JPS61209035A - Polyhydric alcohol in oil type emulsion composition - Google Patents

Abstract

PURPOSE:To obtain a polyhydric alcohol in oil type emulsion composition excellent in viscosity, stability and use properties even in a system having a polar oil component compounded therein, by using clay mineral modified with an org. substance, which is obtained by treating water swellable clay mineral with a specific surfactant, as an emulsifier. CONSTITUTION:60-140mg equivalent of a quaternary ammonium salt type cationic surfactant represented by formula (wherein R1 is a 10-22 alkyl group or a benzyl group, R2 is a methyl group or a 10-22C alkyl group, R3 and R4 are an 1-3C alkyl group or a hydroxyalkyl group and X is a halogen atom or a methylsulfate residue) and 5-200g of a nonionic surfactant with a HLB valve of 2-16 are added to 100g of water swellable clay mineral represented by formula I and the resulting mixture is dispersed in a low b.p. solvent under stirring and the solvent is subsequently removed to obtain an organically modified clay mineral which is, in turn, used in a reduced compounding amount of 0.25-5wt% to obtain a polyhydric alcohol in oil type emulsion composition excellent in temp. stability. As an oil component to be used, all of general oil components can be used in a wide range from polar oil to non-polar oil and this emulsion composition can be utilizing in wide fields of medicine, cosmetics, paint, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyhydric alcohol-in-oil type emulsion composition useful as a cosmetic base or an ointment base, and more specifically, the present invention relates to a polyhydric alcohol-in-oil emulsion composition useful as a cosmetic base or an ointment base. The present invention relates to a polyhydric alcohol-in-oil emulsion composition that can be used in a wide range of applications, including polar oils, and has the characteristics that the resulting emulsion composition has excellent temperature stability.

[Prior Art] Conventionally, in order to obtain a polyhydric alcohol-in-oil type emulsion composition containing polyhydric alcohol as the main internal phase, an emulsifier having an HLB value of 17 is used.
Using a lipophilic surfactant of 12, for example, a polyhydric alcohol fatty acid ester-based surfactant such as glycerin fatty acid ester or sorbitan fatty acid ester, the surfactant is added to the oil phase at a concentration of 0.4
-5. After adding about 0.0 g and heating and dissolving at about 70-80°C, add polyhydric alcohol heated to about the same temperature and stir with a homomixer etc. to obtain the desired polyhydric alcohol-in-oil type emulsion composition. I was getting it.

[Problems to be Solved by the Invention] However, the thus obtained polyhydric alcohol-in-oil type emulsion composition has the disadvantage that it is difficult to obtain a system with excellent temperature stability and usability. For example, regarding temperature stability, at low temperatures, the continuous oil phase tends to separate due to agglomeration of polyhydric alcohols, and at high temperatures, the particle size increases due to coalescence of polyhydric alcohols, causing them to settle to the lower layer. A phenomenon such as oil phase separation, where the upper layer is only an oil phase, is likely to occur. On the other hand, since the external phase is oil, it has advantages in the cosmetics and pharmaceutical fields, such as protecting the skin and imparting flexibility, but on the other hand, it is sticky and has a high skin-occluding ability when used.

One way to improve temperature stability is to increase the viscosity by blending a large amount of wax into the oil phase.This method improves low temperature stability, but during high temperature storage, the blended wax The oil phase separation caused by the coalescence of the polyhydric alcohols cannot be sufficiently improved due to the softening and melting of the polyhydric alcohols, and new problems regarding usability such as spreadability arise.

As a method to improve such usability problems, o
It is preferable to mix polar oils with ester bonds, etc., which are often used in ZW type emulsion systems, but it is preferable to mix polar oils with conventionally used W/○ type emulsion agents in oil, which have excellent stability. It has been difficult to produce polyhydric alcohol type emulsified compositions.

As a result of intensive research to improve the shortcomings of the prior art, the present inventors discovered that by treating water-swellable clay minerals with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant. By using the obtained organically modified clay mineral as an emulsifier, it can be emulsified even in a relatively small amount.
We discovered that a polyhydric alcohol-in-oil emulsion composition with high viscosity, excellent temperature stability, and ease of use can be obtained without the need to incorporate wax or the like, and even with polar oils. Based on this, the present invention was completed.

[Means for Solving the Problems] That is, the present invention provides an organically modified clay mineral obtained by treating a water WB wettable clay mineral with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant. An alcohol-type emulsified composition is provided.

The configuration of the present invention will be described below.

The water-swellable clay mineral used in the present invention is a type of colloidal hydrated aluminum silicate having a three-layer structure, and is generally represented by the following general formula (%) (20), specifically montmorillonite, savonite, and hectorite. Natural or synthetic (in this case, the (OH) group in the formula is completely substituted with fluorine) such as montmorillonite group (commercially available products include pea gum, knivia, laponite, etc.), sodium silicic mica, sodium or lithium. Synthetic mica known as taeniolite (commercially available products include daimonite; manufactured by Tobie Gyo Co., Ltd., etc.).

Examples of products include Daimonite (manufactured by Tobie Gyo Co., Ltd., etc.).

The quaternary ammonium salt type cationic surfactant used in the present invention has the following general formula (wherein, Rt is an alkyl group having 10 to 22 carbon atoms or a benzyl group, R2 is a methyl group or an alkyl group having 10 to 22 carbon atoms, R3 and R4 are an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X is a halogen atom or a methyl sulfate residue.

For example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aracyltrimethylammonium chloride, behenyltrimethylammonium chloride,
Myristyldimethylethylammonium chloride, Cetyldimethylethylammonium chloride, Stearyldimethylethylammonium chloride, Arakyldimethylethylammonium chloride, Behenyldimethylethylammonium chloride, Myristyldiethylmethylammonium chloride, Cetyldiethylmethylammonium chloride, Stearyldiethylmethylammonium chloride, Araki diethylmethylammonium chloride,
Behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, dibehenyldihydroxyethylammonium chloride , and the corresponding bromides, etc., as well as civalmitylpropylethylammonium methyl sulfate and the like.

In implementing the present invention, one or more of these may be arbitrarily selected.

Invention? The second nonionic surfactant used has an HLB value (Note 1) within the range of 2 to 16, with 3 to 12 being generally preferred. For example, polyoxyethylene 2
~30 moles of added C or less is abbreviated as P OE (2-30).

) Oleyl ether, POE (2-35) stearyl ether 1. , POE(2-20) lauryl ether, P
OE (1-20) Alkylphenyl ether, POE
(6-18) Behenyl ether, P OE (5-25
) 2-decyltetradecyl ether, P OE (3-
30) 2-decyltetradecyl ether, POE (
8-16) Ether-type activators such as 2-octyldecyl ether, and POE (4-60) hydrogenated castor oil, P
OE (3-14) fatty acid monoester, POE (6-
30) Ester-type activators such as fatty acid diesters, POE (5-20) sorbitan fatty acid esters, and further POE
(2-30) Glyceryl monoisostearate, P
Ether ester type activators such as OE (10-60) glyceryl triisostearate, P OE (7-50) hydrogenated castor oil monoisostearate, P OE (12-60) hydrogenated castor oil triisostearate, etc. Ethylene oxide addition type surfactants, polyglycerin fatty acid esters such as decaglyceryl tetraoleate, hexaglyceryl triisostearate, tetraglyceryl diisostearate, diglyceryl diisostearate, glyceryl monostearate, glyceryl monoisostearate , glycerin fatty acid esters such as glyceryl monooleate, and polyhydric alcohol fatty acid ester type surfactants. Among these, polyglycerin fatty acid esters higher than triglycerin such as decaglyceryl tetraoleate, hexaglyceryl triisostearate, and tetraglyceryl diisostearate, POE
(2-12) Oleyl ether, P OE (3-1
2) Stearyl ether, P OE (2-10) Lauryl ether, P OE (2-10) Nonylphenyl ether, POE (6-15) Behenyl ether, P
OE (5-20) 2-decyl pentadecyl ether,
POE addition ether type activators such as POE (5-17) 2-decyltetradecyl ether, POE (8-16) 2-octyl decyl ether, and POE (10
-20) POE addition ester type activator such as hydrogenated castor oil, POE (5-14) oleic acid monoester, POE (6-20) oleic acid diester, POE (5-10) sorbitan oleate, P.O.
E (3-1.

5) Glyceryl monoisostearate, POE (10-
40) Ethylene oxide-added nonionic surfactants such as POE-added ether ester type surfactants such as glyceryl triisostearate are particularly preferred. In carrying out the present invention, from among these nonionic surfactants -m
Or two or more types are arbitrarily selected and used.

(Note 1) The HLB value of a nonionic activator is calculated using the soil equation below.

O (Here, Mw represents the molecular weight of the hydrophilic group, and MO represents the molecular weight of the lipophilic group.) The organically modified clay mineral used in the present invention is water-swellable in a low boiling point solvent such as water, acetone, or lower alcohol. A clay mineral, a quaternary ammonium salt type cationic surfactant, and a nonionic surfactant are dispersed and stirred, or a water-swellable clay mineral and a quaternary ammonium salt type cationic surfactant are mixed in advance with a low boiling point. It is obtained by processing in a solvent to obtain a cationically modified clay mineral, followed by treatment with a nonionic surfactant and then removing the low boiling point solvent.

When the quaternary ammonium salt type cationic surfactant and the nonionic surfactant enter the glabella, the interlayer spacing of the water-swellable clay mineral widens, so the long-plane spacing is measured using X-ray diffraction. By this, it is possible to confirm whether or not the quaternary ammonium salt type cationic surfactant and the nonionic surfactant are adsorbed.

Furthermore, if the obtained organically modified clay mineral is subjected to Waxley extraction using chloroform, ether, etc., the surfactant between the layers will be washed away, so the extract can be analyzed by gas chromatography, thermal decomposition temperature measurement, or thermal decomposition ffi. The presence of the surfactant can be confirmed by measurement (DTA-TO measurement, etc.).

The content of the quaternary ammonium salt type cationic surfactant in the organically modified clay mineral used in the present invention is 60 to 140 milliequivalents (hereinafter o+eq) per 100 g of water-swellable clay mineral.
It is abbreviated as ) is preferable. The content of the nonionic surfactant in the organically modified clay mineral is preferably 5 to 2,008 g, and even more preferably 15 to 170 g, per 100 g of the water-Ils clay mineral.

The amount of the organically modified clay mineral blended into the polyhydric alcohol-in-oil emulsion composition according to the present invention is about 0.25 to 5% by weight, preferably 0.5 to 3% by weight.

The oil used in the present invention can be any of the common oils used in cosmetics, pharmaceuticals, etc., and can be used in a wide range from polar oils to non-polar oils. Examples of oils include hydrocarbon oils such as liquid paraffin, squalane, isoparaffin, and branched light paraffins, ester oils such as isopropyl myristate, cetyl isooctanoate, and glyceryl trioctanoate, decamethylpentasiloxane, and dimethyl. Examples include silicone oils such as polysiloxane and methylphenylpolysiloxane. Also petrolatum, macrophristalin wax, lanolin,
Waxes such as peace wax can also be incorporated within the range that does not impair the effects of the present invention. The blending amount of these oils in the polyhydric alcohol-in-oil emulsion composition is approximately 5-90% by weight, preferably 10-80% by weight.

The polyhydric alcohol used in the present invention has two or more hydroxyl groups in the molecule, such as polyethylene glycol,
Examples include liquid polyhydric alcohols such as dipropylene glycol, 1,3-butylene glycol, propylene glycol, and glycerin.

In addition, polyhydric alcohols such as sorbitol and maltitol, which are solid at room temperature, can be dissolved in a small amount of water. Weight percent is preferred.

[Effects of the Invention] The polyhydric alcohol-in-oil emulsion composition of the present invention has a small amount of organically modified clay minerals (about 0.25 to 5% by weight), By controlling the ratio of alcohol phase), it is possible to control the viscosity without adding solidifying agents such as wax, and it is also possible to use highly polar oils, which were difficult to mix in the past. It has excellent storage stability over a wide temperature range.Furthermore, since the organically modified clay mineral used in the present invention is in powder form, it is very easy to handle and store.The present invention has such great advantages. By taking advantage of its characteristics, the polyhydric alcohol-in-oil emulsion composition can be used in a wide range of fields such as pharmaceuticals, cosmetics, and paints.

[Examples] Next, in order to further understand the present invention, the examples are not limited to the following. In the examples, parts and % are all parts by weight.
Weight%.

Example 1 Benzyldimethylstearylammonium chloride, Do4
To 500 ml of an aqueous solution in which 5 g (equivalent to about 100 meq) and 30 g of POE (6) lauryl ether were dissolved at 50°C, 100 g of Veegum (trade name of Vanderbilt, Inc., USA), which is a water-swellable clay mineral, was added and dispersed for about 30 minutes. Disperse and mix thoroughly.

Next, after removing water using a filter, the mixture was dried for about 24 hours to obtain the desired organically modified clay mineral.

Benzyldimethylstearylammonium chloride [
Abbreviated as (A). ) and POE (6) lauryl ether ((
Abbreviated as B). ) adsorption can be determined by X-ray diffraction and DT
The amount of thermal decomposition of the surfactant was measured using the A-TG method, and
1lifI! Judgment was made by comparing it with a natural clay mineral (vegum).

The results are shown in Table 1.

Table 1 *Amounts per 100g of water-wettable clay minerals.

As is clear from Table 1, the interlayer spacing of the organically modified clay mineral of Example 1 is significantly wider than that of the water-swellable clay mineral before treatment. As is clear from the DTA-TO measurement results, this is also caused by the bond between benzyldimethylstearylammonium chloride and POE(6) lauryl ether.

Example 2 POE (16) 2-octyldecyl ether (hereinafter (C
). ) Bentone-38, an organically modified clay mineral, is dissolved in 500@l of ethanol (100 g of montmorillonite is 100 meq of distearyldimethylammonium chloride C (abbreviated as (D)). 100g of organically modified clay mineral (trade name, manufactured by National Red Company, USA) that has not been treated with ) is sufficiently dispersed and mixed using a lab homogenizer.

Next, after removing ethanol with an evaporator,
After drying at 0°C for about one day and night, the desired organically modified clay mineral was obtained.

As in Example 1, the presence or absence of surface modification was evaluated from X-ray diffraction and the amount of surfactant in the Soxhlet extract with chloroform.

The results are shown in Table 2.

(Margin below) Table 2 Displayed in the same way as Zero Table 1.

As is clear from Table 2, even when using the organically modified clay mineral (Bentone-38) that has been treated with the quaternary ammonium salt type cationic surfactant (D), the nonionic surfactant of (C) It was found that the interlayer spacing was further widened by treatment with the agent. Similar to Example 1, this is thought to be caused by the binding of the nonionic surfactant. The amount of quaternary ammonium salt type cationic surfactant extracted by Soxhlet extraction is based on organically modified clay mineral (bentone-3) which has been organically modified by cation exchange reaction.
8) The amount of physically adsorbed quaternary ammonium salt type cationic surfactants (chemically adsorbed cationic surfactants cannot be extracted), and according to the DTA-TO method, all As shown in Example 1, the amount of ammonium salt type cationic surfactant can also be determined.

Example 3. Example 4 One part of the organically modified clay mineral obtained in Example 1 is mixed and dispersed in 50 or 30 parts of liquid paraffin to form an oil phase in advance. Subsequently, 49 parts or 69 parts of glycerin were added at room temperature and thoroughly stirred and mixed with a disper to obtain polyhydric alcohol-in-oil emulsion compositions, which are referred to as Example 3 and Example 4, respectively.

Comparative example 1. Comparative Example 2 3 parts of POE (3 molar adduct) sorbitan monooleate,
48 parts or 28 parts of liquid paraffin, 2 parts of microcrystalline wax, 7 parts of glycerin 47 parts or 67 parts
When heated at 0° C. and stirred and emulsified using a homomixer, polyhydric alcohol-in-oil emulsion compositions were obtained, which are referred to as Comparative Example 1 and Comparative Example 2, respectively.

Comparative Example 3 1 part of Bentone-38, 0.5 parts of glycerol isostearate, and 28.5 parts of liquid paraffin are mixed and stirred to form an oil phase in advance. 70 parts of glycerin was added to this and mixed with stirring using a disper to obtain a polyhydric alcohol-in-oil emulsion composition, which is referred to as Comparative Example 3.

Table 3 shows the viscosity and system stability test results at 0°C, 25°C, and 50°C of the polyhydric alcohol-in-oil emulsion compositions obtained in Examples 3 and 4 and Comparative Examples 1 and 2.3. The viscosity is expressed as a value at a shear rate of 1700 sec-1 in a combinate type viscosity system, and the stability test was performed by evaluating the appearance after being left for 2 weeks using the following evaluation criteria.

0: No separation observed Δ: Separation of the liquid phase (oil phase or aqueous phase) occurred ×: Significant separation of the liquid phase was observed (Table 3) As is clear from Table 3, the present invention The polyhydric alcohol-in-oil type emulsion composition has excellent temperature stability even when the amount of organically modified clay mineral blended is small, and even when adjusted at room temperature, and has a low internal phase (glycerin) ratio. It can be seen that if the viscosity is increased, an excellent polyhydric alcohol-in-oil emulsion composition having high viscosity and little temperature change in viscosity can be obtained without adding solid components such as wax.

Example 5. Example 6 1 part of the organically modified clay mineral obtained in Example 2 was mixed with 30 parts of cetyl isooctanoate or 30 parts of decamethylcyclopentasiloxane to form an oil phase in advance, and then 69 parts of propylene glycol was added at room temperature. and emulsification by stirring with a homomixer to obtain polyhydric alcohol-in-oil emulsion compositions, which are referred to as Example 5 and Example 6, respectively.

Comparative example 4. Comparative Example 5 POE (3 mole adduct) 3 parts of oleyl ether, 30 parts of cetyl iso-octanoate or 30 parts of decamethylcyclopentasiloxane, and 67 parts of propylene glycol were emulsified in the same manner as in Comparative Example 1.2, resulting in an emulsion in oil. Polyhydric alcohol type emulsion compositions were obtained, which are referred to as Comparative Example 4 and Comparative Example 5, respectively.

Table 4 shows the viscosity and stability test results of the polyhydric alcohol-in-oil emulsion compositions obtained in Example 5.6 and Comparative Example 4.5. The viscosity and stability were evaluated using the same method as described above.

(Table 4) As is clear from Table 4, the polyhydric alcohol-in-oil emulsion composition of the present invention shows little change in stability and viscosity over a wide temperature range even when a highly polar oil is used.

Below is the margin example 7 “Seimi” fish! Glossy and vibrant 1) Liquid paraffin 30
．． 0(2) 0.6g of Veegum with 0.2g of benzyldimethylstearylammonium chloride and POE (13)
Organically modified clay mineral obtained by treatment with 0.2 g of diisostearic acid ester 1.0 (3) Salilaric acid 1.0 (4
) Glycerin 68.0 Production method (1), (2), and (3) are mixed and dispersed at room temperature to produce an oil phase in advance. (4) was gradually added to this while stirring with a disper, and the mixture was thoroughly mixed and stirred to obtain the desired concentration.

Example 8 L-process El (1) Squalane 30
．． 0(2) Lanolin
1.0(3) Microcrystalline wax
1.0 (4) 0.5 g of bentone-38 in POE
(14) Organomodified clay mineral treated with 0.05 g of dioleic acid ester and decaglyceryl tetraoleate o, osg 1.2 (5) Chloramphu, Ryo, Nicol 1.0 (6) Propylene glycol 65.8 Production method (1) - (5) were mixed and dispersed to prepare an oil phase in advance, and the desired ointment was obtained according to Example 7.

Example 10 Moisture cream (1) Squalane 2
0.0i2) Cetyl isooctanoate
8.5(3) 1.0 g of pea gum, 0.2 g of benzyldimethylbehenylammonium chloride, 0.1 g of distearyldimethylammonium chloride and P O
E (10) Glycerol triisostearate 0.2
Organomorphic clay minerals obtained by processing g.
1.5 (4) Fragrance
Appropriate amount (5) Ethyl paraoxybenzoate 0.2 (6) Sorbitol
69.8 Manufacturing method According to Example 7, the target moisture cream was manufactured.

Patent applicant Shiseido Co., Ltd. Voluntary writing of procedural amendments) April 24, 1985

Claims (3)

[Claims] (1) Contains an organically modified clay mineral obtained by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant, an oil component, and a polyhydric alcohol. A polyhydric alcohol-in-oil emulsion composition. (2) The content of quaternary ammonium salt type cationic surfactant is 60-140% per 100g of water-swellable clay mineral.
The polyhydric alcohol-in-oil emulsion composition according to claim 1, which is milliequivalent. (3) The polyhydric alcohol-in-oil emulsion composition according to claim 1, wherein the content of the nonionic surfactant is 5 to 200 g per 100 g of water-swellable clay mineral.