JPH11100598A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent compsn. which is lowly irritant and excellent in foam quality, rinsing properties, and high-temp. stability by incorporating a water-swellable clay mineral having specified average particle size. ξ-potential, and purity, an anionic surfactant, and a polyoxyethylene glycerin fatty acid ester into the same. SOLUTION: This compsn. contains 0.01-3 wt.% water-swellable clay mineral having an average particle size (by the dynamic light-scattering method) of 10-5.000 nm, an absolute value of ξ-potential (by the electrophoretic light- scattering method) of 30 mV or higher, and a purity (by the powder X-ray analysis method) of 90% or higher. 0.01-40 wt.% anionic surfactant, and 0.1-10 wt.% polyoxyethylene glycerin fatty acid ester of the formula (R1 to R3 are each H, a 12-22C fatty acid residue, or an amino acid residue provided all of them are not simultaneously H; EO is an ethylene oxide group; and a, b, and c are each the number of moles of ethylene oxide added provided a+b+c is 1-60).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hypoallergenic detergent composition having excellent rinsing properties and foaming properties.

[0002]

2. Description of the Related Art Conventionally, clay minerals have properties such as adsorptivity, binding, suspending, swelling, film-forming, and viscosity increasing properties. Have been. Furthermore, the water-swellable clay mineral has a flaky layer structure,
It has the above properties and exhibits the same thickening effect as a polymer-based thickener. On the other hand, the cleaning agent has a foaming property in addition to the detergency as a basic function. Foam quality can be enhanced by using higher fatty acid salts, which are known to have a large amount of sticky foam as a surfactant, or by using various auxiliary surfactants, but these surfactants cause irritation to the skin. It is not suitable for people with weak skin and people with atopic dermatitis.

As a method of improving the foam quality without excessively using such a surfactant, a method of adding a water-swellable clay mineral has been proposed. For example, foams having improved creaminess by adding a water-swellable clay mineral (Japanese Patent Application Laid-Open No. 1-149715), and foams having reduced foaming power and irritation to the skin of surfactants (Japanese Patent Application Laid-open No. Kaihei 4-372700) and the like are proposed.

[0004] As described above, when a water-swellable clay mineral is added to a detergent composition, it has the effects of making the foamy creamy, improving the foaming power, and having low skin irritation. In addition, due to its layer structure, it has a thickening effect on the detergent composition, and also has an effect that it has an excellent feel during and after use.

However, the smectite, which is a water-swellable clay mineral, tends to separate at high temperatures when it is used in a detergent composition. Further, in the liquid detergent composition,
The water-swellable clay mineral has a thickening effect, but in many cases, due to the coexistence of the electrolyte, the negative charge on the surface of the flaky particles of the clay mineral is easily neutralized and easily aggregated,
Dispersion stability tends to decrease and the thickening effect tends to decrease.

In order to solve these problems, those using a specific viscosity mineral (JP-A-8-269490) and those using a thickening system such as cream (JP-A-60-9239)
9) and the like have been proposed to ensure stability, but the stability is not yet sufficient, and the good feel of the water-swellable viscous mineral during and after use (good rinsing) There was a drawback that it would decrease.

On the other hand, there has been proposed a detergent composition containing a polyoxyethylene glycerin fatty acid ester.
For example, a combination of an anionic surfactant and an amphoteric surfactant to reduce irritation (JP-A-4-12279)
9), which are used in combination with polyethylene glycol dioleate and / or polyethylene glycol diisostearate to improve rinsing properties and usability (Japanese Patent Application Laid-Open No. 8-92)
032) has been proposed.

However, none of these detergents is a detergent containing a water-swellable clay mineral and is not intended to improve a detergent using a water-swellable clay mineral.

Accordingly, the present applicant has previously prepared a detergent composition containing a water-swellable clay mineral and an anionic surfactant,
A liquid detergent composition was proposed in which a water-soluble nonionic polymer substance and a water-soluble anionic polymer substance were combined and used, and the liquid detergent composition was excellent in usability and had good dispersion stability (Japanese Patent Application No. 8-153331). .

However, this liquid detergent composition is not yet satisfactory in stability, feel during use and after use.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a detergent composition which is excellent in foam quality and rinsing properties, and is also excellent in high-temperature stability.

[0012]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems, and as a result, a polyoxyethylene glycerin fatty acid ester was further added to a detergent composition containing a specific clay mineral. By doing so, the foam quality can be improved without excessively blending an active agent for improving the foam quality, the irritation to the skin is suppressed, and the cleaning composition further excellent in rinsing properties and high-temperature stability. It was found that a product was obtained, and the present invention was completed.

According to the present invention, (a) an average particle diameter of 10 to 5000 nm by dynamic light scattering, an absolute value of ζ potential of 30 mV or more by electrophoretic light scattering, and a purity of 90% by powder X-ray analysis. The above water-swellable clay mineral, (b) an anionic surfactant, and (c) the following general formula:

Embedded image (Where R₁~ R_ThreeIs a hydrogen atom, a C12-22 fat
An acid residue or an amino acid residue, provided that R₁~ R_ThreeEverything is water
Except when it is an elementary atom. EO is ethylene oxide
, A, b, and c represent the number of moles of ethylene oxide added.
And a + b + c = 1-60)
It is characterized by containing renglycerin fatty acid ester
A cleaning composition is provided.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the cleaning composition of the present invention will be described in more detail. The water-swellable clay mineral of the component (a) used in the cleaning composition of the present invention includes:
Natural or synthetic montmorillonite, beidellite,
Examples include smectites such as nontronite, saponite, hectorite, sauconite, stevensite, and bentonite, and swelling mica. These clay minerals contain ions that are exchangeable with water molecules between the layers, and exhibit properties different from other clay minerals, such as forming an organic complex and swelling ability. Further, in the present invention,
The clay mineral can be subjected to an ion exchange reaction and used as a high metal ion-substituted clay mineral. This is suitable for further increasing the thickening effect.

The above-mentioned clay mineral has an average particle diameter of 10 to 5000 nm measured by dynamic light scattering, an absolute value of the ζ potential of 30 mV or more measured by electrophoretic scattering, and is determined by powder X-ray analysis. The purity is 90% or more.

If the average particle size of the clay mineral is less than 10 nm, a large amount of the clay mineral is required to thicken the liquid detergent and maintain the shape retention of the cream. Can not be obtained. The average particle size of the clay mineral is preferably from 200 to 2000 nm.

The absolute value of the 鉱 物 potential of the clay mineral is 3
If it is less than 0 mV, the clay particles are likely to be condensed, and aggregates may be settled in the detergent, so that the dispersion stability may be reduced. Furthermore, non-swelling impurities such as calcite, tridymite, cristobalite, quartz, and various inorganic substances are contained in the clay minerals, particularly those collected from nature, which dissolve and release electrolytes. Or cause separation of the cleaning composition. Therefore, the purity of the clay mineral is preferably 90% or more, particularly preferably 95% or more.

Preferred as such clay minerals are:
Montmorillonite, bentonite, and more preferably montmorillonite are preferred in terms of rinsing properties and mildness to the skin.

In the detergent composition of the present invention, the preferred blending amount of the water-swellable clay mineral (a) is 0.01-3.
%, More preferably 0.1 to 1% by weight. If the amount is less than 0.01% by weight, the effect of improving the feeling of use, creaminess of foam, mildness, etc. is not sufficient.
When the content exceeds 3% by weight, the dispersion stability is deteriorated.

Next, as the anionic surfactant (b) used in the detergent composition of the present invention, a carboxylate, a sulfonate, a sulfate ester salt, an alkyl phosphate ester salt or the like may be used. Can be. As the carboxylate, in addition to saturated and unsaturated fatty acids having 12 to 18 carbon atoms, coconut oil fatty acids, hydrogenated coconut oil fatty acids, palm oil fatty acids, hydrogenated palm oil fatty acids, tallow fatty acids, hydrogenated tallow fatty acids, and the like, which are mixtures thereof And fatty acid soaps such as potassium salt, sodium salt, triethanolamine salt, and ammonium salt, alkyl ether carboxylate, N-acyl sarcosine salt, N-acyl β-alanine salt, and N-acyl glutamate. In this case, the alkyl group or the acyl group preferably has 8 to 20 carbon atoms. Specific examples thereof include, for example, potassium laurate, sodium laurate, triethanolamine myristate, sodium myristate, sodium N-lauroylsarcosine, potassium N-myristoylsarcosine, sodium N-lauroylglutamate, N-lauroylmethyl-β-. And alanine sodium.

Examples of the sulfonate include N-acylaminosulfonate, polyoxyethylene sulfosuccinate, etc., and sodium N-cocoylmethyltaurate, sodium N-lauroylmethyltaurate,
-Myristoyl methyl taurine triethanolamine,
N-palmitoylmethyltaurine sodium, sodium polyoxyethylene alkylsulfosuccinate and the like can be mentioned.

Further, examples of the sulfate ester salts include higher alkyl sulfates and polyoxyethylene alkyl ether sulfates. Furthermore, examples of the alkyl phosphate ester salts include triethanolamine monolauryl phosphate, sodium lauryl phosphate, triethanolamine monomyristyl phosphate, and triethanolamine dimyristyl phosphate.

Among these anionic surfactants, fatty acid salts are preferred from the viewpoint of foaming and foam creaminess. More preferably, a potassium salt is preferable.

In the detergent composition of the present invention, the compounding amount of the anionic surfactant (b) is 0.01 to 40.
% By weight, and particularly preferably 10 to 30% by weight from the viewpoint of foaming and creaminess of the foam.

Further, the polyoxyethylene glycerin fatty acid ester of the component (c) used in the cleaning composition of the present invention is a compound represented by the following general formula.

Embedded image (Where R₁~ R_ThreeIs a hydrogen atom, a C12-22 fat
An acid residue or an amino acid residue, provided that R₁~ R_ThreeEverything is water
Except when it is an elementary atom. EO is ethylene oxide
, A, b, and c represent the number of moles of ethylene oxide added.
A + b + c = 1-60)

Specific examples of the polyoxyethylene glycerin fatty acid ester include POE (3) glyceryl monoisostearate, POE (3) glyceryl triisostearate, POE (5) glyceryl monoisostearate, POE (6) Glyceryl monostearate, PO
E (10) glyceryl monolaurate, POE (15)
Glyceryl monooleate, POE (15) glycerin vegetable oil fatty acid ester, POE (15) glyceryl monoisostearate, POE (20) glyceryl monoisostearate, POE (25) glyceryl monoisostearate, POE (25) glyceryl pyro Glutamate isostearate diester, POE (30) glyceryl monomyristate, POE (30) glyceryl monoisostearate, POE (40) glyceryl monoisostearate, POE (40) glyceryl triisostearate, POE (50) glyceryl triester Isostearate, POE (60) glyceryl triisostearate,
POE (40) glyceryl trioleate, POE (1
0) glyceryl monostearate, POE (15) glyceryl monostearate, POE (20) glyceryl monostearate and the like. Here, POE represents a polyoxyethylene chain, and the number in parentheses represents the number of moles of ethylene oxide added.

Among these fatty acids, lauric acid,
Myristic acid, stearic acid, isostearic acid, oleic acid, and pyroglutamic acid are preferred, and more preferred are stearic acid, isostearic acid, and pyroglutamic acid. Further, mono- or diesters of these fatty acids are preferred. Further, the number of moles of ethylene oxide added is a +
b + c = 1 to 30 is preferred.

It is preferable that two or more of these polyoxyethylene glycerin fatty acid esters of the component (c) are blended. In this case, due to the high temperature stability, their positions in the organic conceptual diagram are biased. That is, a combination in which the conceptual values of organic: inorganic are not close to each other is preferable. Specifically, a combination in which the HLB values calculated from the organic: inorganic values are not close, preferably a combination in which the difference in the HLB values is 5 to 15 is desirable. When the HLB value is close, the power of dispersion / emulsification is reduced, and the high-temperature stability is deteriorated.

Here, “organic: inorganic” means that the non-chemically-bonded intermolecular force is obtained as two values of non-polarity and polarity from the chemical structure of an organic compound. The organic property can be obtained by comparing the number of carbon atoms, and the inorganic property can be obtained by comparing the boiling points with hydrocarbons having the same number of carbon atoms. (-CH ₂ -) (actually C) determined one and the organic value 20, the inorganic property (-CH
_When the organic property of _2- ) is 20, the values of other substituents (inorganic groups) are also determined based on the inorganic value of 100 based on the effect of the hydroxyl group (-OH) on the boiling point ("inorganic group"). table"). A graph obtained by plotting (organic: inorganic) as (X: Y) is an “organic conceptual diagram”, and can predict various physicochemical properties of the organic compound.

Next, a method of calculating these will be described. The organic value is calculated from the chemical structure of the organic compound by adding an organic common value to carbon number x 20 if there is an organic common value, and subtracting the value in the inorganic group table if there is a branch. It is determined by summing the values of the corresponding inorganic groups in the basic group table. [References: "Design of emulsified formulation by organic conceptual diagram" (1985) Nippon Emulsion Co., Ltd., Atsushi Fujita, "Organicity: Organic concept by inorganic value", Atsushi Fujita, Masami Akatsuka, "Systematic organic and qualitative analysis ( Mixtures) "(1974) Kazama Shobo, Yoshio Koda, Ryohei Oda, Yoshie Yamori," Organic Conceptual Diagrams-Basics and Applications "(198)
4) Sankyo Publishing, etc.] The HLB value is a balance between hydrophilicity and lipophilicity (Hydrophilic-Lypophi).
The present invention uses a value calculated using the following equation by Oda and Yukimura et al.

(Equation 1)

In the cleaning composition of the present invention, the compounding amount of the polyoxyethylene glycerin fatty acid ester as the component (c) is 0.1 to 10% by weight, preferably 1 to 5% by weight. If the amount is less than 0.1% by weight, the effect of improving high-temperature stability and rinsing properties cannot be sufficiently exhibited, and if it exceeds 10% by weight, these effects are rather reduced.

In the detergent composition of the present invention, the polyoxyethylene glycerin fatty acid ester, which is the component (c), protects the water-swellable viscosity mineral from electrolytes and organic substances in the detergent composition, and also contains higher fatty acids and other fatty acids. It is considered that the system is stabilized by emulsifying the oil component and the activator, and the rinsing properties of the water-swellable clay mineral are supplemented by its good rinsing properties.

The cleaning composition of the present invention may contain various optional components, if necessary, in addition to the above essential components. Examples of these optional components include nonionic surfactants, amphoteric surfactants, polyhydric alcohols, water-soluble polymers, drugs, bactericides, preservatives, humectants, antioxidants,
Chelating agents, UV inhibitors, fragrances, dyes and the like can be mentioned.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

Example 1 A predetermined amount of polyoxyethylene glycerin fatty acid ester, 1,3-butylene glycol, fatty acid, sorbitol and sodium N-lauroyl-N-methyl-β-alanine shown in Table 1 was mixed and dissolved by heating. To prepare a mixture (I) at 70 ° C. Separately, bentonite is dispersed in hot water at 70 ° C. to prepare a mixture (II). Next, the mixture (II) was added to the mixture (I), and the mixture was stirred at 70 ° C. for 10 minutes to homogenize, then neutralized with KOH, and then mixed with POH.
Other ingredients such as EG 1500, methyl paraben, hydroxyethane diphosphonic acid are added. The mixture was cooled to room temperature while stirring, and a perfume was added to homogenize the mixture to obtain a detergent composition. The performance of the cleaning composition was evaluated by the following method, and the results are shown in Table 1.

Examples 2 to 8 and Comparative Examples 1 to 6 Using the components shown in Table 1, cleaning compositions of Examples 2 to 8 and Comparative Examples 1 to 6 were produced in the same manner as in Example 1. .
The performance of each cleaning composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1. The evaluation of foaming properties, foam creaminess, and rinsing properties by panelists is shown in Table 1 as average values.

The evaluation method and evaluation criteria for the performance of the detergent composition are shown below. <Bubbling> Twenty women (specialized panelists) performed a sensory test on foaming with hands and face and evaluated according to the following criteria. ◎: Foaming quickly, the amount of foam is abundant and the amount of foam is not easily broken. ○: Foaming and the amount of foam are moderate. △: Foaming slightly, but disappearing immediately. ×: Almost no foaming.

<Creamy property of foam> A detergent composition containing no water-swellable clay mineral, anionic surfactant and polyoxyethylene glycerin fatty acid ester alone was used as a standard product, and the following panel was prepared by 10 panelists. Evaluation was based on criteria. 3: The creaminess of the foam is considerably better than the standard product. 2: The creaminess of the foam is better than the standard product. 1: The creaminess of the foam is comparable to the standard product. 0: Compared with the standard product. Then, the creaminess of the foam was inferior. Next, it was judged according to the following criteria from the average evaluation score of 10 panelists. In addition, the thing which evaluation was (circle) or more evaluated that the creaminess of foam was good. ◎: Average evaluation point is 2.5 or more ：: Average evaluation point is 2 or more and less than 2.5 Δ: Average evaluation point is 1 or more and less than 2 ×: Average evaluation point is less than 1

<Rinseability> 20 women (specialized panelists)
However, a sensory test was performed by washing the face and evaluated according to the following criteria. ◎: The slick disappears easily by simple rinsing ○: The slick disappears by increasing the number of times of rinsing △: The slick does not disappear without a large number of rinsing ×: The slick remains forever and is unpleasant

<High Temperature Stability> The detergent was put in a 50 mL vial in an amount of 50 g and stored at 40 ° C. for one month, and then the presence or absence of separation was evaluated. A: Neither separation nor aggregation of the water-swellable clay mineral was observed at all, and there was almost no difference in viscosity from the initial. ：: Separation and aggregation of the water-swellable clay mineral were not observed at all. Δ: Separation of the water-swellable clay mineral was slightly observed.
No aggregation is observed. ×: Separation of water-swellable clay mineral is clearly observed, and aggregation is also observed.

<Mildness to Skin> Twenty women (specialized panelists) sensuously compared the mildness to skin according to the following criteria after using the product of the present invention and the comparative product. The results were evaluated according to the following criteria. ◎: 12 or more people who answered mild ○: 10 to 11 people who answered mild △: 6 to 9 people who answered mild ×: mild 5 or less people answered

[0042]

[Table 1- (1)]

[0043]

[Table 1- (2)]

[0044]

[Table 1- (3)]

[0045]

[Table 1- (4)]

[0046]

[Table 1- (5)]

[0047]

[Table 1- (6)]

[0048]

The cleaning composition of the present invention is obtained by mixing a specific polyoxyethylene glycerin fatty acid ester with a cleaning composition containing an anionic surfactant as a surfactant and a specific clay mineral. The polyoxyethylene glycerin fatty acid ester protects clay minerals from electrolytes and organic substances in the detergent composition and stabilizes the system, so that it has excellent foaming properties such as rinsing properties, and furthermore, for skin and the like. Hypoallergenic.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1:68) (72) Inventor Atsushi Ichiyanagi 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (1)

[Claims] (1) An average particle size of 10 to 10 according to a dynamic light scattering method.
5000 nm, absolute value of zeta potential by electrophoretic light scattering
30mV or more, purity 90% or more by powder X-ray analysis
A water-swellable clay mineral, (b) an anionic surfactant,
(C) the following general formula: (Where R₁~ R_ThreeIs a hydrogen atom, a C12-22 fat
An acid residue or an amino acid residue, provided that R₁~ R_ThreeEverything is water
Except when it is an elementary atom. EO is ethylene oxide
, A, b, and c represent the number of moles of ethylene oxide added.
And a + b + c = 1-60)
It is characterized by containing renglycerin fatty acid ester
Cleaning composition.