JPH10237496A - Smectite-containing liquid detergent composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition being excellent in stability against separation after long-term storage and safe to man and having high foamability and high detergency by mixing a smectite clay mineral with anionic, nonionic, amphoteric and/or semi-polar surfactants and a dispersion stabilizer being a specified copolymer in a specified mixing ratio. SOLUTION: This composition comprises 0.01-10wt.% smectite clay mineral (e.g. montmorillonite), 0.1-40wt.% anionic surfactant, 0.1-40wt.% nonionic surfactant, 0.1-40wt.% amphoteric and/or semi-polar surfactants and 0.01-5wt.% dispersion stabilizer being a copolymer having a molecular weight of 50,000-2,000,000 as measured by viscosimetry and comprising repeating units of formula I (wherein R<1> is H, an alkali metal, an unsubstituted-alkanol-substituted ammonium or a 1-4C alkyl) and repeating units of formula II (wherein R<2> is R<1> ) in a ratio of the repeating units of formula I to those of formula II of desirably 2/8 to 7/3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a low-viscosity liquid detergent having a viscosity of not more than 2000 cp at 20 ° C., such as a kitchen detergent, a shampoo, a body soap, and a liquid facial cleanser, in which a smectite clay mineral is stably dispersed. In particular, the present invention relates to a liquid detergent composition containing a smectite-based clay mineral having excellent separation stability during long-term storage, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, there has been a demand for cleaners that are friendly to human skin and the environment. Surfactants used in liquid cleaners have high foaming properties and detergency, but are anionic, which have strong skin irritation. From the surfactant-based composition, reduce the blending amount of anionic surfactant, shift to a nonionic surfactant mixed system with weaker skin irritation, and further amphoteric surfactant or semipolar surfactant Anionic surfactant, which is blended and has the excellent foaming and cleaning properties of anionic surfactant, while keeping the skin irritation as low as possible.
Liquid detergents comprising a mixed composition of a nonionic surfactant and an amphoteric surfactant and / or a semipolar surfactant are mainly used.

[0003] In order to further improve the performance, a smectite-based clay mineral having extremely low irritation to human skin and high stability is added to the above-mentioned mixed composition to improve the feeling of use or the feeling after use. A liquid cleaning composition has been proposed (Japanese Patent Application Laid-Open No. Hei 7-116469).
Further, in order to improve the feeling of use and to improve the inconvenience in handling due to the low viscosity, a composition in which a certain smectite-based clay mineral is blended as a colloid silicate with N-acyl glutamate has also been proposed. (JP-A-7-11288).

[0004] On the other hand, the quality stability of commodities is becoming stricter year by year, and it is required that the quality does not change even immediately after production or even after long-term storage. One of the factors that greatly deteriorates the quality of a product during storage for a long period of time is separation stability. That is, when a practical product undergoes such separation, the composition of each separated phase is different, and when actually used at home, for example, the performance of the liquid cleaning agent discharged from the container may vary depending on the location (height position). ) And is not preferred. Further, in general, in the separation, since a composition having a high specific gravity is precipitated in the lower layer, it is considered that the viscosity of the bottom of the container becomes extremely high and it becomes difficult for the detergent to be removed from the container, which significantly lowers the commercial value.

[0005] Further, since the liquid detergent composition to which the present invention is applied has a practically preferable appearance which is low in viscosity and nearly transparent or translucent, most of such liquid compositions are transparent. It is put on the market in a simple container. Therefore, when the contents are separated, the appearance is remarkably deteriorated and the commercial value is spoiled, which is not preferable.

In the case of a liquid detergent, a long-term storage period is 2
The year is one guide. That is, at least 2
It is important to maintain stable performance without separation for years. As a deterioration promotion test method for guaranteeing the separation stability for two years, a storage stability test at 50 ° C. and a freeze-recovery test are usually used. In other words, in order to be stable at room temperature for two years, it is necessary that the stability test is stable for 4 weeks in the case of the storage stability test at 50 ° C., and it is important that the separation is not performed even after the freeze-recoverability test is repeated five times. become.

However, the smectite clay mineral is an inorganic substance, and after dispersion, has a particularly good flowability of 2000 cp.
When dispersed in the following aqueous solution of a low-viscosity surfactant, its specific gravity is about 2.5, depending on the type, and thus separates and sediments by long-term storage like other inorganic particles. This phenomenon also occurs in the smectite-containing liquid detergent composition described above, and has a drawback that the separation stability is poor when stored at 50 ° C. for a long time or when freeze-recovery is repeated. It has been found that such a separation phenomenon is promoted by a certain type of surfactant, and particularly, in a composition containing an amphoteric surfactant and / or a semipolar surfactant, the separation is remarkably promoted. Also, with liquid detergent,
It was also found that compositions with lower viscosity were easier to separate.

That is, a low viscosity containing a smectite clay mineral and an anionic surfactant, an amphoteric surfactant and / or a semipolar surfactant, and a nonionic surfactant, particularly, a viscosity at 20 ° C. of 2000 cp or less. Liquid detergent compositions have the disadvantage that the separation stability of smectite-based clay minerals is extremely poor, which is not preferred in practice.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a smectite-based smectite surfactant comprising a mixed composition of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and / or a semipolar surfactant. Smectite-containing liquid that solves the problems of liquid detergent compositions containing clay minerals, is gentle to humans, has high foaming properties and detergency, has excellent usability, and has stable performance even after long-term storage. It is an object to provide a detergent composition and a method for producing the same.

[0010]

Means for Solving the Problems As a result of earnest studies, the present inventors have found that the separation stability can be greatly improved by blending a dispersion stabilizer or optimizing the blending order of each component. Thus, the present invention has been completed. That is, the addition of the dispersion stabilizer improves the dispersibility. In addition, smectite clay minerals are usually negatively charged, and when a slightly positively charged amphoteric surfactant or semipolar surfactant is added, the two attract each other to form a complex, and a water-insoluble hydrophobic substance is formed. Substance. Then, if left as it is, aggregation occurs with each other, and the complex precipitates and separates. As described above, in a composition containing a smectite clay mineral and an amphoteric surfactant or a semipolar surfactant or both of them, it is extremely difficult to stably disperse the smectite clay mineral. Therefore, in order to prevent such agglomeration and separation, first, the smectite clay mineral is finely dispersed in advance with an anionic surfactant having a high dispersibility, and then the amphoteric surfactant is added. It has been attempted to uniformly disperse the smectite-based clay mineral by preventing contact with an agent and preventing the formation of a complex between the two.

However, according to the study of the present inventors, although the dispersion obtained by such a blending method can finely disperse the smectite-based clay mineral, it can be subjected to a storage stability test at 50 ° C. or a freeze recovery. It was found that the separation was easy and the separation stability was extremely poor. Conversely, as in the present invention, a smectite-based clay mineral and an amphoteric surfactant or a semipolar surfactant are preliminarily mixed to form an unstable complex, and then dispersed with an anionic surfactant. Then, it was found that when the mixture was stabilized with a nonionic surfactant and further a dispersion stabilizer was added, the separation stability was remarkably improved, and the present invention was completed.

That is, the smectite-containing liquid detergent composition of the present invention has a smectite-based clay mineral of 0.01 to 10%.
0.1% to 40% by weight of an anionic surfactant, 0.1 to 40% by weight of a nonionic surfactant, and at least one of an amphoteric surfactant and a semipolar surfactant.
1 to 40% by weight and 0.01 to 5% by weight of a dispersion stabilizer, wherein the dispersion stabilizer is a repeating unit represented by the following general formula (I):

Embedded image (Wherein R ¹ is a hydrogen atom, an alkali metal, an unsubstituted alkanol group-substituted ammonium group or an alkyl group having 1 to 4 carbon atoms) A repeating unit represented by the following general formula (II):

Embedded image (Wherein R ² is a hydrogen atom, an alkali metal, an unsubstituted alkanol group-substituted ammonium group or an alkyl group having 1 to 4 carbon atoms), and has a molecular weight of 50,000 to 200 as determined by a viscosity method.
It is characterized by being a copolymer of 10,000.

[0013] The method for producing a smectite-containing liquid detergent composition of the present invention is characterized in that the smectite-based clay mineral is added to the smectite-based clay mineral in an amount of 0.1%.
0.1 to 10% by weight, 0.1 to 4% of anionic surfactant
0% by weight, 0.1 to 40% by weight of a nonionic surfactant, 0.1 to 40% by weight of at least one or more of an amphoteric surfactant and a semipolar surfactant, and 0.01 of a dispersion stabilizer. -5% by weight, and the dispersion stabilizer comprises a repeating unit represented by the following general formula (I):

Embedded image (Wherein R ¹ is a hydrogen atom, an alkali metal, an unsubstituted alkanol group, a substituted ammonium group or an alkyl group having 1 to 4 carbon atoms) A repeating unit represented by the following general formula (II):

Embedded image (Wherein R ² is a hydrogen atom, an alkali metal, an unsubstituted alkanol group-substituted ammonium group or an alkyl group having 1 to 4 carbon atoms), and has a molecular weight of 50,000 to 200 as determined by a viscosity method.
In preparing a liquid detergent composition which is a copolymer of 10000, 1) mixing an aqueous dispersion of a smectite-based clay mineral with an amphoteric surfactant and / or a semipolar surfactant, 2) Mixing the mixed solution obtained in the above step 1) with an anionic surfactant; 3) mixing the mixed solution obtained in the above step 2) with a nonionic surfactant; 4) further mixing It is characterized in that the mixture obtained in the above step 3) is mixed with a dispersion stabilizer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a surfactant to be incorporated in a cleaning composition will be described. As the anionic surfactant used in the present invention, an anionic surfactant such as a normal soap, a sulfonate, a sulfate, a phosphate, an acylamino acid or the like is used. Among these anionic surfactants, examples of the soap include saturated or unsaturated fatty acid (C ₈ -C ₂₀ ) salts. Examples of the sulfonate-based anionic surfactant include a linear or branched alkyl (C ₈ -C ₂₃ ) sulfonic acid salt, a linear alkyl (C ₈ -C ₂₂ ) sulfonic acid salt, and a long-chain olefin (C _8). -C ₂₂₎ sulfonic acid salts. Examples of the sulfate-based anionic surfactant include long-chain monoalkyl (C _{8 to} C ₂₂ ) sulfate and polyoxyethylene (1 to 6 mol) long-chain alkyl (C _{8 to} C ₂₂ ) ether sulfate. , polyoxyethylene (1-6 moles) alkyl (C ₈ -C ₁₈₎ phenyl ether sulfuric acid ester salts and the like, as the phosphate-based anionic surfactant, for example, long-chain monoalkyl, dialkyl or sesqui Alkyl (each alkyl group has 8 to 22 carbon atoms) phosphate, polyoxyethylene (1 to 6 mol) monoalkyl, dialkyl or sesquialkyl (each alkyl group has 8 to 2 carbon atoms)
2) phosphate and the like.

N-acylamino acids and salts thereof are suitable as acylamino acid-based anionic surfactants, such as N-acyl-N-methylglycine salt and N-acyl-N-methyl-β. -Alanine salts, N-acyl glutamates and the like. N-acyl-N-
Examples of the methylglycine salt include N-lauroyl-N
-Methylglycine, N-myristoyl-N-methylglycine, N-palmitoyl-N-methylglycine, N-stearoyl-N-methylglycine, N-cocoyl-N-
Those having a straight-chain or branched-chain saturated or unsaturated acyl group having 8 to 22 carbon atoms, such as methylglycine, may be mentioned.

Examples of the N-acyl-N-methyl-β-alanine salt include N-lauroyl-N-methyl-β-alanine.
Alanine, N-myristoyl-N-methyl-β-alanine, N-palmitoyl-N-methyl-β-alanine, N
8 to 2 carbon atoms such as stearoyl-N-methyl-β-alanine, N-cocoyl-N-methyl-β-alanine
Those having two linear or branched saturated or unsaturated acyl groups are exemplified.

The N-acylglutamic acid salt includes, for example, a linear or branched chain having 8 to 22 carbon atoms such as N-lauroylglutamic acid, N-myristoylglutamic acid, N-palmitoylglutamic acid, N-stearoylglutamic acid and N-cocoylglutamic acid. And those having a saturated or unsaturated acyl group.

In the present invention, as other anionic surfactants, for example, organic sulfonates such as dialkyl sulfosuccinates and sulfates of alkyl alcohol ethers, organic carboxylate salts, and derivatives of these acids are used. You can also. Examples of the salt of the anionic surfactant in the present invention include alkanolamine salts such as sodium, potassium, and magnesium or alkali earth metal salts such as magnesium, monoethanolamine, diethanolamine, and triethanolamine; lysine;
And basic amino acid salts such as arginine.

The amphoteric surfactants and semipolar surfactants used in the present invention include, for example, amidobetaine-type amphoteric surfactants, amidosulfobetaine-type amphoteric surfactants, betaine-type amphoteric surfactants, and sulfobetaine-type amphoteric surfactants Surfactants, imidazolinium-type amphoteric surfactants, tertiary amine oxide-type semipolar surfactants and the like can be mentioned. Specific examples of the above surfactant include, for example, long-chain alkyl (C
₈ -C ₂₂₎ betaines, long chain alkyl (C _{8 ~C 22)} sulfobetaine, long chain alkyl (C _{8 ~C 22)} amine oxide, and the like.

Examples of the nonionic surfactant used in the present invention include polyoxyethylene (1 to 20 mol) long-chain alkyl (primary or secondary C _{8 to} C ₂₂ ) ether,
Polyoxyethylene (1 to 20 mol) alkyl (C ₈ to
_C18 ) phenyl ethers, oxyalkylene addition compounds such as polyoxyethylene polyoxypropylene block copolymers, and higher fatty acid alkanolamides or alkylene oxide adducts thereof.

In the present invention, these surfactants may be used alone or in combination of two or more, but it is necessary that the total amount of the surfactants does not exceed 50% by weight. Is necessary to keep the viscosity of the product at 2000 cp or less and maintain good fluidity in the product. Raw materials of the smectite clay mineral used in the present invention include montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite and the like. These clay minerals have exchangeable ions with water molecules between the layers and exhibit properties different from other clay minerals, such as forming an organic complex and swelling ability. Such smectite-based clay minerals, which are produced from nature, include, for example, those containing montmorillonite, from Wenjun Mining Co., Ltd. Wenger, Kunimine Kogyo Co., Ltd.
Kunipia G and Kunipia F from the company, Western Bond from American Colloids, Yellowstone from Dresser Minerals, and the like. K and the like, and those containing hectorite are commercially available from American Colloids, such as Hectaprite AW, Hectaprite 200 and Benton EW, and Macaloids from National Reed. Various types of synthetic smectites are also sold, and Ionite H is marketed by Mizusawa Chemical Industry Co., Ltd., SWN and SAN are sold by Corp Chemical Co., Ltd., and Lapoinite is marketed by Laportindustry.

Further, as a raw material of the smectite clay mineral of the present invention, an alkali-treated acid clay may be used. Acid clay usually has a pH of 1% aqueous solution dispersion of 5%.
6 below, the degree of swelling is 10ml / 2g or less, SiO ₂ and A
The content of l ₂ O ₃ is SiO ₂ / Al ₂ O ₃ = 6 to 1 in molar ratio.
0. These include Nakajo, Niigata Prefecture,
Acid clay from Koto, Kamikatani, Itoigawa, acid clay from Mizusawa, Yamagata Prefecture, Kawasaki, Matsune, Kamikatani, Mikawa, Ome, Kamisami, etc. Fuller's earth, Florida from USA
e earth, Warkel erde from Germany and the like. The exchangeable cations present in the acid clay include sodium ions, potassium ions, magnesium ions, iron ions and the like. These acid clays can be treated in the same manner as the above clay minerals by alkali treatment.

More preferably, the smectite-based clay mineral used in the present invention has an average particle size of 10 to 5000 nm measured by a dynamic light scattering method, and an absolute value of ζ potential of 30 mV or more measured by an electrophoretic light scattering method. , Powder X
Those having a purity of 90% or more determined by a line diffraction method are mentioned. This average particle size and zeta potential can result in a sample
m, added to distilled water and ultrasonically dispersed for 60 minutes, the average particle diameter was 20 ° C., and the refractive index was 1.33.
1. Measurement of particle size of swelling gel particles of clay mineral by light scattering method under conditions of viscosity 0.951 cps and angle 90 °, ζ potential was determined by using an electrophoretic light scattering photometer, scattering angle 20
The values measured at room temperature are shown below. The purity was determined by X-ray diffraction using a powder method. In the obtained X-ray diffraction diagram, the sum Sc of the peak areas attributed to the smectite-based clay mineral was determined.
And the sum Sx of the peak areas belonging to other crystals are values obtained by the following equation (1).

[0024]

(Equation 1)

The smectite clay mineral used in the present invention can be obtained, for example, by simply suspending the raw clay in water and separating the supernatant, but suspending the raw clay mineral in water. This is 50,000 seconds
^It is advantageous to prepare by swelling with stirring at a shear rate of ^-1 or more and then separating the supernatant. This swelling treatment swells the raw clay with water and, as a supernatant, a component having an excellent thickening effect as impurities, for example, calcite, tridymite, cristobalite,
Since it is a step for separating from quartz, it is preferable to carry out by a wet method, and a dry method such as air classification is generally not preferable.

As described above, the stirring in the suspension treatment is performed at 50,000 sec ^-1 or more, preferably 70,000 sec ^-1.
It is advantageous to carry out under an ultra-high shear rate of not less than sec ^-1 , but the required time is short if the shear rate is high and long if the shear rate is low, but is usually 1 second to 24 hours, preferably Is 1 minute to 5 hours. If it is too short, not only is not sufficient shearing performed, but also the content of the clay mineral in the supernatant decreases, which is not economical. If it is too long, the clay mineral becomes amorphous and the thickening effect is reduced.

As a shearing means at this time, a homogenizer which gives a shearing, breaking and dispersing action through a narrow gap,
A colloid mill, a jet pulverizer and the like are suitable. It is desirable that the width of the gap at this time be 0.5 mm or less. In order to obtain effective shearing at this time, the viscosity of the clay mineral suspension at 25 ° C.
It is necessary to be 0000 cps or less, preferably 1000 cps or less. If the viscosity exceeds 50,000 cps, the shear stress increases significantly,
It becomes impossible to obtain a shear rate of sec ^-1 or more,
In some cases, the yield value of the suspension is exceeded, causing an agitation in the agitated part, and the suspension cannot be subjected to sufficient shearing force.

Next, the supernatant is advantageously separated by centrifugation. The processing time by this centrifugation is about 5 seconds to 100 hours, preferably 1 minute to 24 hours. The stirring process and the process of obtaining the supernatant can be performed at a temperature of 0 to 105 ° C.
It is preferable to carry out in the range of 0 to 90 ° C.

Examples of the salt of the smectite clay mineral include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium and calcium, alkanolamine salts such as monoethanolamine, diethanolamine and triethanolamine, lysine and arginine. And the like. These are 1 if necessary
Used in species or two or more. The supernatant containing the smectite-based clay mineral thus obtained may be directly blended into the detergent composition, or, in some cases, concentrated or dried to a powder or flake form. To the detergent composition.

The anionic surfactant of the present invention has a foaming property,
Used for the purpose of improving detergency. For this reason, it is important that the blending amount of the anionic surfactant is 0.1% to 40%, preferably 0.1% to 20%. If the amount is less than 0.1%, sufficient foaming properties and detergency cannot be obtained, which is not preferable as a detergent. In addition, the blending amount is 40%
In the case of exceeding, the foaming property and the detergency can be sufficiently obtained, but the skin irritation is increased and the hand may be roughened. The amphoteric or (and / or) semipolar surfactant of the present invention is used for the purpose of reducing skin irritation and the like of the above-mentioned anionic surfactant and making it difficult to cause rough hands. For this reason, the compounding amount of the amphoteric or (semipolar surfactant) is 0.1
It is important that it is ４０40%, preferably 0.1-20%. If the amount is less than 0.1%, the skin irritancy of the anionic surfactant cannot be improved, resulting in unfavorable hand roughness. If the amount is more than 40%, the skin irritation is improved, and a hand-friendly detergent can be obtained. The nonionic surfactant of the present invention has an improved foaming property or a high detergency against oil stains and the like, and is an essential component for kitchen detergents. For this reason, the amount is 0.1 to 40%, preferably 0.1 to 20% by weight. If the compounding amount is less than 0.1%, the detergency against oil stains is undesirably reduced. If the amount exceeds 40%, the foaming power is undesirably reduced.

Further, the liquid detergent composition of the present invention is a liquid having fluidity, and preferably has a viscosity of 2000 cp or less. For this reason, the amount of the anionic surfactant is 0.1% to 40%, preferably 0.1% to 20%, and the amount of the amphoteric surfactant is 0.1% to 40%, preferably 0.1%. 1
% To 20%, 0.1% of non-ionic surfactant
To 40%, preferably 0.1% to 20%, and the amount of the smectite clay mineral is 0.01% to 10%, preferably 0.1%.
1% to 5%, and the compounding amount of the dispersion stabilizer is 0.01%
It is important that it is between 5% and 5%. When the content of each surfactant is less than 0.1%, the performance as a detergent cannot be obtained. The amount of each surfactant is 40
%, The fluidity of the liquid detergent is greatly reduced,
It is difficult for consumers to use it during actual use, which is not preferable. Also, when the smectite-based clay mineral exceeds 10%, the viscosity of the detergent is undesirably higher than 2000 cp. In the cleaning composition of the present invention, a dispersion stabilizer for the purpose of stabilizing the dispersion of the smectite-based clay mineral in the product is used.

The dispersion stabilizer of the present invention is represented by the following general formula (I):

Embedded image (Wherein R ¹ is a hydrogen atom, an alkali metal, an unsubstituted alkanol group-substituted ammonium group or an alkyl group having 1 to 4 carbon atoms),
Formula (II) below

Embedded image (Wherein R ² is a hydrogen atom, an alkali metal, an unsubstituted alkanol group-substituted ammonium group or an alkyl group having 1 to 4 carbon atoms), and a copolymer comprising at least one repeating unit represented by the formula (1) is preferably used. .

R ¹ and R in the general formulas (I) and (II)
^{In 2} , the alkali metal is, for example, sodium or potassium, and the unsubstituted or alkanol-substituted ammonium group is, for example, an ammonium group or an alkanol-substituted ammonium group having 1 to 4 carbon atoms, specifically, monoethanol, Diethanol, triethanol, monopropanol, dipropanol, an ammonium group substituted with a tripropanol group, etc.
Examples of the alkyl group 4 include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group. Examples of such a copolymer include methacrylic acid-acrylic acid copolymer, methacrylic acid alkyl ester-acrylic acid copolymer, methacrylic acid-acrylic acid alkyl ester copolymer, and methacrylic acid alkyl ester-acrylic acid Alkyl ester copolymers and their salts (alkali metal salts, ammonium salts,
To 4 alkanolamine salts).

It is important that the dispersion stabilizer of the present invention has a molecular weight of 50,000 to 2,000,000, preferably 150,000 to 1,500,000 as determined by a viscosity method. When the molecular weight is less than 50,000, the effect of stabilizing the dispersion is not sufficient, and it is not preferable because it separates during long-term storage and lowers the performance of the product. Conversely, 20
If it exceeds 10,000, the thickening effect of the dispersion stabilizer significantly increases and the viscosity of the product is increased, and the gelation of the product is severely caused, making it difficult for the liquid to flow out of the container, It is not preferable because the solution speed in water is slowed down and the foaming property is reduced, leading to lower performance. Further, the copolymer of the present invention preferably has a molar ratio of the repeating unit represented by the general formula (I) to the repeating unit represented by the general formula (II) of 2: 8 to 7: 3.

The dispersion stabilizer of the present invention comprises 0.01% to 5%
It is suitably used, and more preferably 0.1% to 2%. When the amount is less than 0.01%, the dispersion stabilizing effect cannot be sufficiently obtained, and the smectite-based clay mineral is separated during long-term storage, and sufficient performance as a detergent cannot be obtained. Conversely, if the blending amount is 5% or more, the dispersion stabilizing effect has already reached saturation, and further effects cannot be expected, as well as the product viscosity increases, making it difficult for the liquid to come out of the container. . Further, when the dispersion stabilizer is produced by the method of the present invention, the effect of the dispersion stabilizing agent is remarkably increased, so that it can be used more safely even after long-term storage, which is preferable.

These smectite-based clay minerals, each having different properties, such as anionic, amphoteric or (and) semipolar,
In a liquid detergent composition comprising a nonionic surfactant and a dispersion stabilizer, it is important to mix each component in a specific mixing order in order to sufficiently exhibit its performance. That is, first, an amphoteric or (and / or) semi-polar surfactant is mixed with a dispersion of a smectite clay mineral, then an anionic surfactant is mixed, and then a nonionic surfactant is mixed, and then the dispersion is stabilized. Mix the ingredients.

In general, it is known that anionic surfactants are more excellent in dispersibility of inorganic particles than other surfactants. Therefore, the smectite clay mineral is finely dispersed in the dispersion of the smectite clay mineral when the anionic surfactant is first mixed. However, although the composition thus obtained has excellent dispersibility immediately after production, it is easily separated by subsequent storage. In addition, a composition obtained by first mixing a nonionic surfactant is easily separated by long-term storage. Although the cause is still unknown, if the amphoteric or semipolar surfactants that form a complex with the anionic substance are subsequently mixed, uniform mixed micelles are not formed with each other, and the anionic surfactant And the concentration of amphoteric surfactant on the outermost surface of the particles on which the nonionic surfactant is adsorbed increases, and some of the amphoteric surfactants orient the alkyl groups outward, so that the particle surface is partially It can also be considered that they become hydrophobic and cause aggregation with each other. Further, the dispersion stabilizer is added after blending the surfactant. When mixing before or during the mixing of the surfactant, not only a sufficient dispersion stabilizing effect cannot be obtained, but also, for example, when mixing before the surfactant, particles adhering to the wall of the container are recognized and uniform. A dispersion is not obtained, and sedimentation and separation occur in a short time even at room temperature, which is not preferable.

Therefore, when producing the liquid detergent of the present invention, first, an amphoteric surfactant and / or a semipolar surfactant are added to a dispersion of a smectite-based clay mineral to form a complex of both. It is important to prevent and stabilize the highly reactive amphoteric surfactant and / or semipolar surfactant from reacting with other components during storage. At this time, insoluble particles are precipitated and coagulated with the formation of the complex to form a gel-like substance. This gel-like substance is formed in a state easily dispersed by an anionic surfactant to be subsequently mixed. For this purpose, it is important to adjust the mixing speed of the amphoteric surfactant and / or the semipolar surfactant and to control the deposition rate of the complex of both. That is, the composite thus obtained is finely dispersed again by the next mixed anionic surfactant, and the finely dispersed particles are then stabilized by the nonionic surfactant having a strong hydration power. Is done.

As a mixing method, for example, a smectite-based clay mineral is charged into a mixing tank having ordinary stirring blades, and then, while stirring, an amphoteric surfactant or / and a semipolar surfactant, an anionic surfactant, a non-ionic surfactant, What is necessary is just to mix in order of the ionic surfactant in order. In this case, it is preferable that the mixed solution of the amphoteric surfactant and / or the semipolar surfactant is continuously added to the liquid as described above. At this time, in the mixing of the tank, 10 seconds to 30 minutes, preferably 15 seconds to 1 minute
Add at 0 minutes. If less than 10 seconds, the smectite-based clay mineral and the amphoteric surfactant or semipolar surfactant form a more hydrophobic complex at once, so that ultrafine particles are precipitated, forming a hard gel-like substance, Even anionic surfactants do not disperse, resulting in poor dispersion stability immediately after production. On the other hand, when the time exceeds 30 minutes, the resulting composites aggregate with each other to form hard and large aggregated particles. Since such particles are not finely dispersed by the anionic surfactant and have a high density, when stored, separation occurs in a short time, which is not preferable. Further, the pipes may be mixed using a line mixer or a motionless mixer.

The cleaning composition of the present invention may further contain, in addition to the above essential components, a polyhydric alcohol such as glycerin or polyethylene glycol, if necessary, as long as the effects of the present invention are not impaired. , Solubilizers such as lower allyl sulfonate and ethanol such as xylene sulfonate, toluene sulfonate and benzoate, fragrance,
Dyes, enzymes, binders, chelating agents, medicinal ingredients, water-soluble polymers and the like can also be added.

[0041]

According to the present invention, a liquid detergent composition can be obtained by finely dispersing a smectite-based clay mineral and exhibiting excellent separation stability, which is an industrially extremely advantageous method.

[0042]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. Prior to this, test methods adopted in the examples will be described below. Test method 1) Storage stability test at 50 ° C. A sample is placed in a glass bottle, sealed, and stored in a thermostat adjusted to 50 ° C. Samples in glass bottles over time
The phase separation is determined by the naked eye, and the ratio of the volume of the separated upper layer to the entire sample is measured and defined as the degree of separation. The larger the degree of separation, the lower the separation stability.

2) Freeze-Restoration Test A 50 cc sample was placed in a 50 cc glass colorimetric tube.
It is placed in a thermostat at 20 ° C. and kept frozen for 16 hours. Thereafter, the colorimetric tube is removed and the ice is melted at room temperature.
After standing for 8 hours, the separation of the sample is visually determined. This operation is repeated five times. The ratio of the volume of the separated transparent upper layer to the whole sample is measured and defined as the degree of separation. The larger the degree of separation, the lower the separation stability.

3) Dispersibility of smectite A half of the sample is placed in a glass vial, inverted, and the sample is dropped on a glass wall and left as it is. After the sample liquid has finished dripping, observe the deposit on the wall of the vial. Judgment criteria: ：: No adhering particles were observed, and the tube wall was transparent. X: Adhered particles are observed.

Examples 1 to 3 Kitchen detergents having the following compositions were prepared. A: Smectite 3% dispersion 16.7% (Kunimine Kogyo Co., Ltd. Na-type montmorillonite, Kunibia G) B: Amphoteric surfactant 30% aqueous solution of amidopropyl betaine laurate 16.7% C: Anionic surfactant Polyoxyethylene (p = 5) 33.3% Lauryl ether sulfate ether Na 30% aqueous solution D: Nonionic surfactant Lauric acid ethanolamide 100% aqueous solution 12.0% E: Dispersion stabilizer 25% dispersion 2. 0% Others: Ethanol 6.0% pH adjuster: 50% aqueous solution of paratoluenesulfonic acid 8.0% Fragrance 0.2% Deionized water 5.1%

1.02 kg of ion-exchanged water is placed in a stirring tank, and a 3% smectite dispersion (component A) is stirred while stirring.
3.34 Kg were uniformly dispersed. After adding 1.20 kg of ethanol to this dispersion, 3.34 kg of amide propyl betaine laurate (component B) was uniformly blended,
Then, 6.66 kg of polyoxyethylene (p = 5) lauryl ether sulfate Na (component C) was uniformly mixed, and then lauric acid ethanolamide (component D) .2.
An almost transparent dispersion was obtained by uniformly mixing 40 kg. Further, to this dispersion was added 0.40 kg of a methacrylic acid / ethyl acrylate / butyl acrylate copolymer (component E) shown in Table 1 as a smectite dispersion stabilizer, and the pH was adjusted to 7 with paratoluenesulfonic acid. After the adjustment, add 0.04 Kg of fragrance and continue stirring for 30 minutes.
Kg was prepared. In any of the samples, particles adhered to the tube wall were not recognized and were uniformly dispersed. Further, the obtained sample was subjected to a storage stability test at 50 ° C. and a freeze recovery test, and the separation stability (separation degree) during long-term storage was evaluated. The results are shown in Table 1. On the other hand, using the dispersion stabilizers of Comparative Examples 1 and 2 in Table 1, kitchen cleaners were prepared in the same manner as in the examples, and used as comparative examples.

No separation was observed in any of the samples of the examples within the scope of the present invention even after storage at 50 ° C. for 4 weeks. In addition, no separation was observed even after the freeze-recoverability test, indicating that the separation stability was extremely good and the storage stability was excellent. On the other hand, in Comparative Examples 1 and 2 outside the scope of the present invention, a large separation was observed after the 50 ° C storage stability test and the freeze-recoverability test, and the separation stability was extremely poor, which had practical problems. Not preferred. The viscosity was measured at 20 ° C using a B-type viscometer.
Was measured.

[0048]

[Table 1] Table 1: Examples Comparative Examples Detergent composition (% by weight) 12 3 12 A component: clay mineral 0.5 0.5 0.5 0.5 0.5 B component: lauric amide 55 55 55 propyl betaine C component : Polyoxyethylene (p = 5) 10 10 10 10 10 Lauryl ether sulfate Na D component: Lauric acid 12 12 12 12 12 Ethanolamide E component: MAA / EA / BuA = 34/59/7 copolymer Molecular weight = 200,000 0.5----Molecular weight = 700,000-0.5---Molecular weight = 1.5 million--0.5--Molecular weight = 30,000---0.5- Molecular weight = 2.5 million----0.5 Ethanol 6 6 6 6 6 Para Toluenesulfonic acid 4 4 4 4 4 Flavor 0.2 0.2 0.2 0.2 0.2 Performance evaluation Product viscosity (cp) 300 400 500 250 3500 Dispersibility ○ ○ ○ × × Separation (vol%) Store at 50 ° C for 4 weeks 0 0 0 43 21 Freezing and reconstitution 0 0 0 30 10 Note) MAA: methacrylic acid EA: ethyl acrylate BuA: butyl acrylate

Example 4 A sample having the following composition was prepared. A: Smectite 2% dispersion [Kunimine Industries Co., Ltd. Montmorillonite, Kunipia G] 25.0% B: Semipolar surfactant C ₁₂ alkyldimethylamine oxide 30% aqueous solution 23.3% C: Anionic surfactant C ₁₂ 55% aqueous solution of 9.9% sodium alkylbenzenesulfonate, polyoxyethylene (p = 3) alkyl (C ₁₂ ~C ₁₈₎ 6.7% ether sulfate sodium salt 30% aqueous solution of D: nonionic surfactant C ₁₂ Alkyl dimethyl diethanolamide 100% aqueous solution 5.0% E: Dispersion stabilizer (25%) 2.0% (Leo Earl MS-200 manufactured by Lion Corporation) Other components 100% aqueous ethanol 4.0% polyethylene glycol ( PEG # 1000) 60% aqueous solution 1.7% sodium benzoate 100% powder 1 7% Perfume 0.2% Ion-exchanged water 20.5%

20.5 Kg of ion-exchanged water and 25.0 Kg of a 2% smectite dispersion were placed in a stirring tank, and PEG # 1000 was added to the mixture while stirring with a stirring blade rotating at a peripheral speed of 0.1 to 5 m / sec. After adding 7 kg and 4 kg of ethanol, surfactants B, C and D were blended according to the blending order of Example 4 in Table 2. That is, first,
The component B was mixed and stirred for 20 minutes. Next, after mixing the component C, the component D was mixed. Thereafter, 1.7 kg of sodium benzoate, 0.2 kg of fragrance and 2.0 parts of dispersion stabilizer (LION Co., Ltd. Leoal MS-200) E were added.
Kg was blended to obtain a liquid detergent. The resulting translucent sample did not show any particles attached to the tube wall and was uniformly dispersed.
Further, the obtained sample was subjected to a storage stability test at 50 ° C. and a freeze recovery test, and the separation stability (separation degree) during long-term storage was evaluated. In addition, the dispersion stabilizer Leoar MS-200 is methacrylic acid / ethyl acrylate /
It is a copolymer of butyl acrylate = 34/59/7 (weight average molecular weight 1.5 million, solid content 25%).

On the other hand, a liquid detergent composition was prepared in the same manner as in Example 4 by the blending method of Comparative Examples 3 and 4 in Table 2 and used as a comparative example. All samples of Example 4 within the scope of the present invention were at 50 ° C.
No separation was observed even after storage for 4 weeks and after the freeze reconstitution test, and the separation stability was extremely good. On the other hand, Comparative Examples 3 and 4 outside the scope of the present invention all show large separation after storage stability test and freeze-recoverability test at 50 ° C., have extremely poor separation stability, and have problems in practical use. Absent.

[0052]

[Table 2]Table 2: Example 4 (Blending method and evaluation result) Degree of separation (vol%) 50 ℃ freezing Combination method Dispersibility Preservation Restorability Example 4 After mixing the B component into the smectite dispersion, Mix C component, then D component Comparative Example 3 After mixing the D component with the smectite dispersion liquid ○ 8 15 Mix B component, then mix C component Comparative Example 4 After mixing the C component into the smectite dispersion liquid ○ 15 25 Mix component D, then compound component B

Example 5 A sample having the following composition was prepared. A: Smectite 2% dispersion [Kunimine Industries Co., Ltd. Montmorillonite, Kunipia G] 20.0% B: Amphoteric surfactant 30% aqueous solution of lauric amide propyl betaine 23.3% C: Anionic surfactant N- Lauroyl-N-methyl-β-alanine sodium 15.0% 30% aqueous solution Polyoxyethylene (p = 3) alkyl (C ₁₂ -C ₁₈ ) 6.0% Ether sulfate sodium salt 30% aqueous solution D: Nonionic interface Activator C ₁₂ alkyldimethyldiethanolamide 100% aqueous solution 20.5% E: Dispersion stabilizer (25%) 2.0% (Lion Earl MS-200 manufactured by Lion Co.) Other components Ethanol 100% aqueous solution 6.0 % Sodium benzoate 100% Powder 3.0% Fragrance 0.2% Deionized water 4.0%

4 kg of ion-exchanged water and 20.0 kg of a 2% smectite dispersion were placed in a stirring tank, and the peripheral speed was 0.1 to 5 m.
After adding 6 kg of ethanol while stirring by rotating the stirring blade at 20 / sec, the amphoteric surfactant B, ie, a 30% aqueous solution of amidopropyl betaine laurate was used.
3 Kg were mixed and stirred for 20 minutes. Then, anionic surfactant C, that is, 15 kg of a 30% aqueous solution of sodium N-lauroyl-N-methyl-β-alanine, a 30% aqueous solution of sodium salt of polyoxyethylene (p = 3) alkyl (C ₁₂ -C ₁₈ ) ether sulfate Are mixed in the order of 6 kg, and then the nonionic surfactant D, ie, C
₁₂ % alkyldimethylethanolamide 100% solution 2
0.5 kg was mixed. Thereafter, 3.0 kg of sodium benzoate, 0.2 kg of fragrance, and 2.0 kg of a dispersion stabilizer (Lion Co., Ltd., Leoar MS-200) E were blended to obtain a liquid detergent. The resulting translucent sample did not show any particles attached to the tube wall and was uniformly dispersed. Also,
The obtained sample was subjected to a storage stability test at 50 ° C. and a freeze reconstitution test, and the separation stability during long-term storage was evaluated.

On the other hand, in Example 5, a liquid detergent composition was prepared by a compounding method in which surfactant C was first added, surfactant B was added, and finally surfactant D was mixed.
And The samples of Example 5 within the scope of the present invention were all 5
No separation was observed after storage at 0 ° C. for 4 weeks and after the freeze reconstitution test, and the separation stability was extremely good. In contrast,
In Comparative Example 5 outside the scope of the present invention, 12% separation was observed in the 50 ° C. storage stability test, and 10% separation was observed in the freeze recovery test, and the separation stability was extremely poor, and there was a practical problem. Not preferred.

Claims (4)

[Claims] 1. A smectite clay mineral of 0.01 to 10
0.1% to 40% by weight of an anionic surfactant, 0.1 to 40% by weight of a nonionic surfactant, and at least one of an amphoteric surfactant and a semipolar surfactant.
1 to 40% by weight and 0.01 to 5% by weight of a dispersion stabilizer, wherein the dispersion stabilizer comprises a repeating unit represented by the following general formula (I): (Wherein R ¹ is a hydrogen atom, an alkali metal, an unsubstituted alkanol group-substituted ammonium group or an alkyl group having 1 to 4 carbon atoms) A repeating unit represented by the following general formula (II): (Wherein R ² is a hydrogen atom, an alkali metal, an unsubstituted alkanol group-substituted ammonium group or an alkyl group having 1 to 4 carbon atoms), and has a molecular weight of 50,000 to 200 as determined by a viscosity method.
A smectite-containing liquid detergent composition, which is a copolymer. 2. The copolymer according to claim 1, wherein the dispersion stabilizer has a molar ratio of the repeating unit represented by the general formula (I) to the repeating unit represented by the general formula (II) in the range of 2: 8 to 7: 3. The smectite-containing liquid detergent composition according to claim 1, which is a coalesced product. 3. A smectite clay mineral of 0.01 to 1
0% by weight, 0.1 to 40% by weight of an anionic surfactant, 0.1 to 40% by weight of a nonionic surfactant, and 0 to 40% by weight of at least one of an amphoteric surfactant and a semipolar surfactant. 0.1 to 40% by weight and a dispersion stabilizer 0.01 to
A dispersion unit containing 5% by weight of a dispersion stabilizer represented by the following general formula (I): (In the formula, R ¹ is a hydrogen atom, an alkali metal, an unsubstituted alkanol group-substituted ammonium group or an alkyl group having 1 to 4 carbon atoms.) A repeating unit represented by the following general formula (II): (Wherein R ² is a hydrogen atom, an alkali metal, an unsubstituted alkanol group-substituted ammonium group or an alkyl group having 1 to 4 carbon atoms), and has a molecular weight of 50,000 to 200 as determined by a viscosity method.
In preparing a liquid detergent composition which is a copolymer of 10000, 1) mixing an aqueous dispersion of a smectite-based clay mineral with an amphoteric surfactant and / or a semipolar surfactant, 2) Mixing the mixed solution obtained in the above step 1) with an anionic surfactant; 3) mixing the mixed solution obtained in the above step 2) with a nonionic surfactant; 4) further mixing A method for producing a smectite-containing liquid detergent composition, comprising mixing the mixture obtained in the above step 3) with a dispersion stabilizer. 4. A copolymer wherein the dispersion stabilizer has a molar ratio of the repeating unit represented by the general formula (I) to the repeating unit represented by the general formula (II) in the range of 2: 8 to 7: 3. The method for producing a smectite-containing liquid detergent composition according to claim 3, which is a coalescence.