (e) component quaternary ammonium compounds are contained in the aqueous composition in the range of 0.002 to 0.5 mass%, more preferably 0.004 to 0.3 mass%, and still more preferably 0. 0.004 to 0.1% by mass. Within this range, even when the dirt load is large, a good sterilization effect can be obtained, which is economically advantageous.

  In the aqueous composition, the surfactant represented by the general formulas (3) to (5) of the component (e) is a surfactant of the present invention even if it has foaming properties. It should not be considered and therefore not included in the surfactant concentration range. By the way, when (e) component is further mix | blended using an anionic surfactant as (a) component, there exists a possibility that a property of each other may be offset, and a caution is required for the mixing | blending. Specifically, when the component (e) is blended, the concentration of the anionic surfactant is preferably 1/2 or less (mass ratio) with respect to the component concentration (e). It is preferable to use a combination of component (i) and component (ii).

  In the present invention, the concentration of the organic compound other than the component (a), the component (b), the component (d), and the component (e) [hereinafter referred to as the component (f)] does not affect the foaming effect of the present invention. Considered to the extent that the feel of the treated surface is not degraded.

  You may mix | blend ethanol with the aqueous composition of this invention as an organic compound other than the above.

  The pH at 20 ° C. of the aqueous composition according to the present invention is 6.0 to 8.0 neutral for reducing the substrate damage property of the object for cleaning the object in the environment where there is little oil stain such as living It is preferable to set it to 8.5 to 12.5 when it is intended for kitchen stains mainly composed of oil stains. In order to adjust to such pH, acid agents such as hydrochloric acid, sulfuric acid, phosphoric acid and other organic acids can be blended in addition to hydroxycarboxylic acids such as citric acid, succinic acid and lactic acid. In addition to sodium, potassium carbonate and alkanolamine, an alkali agent selected from sodium hydroxide and potassium hydroxide can be used.

  In addition, polymer thickeners such as xanthan gum and polyethylene glycol, hydrotropes such as paratoluene sulfonate and cumene sulfonate, chelating agents such as organic phosphonic acid and ethylenediamine tetraacetate, antibacterial and antifungal agents, Although a fragrance | flavor component etc. can be mix | blended unless the foamability and stability of this aqueous composition are impaired, a caution is required for the compounding quantity.

  Implementation of the foaming method of the present invention is achieved by passing an aqueous composition in which the above-mentioned component (a), component (b), and other optional components are dissolved in water, through a foaming device, as a foam composition. can get. In the aqueous composition, water is blended as the remainder of the component (a), the component (b) and other optional components. Specifically, water is preferably 75% by mass or more, more preferably 80% by mass in the aqueous composition. Occupy more than 50%.

  Foaming consists of foam of the aqueous composition and gas (typically air). Moreover, it is preferable that the bubble which comprises a foam-like composition is an average particle diameter of 1-10000 micrometers, Furthermore, it is 10-5000 micrometers, Especially 100-3000 micrometers. Further, the viscosity of the aqueous composition before foaming is preferably 30 mPa · s or less, more preferably 10 mPa · s at 20 ° C. The viscosity as used in the present invention is measured as follows. First, a B-type viscometer model BM manufactured by TOKIMEC. INC is prepared with a rotor of rotor No. 1. The sample is filled into a tall beaker and prepared at 20 ° C. in a constant temperature bath at 20 ° C. A sample prepared at 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.

  As a foaming device capable of achieving such foaming, foaming was achieved by impregnating a liquid composition into a flexible and breathable flexible material capable of holding a solution such as sponge, fabric, and non-woven fabric and rubbing it by hand. However, it is preferable to use a method in which bubbles are formed by a mechanism that forms bubbles by taking in air during discharge by a pump or squeeze operation. In the present invention, it is most preferable to use a foaming device using a discharge means having a mechanism for forming bubbles by taking in air during discharge.

  As a container having a foaming device by a discharge means having a mechanism for forming bubbles by taking in air at the time of such discharge, particularly as a trigger type spray container, as shown in FIG. An accumulator spray container that includes a container main body 1, a front portion 16 that includes a foam ejection nozzle at the front, and pressurizes liquid with a trigger 2 can be used.

  As shown in FIG. 2, this spray container has a plate-like body 3 made of synthetic resin attached to the front portion of the spray-container main body 1, and this plate-like body 3 is provided with a cylindrical protrusion 4. An annular convex portion for fitting is provided on the outer peripheral surface of the cylindrical projecting portion 4. The plate-like body 3 is provided with a columnar portion 8 that is slightly shorter than the cylindrical protruding portion 4 at the center position of the cylindrical protruding portion 4.

  Further, the plate-like body 3 inside the cylindrical projecting portion 4 is provided with a liquid discharge path 5 that communicates with a spout of a pump mechanism (not shown). As shown in FIG. 2, a longitudinal groove-shaped linear flow channel 10 is provided opposite to the outer peripheral portion of the tip of the cylindrical portion 8, and the swirl flow channel 9 is disposed outside the linear flow channel 10. It is provided.

  Further, the swirl flow passage 9 is opposed to the outer peripheral portion of the tip portion of the cylindrical portion 8 by shifting the position by 60 degrees in the circumferential direction from the portion where the straight flow passage 10 and the swirl flow passage 9 are provided. It is provided. The head portion 16 that is rotatably fitted to the column portion 8 is made of synthetic resin, and is provided with a top plate 17 at a position slightly closer to the front portion than the center portion. A cylindrical portion 19 is provided, and an inner surface of the cylindrical portion 19 is provided with an annular concave portion into which an annular convex portion provided on the outer peripheral surface of the cylindrical protruding portion 4 is fitted. An annular groove 20 is provided on the inside.

  A cylindrical portion 24 is provided on the top plate 17 on the inner side of the cylindrical portion 19 toward the rear. The cylindrical portion 24 is tightly fitted to the columnar portion 8 so as to be rotatable. As shown in FIG. 2, a liquid passage 27 communicating with the liquid pouring path 5 of the plate-like body 3 is provided inside the portion 24.

  And the nozzle 26 of the liquid ejection part 25 is provided in the center part of the top plate 17 inside the cylindrical part 24, and also, as shown in FIG. The ejection paths 29 are provided so as to face each other.

  Then, at the position shown in FIG. 2, the swirl flow channel 9 and the straight flow channel 10 of the cylindrical portion 8 are formed so as to communicate with the swirl flow channel 28 and the straight flow channel 29 on the rear surface of the top plate 17, respectively. It is. The liquid flow outlet 25 is formed by the swirl flow passage 9, the swirl flow ejection passage 28 communicating with the swirl flow passage 9, the straight flow ejection passage 29 communicating with the straight flow passage 10, and the nozzle 26. It is formed.

  A circular recess 18 whose center coincides with the center of the nozzle 26 is provided at the front portion of the top plate 17 of the head 16, and an annular recess is provided on the inner surface of the peripheral wall of the circular recess 18. A cylindrical resin wall 35 made of synthetic resin is fitted into the circular concave part 18, and an annular convex part formed on the outer peripheral surface of the cylindrical cylindrical wall 35 engages with the annular concave part of the circular concave part 18 to form a cylinder. A cylindrical wall 35 is fitted into the circular recess 18 and the cylindrical wall 35 surrounds the front of the nozzle 26.

  The cylindrical wall 35 is provided with an air inflow path 36 provided in the longitudinal direction at the outer peripheral edge, and protrudes toward the center of the cylindrical wall 35 on the inner surface of the end of the cylindrical wall 35. Five screens 40 are provided. The screen 40 is formed to have a length that does not reach the center of the cylindrical partition wall 35, and a through-hole shape is formed between the distal ends of the five screens 40 at the center position of the cylindrical partition wall 35. A portion 42 is formed.

  When the container body is filled with an aqueous composition and the trigger mechanism 2 is operated to operate a pump mechanism (not shown), the liquid passes from the liquid discharge path 5 through the liquid path 27 and is used for the swirl flow path 9 and the linear flow path. It is sent to the flow path 10 and reaches the swirl flow ejection path 28 provided in the head 16 from the swirl flow path 9 and reaches the straight flow ejection path 29 provided in the head 16 from the straight flow path 10.

  Then, a swirl flow is ejected from the swirl flow ejection path 28, and a linear flow is ejected from the linear flow ejection path 29 and ejected as particles from the nozzle 26. The ejected particles collide with the screen 40 and scatter. The spray particles that collide and scatter are mixed with other spray particles and mixed with the air sucked from the air inflow path 36 to form very fine bubbles, and the void 43 and the through-hole-shaped portion. 42 is ejected from the cylindrical wall 35.

  Then, the spray flow that has flown to the center of the cylindrical wall 35 advances the through-hole-like portion 42 vigorously without being blocked by the screen 40, and accelerates the forward speed of the foam that advances through the void 43. , Bubbles are ejected vigorously, and no dripping occurs.

  When the aqueous composition has a low viscosity, for example, a viscosity at 20 ° C. of 30 mPa · s or less, a series of liquid flows are smooth, that is, a sufficient liquid flow rate and flow velocity can be obtained in each flow path.

  As a result, rich and creamy foam can be directly attached to the clothing to be cleaned.

  In addition to FIGS. 1 and 2, examples of the apparatus for mechanically forming bubbles include those having a porous film in the discharge path. Here, examples of the porous film include a sponge, a sintered body, and a net. In particular, if the aqueous composition remaining on the porous membrane clogged due to drying and solidification, the solidified material can be immediately dissolved by the flow of bubbles during the next discharge, so that the clogging can be eliminated. It is preferable to use the net. In this case, the net mesh is preferably 50 to 500 mesh, more preferably 150 to 400 mesh. By using a mesh net in this range, creamy foam can be generated. Moreover, as a material of such a mesh, nylon, polyester, etc. can be illustrated preferably. Specifically, a foam discharge mechanism as shown in FIG. 3 can be exemplified.

  In the foam discharge container 310 of FIG. 3, a cap 312 is screwed into an opening 311 a of a squeeze container main body 311, and a gas-liquid mixing unit 313 is provided at the center position inside the cap 312. The gas-liquid mixing part 313 has a structure in which a tube connecting part 313a and a porous film 313b are disposed.

  Further, in the foam discharge container 310, the dip tube 314 is fitted to the tube connecting part 313a of the gas-liquid mixing part 313 through a certain gap and is supported by the cap 12 in a state of communicating with the gas-liquid mixing part 313. In addition, a dip tube 314 is inserted into the container body 311. An openable / closable nozzle part 315 is screwed to the discharge side (upper side in the figure) of the gas-liquid mixing part 313 of the cap 312, and the nozzle part 315 is closed by rotating 90 degrees with respect to the cap 312. Switching between the position and the open position is set. In the closed position, the annularly projecting sealing portion 316 of the nozzle portion 315 is in close contact with the plug portion 317 located above the gas-liquid mixing portion 313, and in the open position, the seal ring portion 316 is isolated from the plug portion 317 and discharged. Form a road. The discharge port 318 of the nozzle portion 315 is provided with a porous membrane fixture 318a and a porous membrane 318b at the tip thereof, and the porous membrane 318b is fitted and fixed by the porous membrane fixture 318a. ing.

  In the foam discharge container 310, a ball valve 322 is disposed in the air return path 321 of the cap 312. The ball valve 322 is in close contact with the seal portion 321a above the air return path 321 when foam is discharged. The pressure in the container main body 311 is increased by squeezing. Then, the ball valve 322 is locked to the protrusion 321b below the air return path 321 after the foam discharge is finished, and external air is discharged by the negative pressure in the container due to the container restoring force of the container body 311 released from squeeze. Introduce into the container body 311. The foam discharge container 310 discharges foam by the following operation.

  (1) By rotating the nozzle portion 315, the seal ring portion 316 of the nozzle portion 315 is isolated from the plug portion 317 of the cap 312 to form a bubble discharge path indicated by an arrow X in FIG.

  (2) By manually squeezing the container main body 311, air (or liquid) directly introduced into the gas-liquid mixing unit 313 of the cap 312 and the gas-liquid mixing unit 313 through the dip tube 314 are introduced. A bubble is formed by mixing liquid (or air) and passing through the porous film 313b, and this bubble passes through the bubble discharge path X described above, and the porous portion provided at the tip of the discharge port 318 of the nozzle portion 315. The ink is discharged from the discharge port 318 through the film 318b. At this time, the ball valve 322 is brought into close contact with the seal portion 321a of the air return path to increase the pressure in the container body 311.

  (3) After the foam is discharged, the ball valve 322 is locked to the protrusion 321b of the air return path 321 and external air is drawn by the negative pressure in the container due to the container restoring force of the container body 311 released from squeeze. 3 is introduced into the container body 311 from the air return path indicated by the arrow Y. At this time, the external air tries to pass through the reverse path of the foam discharge path X described in (2) above, but the residual foam in the porous film 318b becomes resistance, and therefore passes through the air return path Y described above. . In addition, when the residual foam of the porous film 318b becomes resistance and air introduction into the air return path Y is gentle, the air return path 321 and the ball valve 322 may be provided at a position that directly communicates with the outside of the cap 312. .

  Examples of the trigger type sprayer having a foaming device include a trigger having a discharge device described in JP-A-11-100594 and registered utility model No. 3044068, JP-A-2000-185247, JP-A-2001-2001. No. 334178, JP-A No. 2002-20266, JP-A No. 7-256162, JP-A No. 8-71463, JP-A No. 9-285746, JP-A No. 10-85637, JP-A No. 7-9451 Reference can be made to Japanese Laid-Open Patent Publication No. 7-9492.

  Examples of squeeze formers include: Japanese Utility Model Publication No. 58-174272, Japanese Utility Model Publication No. 62-42787, Japanese Patent Publication No. 52-16567, etc. Examples of the pump former that discharges water include Japanese Utility Model Laid-Open No. 3-7963 and Japanese Utility Model Laid-Open No. 62-103458.

The present invention provides, as a preferred embodiment of the method for improving foaming, a foam-coated cleaning agent obtained by filling the aqueous composition according to the present invention into a container equipped with a foaming device. Most preferably, the following aspect is mentioned.
(A) (i) component and (ii) component are 0.1-1.0 mass% in total [However, (i) component / (ii) component is 95 / 5-60 / 40 by mass ratio.] Or 0.1 to 1.0% by mass in total of component (i) and component (iii) [provided that component (i) / component (iii) is in a mass ratio of 95/5 to 30/70]
(B) 5-10% by mass of a water-soluble organic solvent selected from propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether
(C) and / or (d) Alkaline agent (alkanolamine, sodium carbonate, potassium carbonate) 0.5-1% by mass
(E) Quaternary ammonium compound 0.002-0.1 mass%
(F) Other organic compounds (organic solvent, fragrance, etc.) 0.01 to 5.0% by mass
And a washable aqueous composition having a pH (20 ° C.) of 8.5 to 11.5 containing the remaining water, and has a mechanism for forming bubbles by taking in air when discharging the aqueous composition. Foam-applied detergent obtained by filling a container equipped with a foaming device of a trigger type sprayer type (the most preferable one having the mechanism of FIG. 2) by a discharge means.

Example 1
When an aqueous composition containing 0.5% by mass of lauric acid amidopropyl-N, N-dimethylacetic acid betaine as component (a) and diethylene glycol monoethyl ether as component (b) are blended at the concentrations shown in Table 1. The foaming property and the rate of foaming increase were evaluated. The foamability and the foam increase rate were evaluated by the following methods. The results are shown in Table 1.

<Foamability>
Spray 200 times into a 200 ml plastic graduated cylinder (inner diameter 4 cm) using the container equipped with the trigger type sprayer shown in FIGS. 1 and 2 and use the following formula from the mass of the aqueous solution and the volume of the foam. Foamability (ml / g) was calculated.
Foaming property (ml / g) = foam volume (ml) / aqueous solution mass (g)

<Foam increase rate>
(B) The foaming property (h ₀ ) when the component is not used (reference composition) and the foaming property (foaming property h _{1 of} composition ₁ ) when the compounds in the table are used are compared, The foaming increase rate was calculated by the following formula and evaluated.
Foam increase rate (%) = (h ₁ / h ₀ ) × 100

  From this result, it was confirmed that even in the case of a system having a low surfactant concentration, the foamability is improved without impairing the foam stability by increasing the component (b).

Example 2
Foaming when an aqueous composition containing the surfactants A to E in Table 2 (component (a)) at the concentration in Table 2 and the compound in Table 2 (component (b)) at the concentration in Table 2 Properties and foaming increase rate were measured in the same manner as in Example 1. The results are shown in Table 2. In Table 2, the mass% in () of the surfactant and the compound is the mass% in the aqueous composition.

(Note) The components in the table are as follows.
Surfactant A: Amidopropyl laurate-N, N-dimethylacetate betaine Surfactant B: Lauryldimethylamine oxide Surfactant C: Sodium caprate Surfactant D: Alkyl polyglucoside (10 carbon atoms) , 12 and 14 linear alkyl groups, average sugar condensation degree 1.4)
-MFG: Propylene glycol monomethyl ether-EDG: Diethylene glycol monoethyl ether-BDG: Diethylene glycol monobutyl ether-Monoalkyl glyceryl ether: A mixture of isomeric and linear compounds with 5 carbon atoms in the alkyl group

Example 3
Table 3 shows formulation examples of the aqueous detergent for foam-type coating and cleaning with improved foamability according to the present invention. This is sprayed and bubbled through the foaming device.

(Note) The components in Table 3 are the same as those in Table 2. Sanizole C is benzalkonium chloride (a mixture of 12 and 14 carbon atoms in the alkyl chain), manufactured by Kao Corporation, and EDTA3Na is ethylenediaminetetraacetic acid 3Na salt.

It is a figure which shows an example of the trigger type spray container used by this invention. It is sectional drawing of the former of a trigger type spray container. It is a partial expanded sectional view of the foam discharge container used by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 25 Liquid ejection part 26 Nozzle 28 Swirling flow ejector 29 Linear flow ejector 35 Cylindrical wall 36 Air inflow path 40 Screen 42 Through-hole part 310 Foam discharge container 311 Container main body 313 Gas-liquid mixing part 313b Porous film | membrane 315 Nozzle part 318 Discharge port 318a Porous film X Foam discharge path Y Air return path

Claims (3)

The foamability of a surfactant aqueous solution having a surfactant concentration of 2% by mass or less is determined based on the water-soluble organic solvent represented by the following general formula (I-1) and the water-soluble organic represented by the following general formula (I-2). A method for improving foamability of an aqueous surfactant solution, which is improved by using one or more water-soluble organic solvents selected from solvents.
R′O (C ₂ H ₄ O) _m (C ₃ H ₆ O) _n R ″ (I-1)
[Wherein, R ′ and R ″ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group, and at least one of R ′ and R ″ is a hydrogen atom. It is. m represents a number from 0 to 5, and n represents a number from 0 to 3. When both m and n are 0, R ′ is an alkyl group having 3 to 5 carbon atoms. ]

The surfactant has an amine oxide type surfactant (i) having one hydrocarbon group having 8 to 18 carbon atoms and two hydrocarbon groups having 1 to 3 carbon atoms and an alkyl group having 8 to 16 carbon atoms. And a combination of an alkyl glycoside type nonionic surfactant (ii) having an average degree of condensation of 1 to 3 or a combination of (i) and a fatty acid salt (iii) having 8 to 16 carbon atoms. Item 2. A method for improving foamability of an aqueous surfactant solution according to Item 1. The method for improving foamability of an aqueous surfactant solution according to claim 1, wherein the surfactant is an amphoteric surfactant represented by the following general formula (II).

[Wherein, R ²⁰ represents an alkyl group or alkenyl group having 9 to 23 carbon atoms, and R ²¹ represents an alkylene group having 1 to 6 carbon atoms. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and p is a number of 0 or 1. R ²² and R ²³ are an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ²⁴ is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. D is a group selected from —SO ₃ ⁻ , —OSO ₃ ⁻ and —COO ⁻ . ]

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