JP2001058923A - Two-layer water-in-oil type emulsified composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of becoming a homogeneously mixed water-in-oil type emulsified composition through shaking and mixing the subject composition, and whose oil-water interface thereof stably separates into two layers after the lapse of a given time by including a specific silicone, specific oil and water. SOLUTION: This composition is obtained by including (A) 0.01-0.5 wt.% of a polyether-modified silicone of the formula [A is methyl, phenyl or B; B is a polyoxyalkylene of the formula: C3H6O(C2H4O)a(C3H6O)bR'(R' is H, an acyl, or 1-4C alkyl; (a) and b are each 5-50) ; R is methyl or phenyl; m is 50-1,000; n is 1-40; wherein having at least one polyoxyalkylene in the molecule and also >=40 wt.% of the polyoxyalkylene therein and the molecular weight of the polyether-modified silicone is >=30,000], (B) 5.0-80.0 wt.% of a silicone oil, (C) water, and if necessary, (D) a lower alcohol and (E) e.g. a polyhydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a two-layer water-in-oil emulsion composition, and more particularly, to a water-in-oil emulsion composition by shaking and mixing without using a surfactant. The present invention relates to a two-layer water-in-oil emulsified composition wherein the oil-water interface is stably divided into two layers after being obtained and after a certain period of time.

[0002]

2. Description of the Related Art Conventionally, a two-layer emulsion composition is obtained by shaking and mixing with a surfactant, and after a certain period of time, an oil-water interface is divided into two layers. It is known to have features.

[0003]

However, in order to obtain a stable water-in-oil emulsion at the time of shaking and mixing, a surfactant must be conventionally added as an emulsifier. When the oil-water interface separates into two layers after a lapse of time, there has been a disadvantage that some emulsified layers are present on the oil-water interface in an unstable state, which is undesirable in appearance.

In order to solve this drawback, a polyether-modified silicone is used as an emulsifier (Japanese Patent Publication No. 5-32).
No. 363), various additives have been tried, but the solution has not yet been solved.

As described above, a water-in-oil emulsion composition is obtained by shaking and mixing, and after a certain period of time, the oil-water interface is stably divided into two layers. Obtaining a product is difficult in terms of emulsion stability, and a solution has been desired.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above circumstances, and as a result, have found that a high-molecular-weight polyether-modified silicone having a specific polyoxyalkylene group content as an emulsifier has a specific compounding amount. A water-in-oil type emulsion composition that is uniformly mixed by shaking / mixing by using in water, and after a certain period of time, the oil-water interface is stably divided into two layers. It was found that a product was obtained, and the present invention was completed.

That is, the present invention provides (a) one or more polyether-modified silicones represented by the following general formula (1) in an amount of 0.01 to 0.2 with respect to the total amount of the emulsified composition.
5% by weight and (b) a silicone oil content of 5.0 to 80.0
A two-layer water-in-oil type emulsion composition characterized by being blended with water (c) by weight and (c) water.

[0008]

Embedded image

[In the formula, A represents a methyl group, a phenyl group or B described later, and B represents a general formula: -C ₃ H ₆ O (C ₂ H
_{4 O) a (C 3 H} 6 O) bR '( where, R' is hydrogen atom, an acyl group, and a group selected from the group consisting of alkyl group having 1 to 4 carbon atoms, a is 5 to An integer of 50, b
Is an integer of 5 to 50. ), R is a methyl group or a phenyl group, m is an integer of 50 to 1000, and n is an integer of 1 to 40. However, at least one has a polyoxyalkylene group in the molecule. Further, the polyoxyalkylene group is contained in the molecule in an amount of 40% by weight or more, and the molecular weight of the polyether-modified silicone is 30,000 or more. ]

According to the present invention, a water-in-oil emulsion composition can be obtained by shaking and mixing by using a polyether-modified silicone as an emulsifier without using a surfactant as an emulsifier. After some time,
A two-layer water-in-oil emulsion composition in which the oil-water interface is stably divided into two layers is obtained.

Hereinafter, the configuration of the present invention will be described. The polyether-modified silicone (a) used in the present invention is an organopolysiloxane having a polyoxyalkylene group represented by the general formula (1).

The polyether-modified silicone molecule must contain at least 40% by weight of a polyoxyalkylene group. Specific examples of the acyl group of R ′ in the polyoxyalkylene group include a formyl group, an acetyl group, a propionyl group, a butyroyl group, an acryloyl group, a benzoyl group, and a toluoyl group. Specific examples of the group include a methyl group, an ethyl group, i
-Propyl group, n-propyl group, t-butyl group and n-butyl group are exemplified.

In the polyoxyalkylene group,
When a or b is less than 5, the polyether-modified silicone does not show a sufficient emulsifying effect, and
When b is more than 50, the obtained two-layer water-in-oil emulsion composition has a sticky feeling.

The content of the polyoxyalkylene group is at least 40% by weight, preferably in the range of 40 to 70% by weight. This means that the polyoxyalkylene group content is 40
If the amount is less than 70% by weight, the emulsifiability of non-polar oils other than silicone oil is reduced, and if the amount is more than 70% by weight, the obtained emulsified composition becomes sticky. Further, m is an integer of 50 to 1000, and n is 1 to
It is an integer of 40. This is because when m is less than 50 and n is less than 1, the emulsifying effect is insufficient, and when m exceeds 1000 and n exceeds 40,
This is because the obtained emulsion composition has a sticky feeling.

The polyether-modified silicone used in the present invention has a molecular weight of 30,000 or more,
00 or more is preferable. This is because when the molecular weight of the polyether-modified silicone is less than 30,000, the emulsifying ability for non-polar oil components other than silicone oil is reduced.

As the polyether-modified silicone in the present invention, TS Polymer 50-D5 (manufactured by Dow Corning Toray Silicone Co., Ltd.) is commercially available.

The amount of the polyether-modified silicone used in the present invention is from 0.01 to 0.5% by weight, preferably from 0.03 to 0.1% by weight. If the blending amount of the polyether-modified silicone is less than 0.01% by weight, a stable emulsified state cannot be obtained, and the emulsion will be separated when applied to the skin. On the other hand, if the content exceeds 0.5% by weight, it takes a considerable time to return to the original two-layered shape after shaking and mixing, which is not preferable in appearance.

The silicone oil (b) used in the present invention includes, for example, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, etc. Diorganopolysiloxanes; cyclic siloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tetramethyltetraphenyltetracyclosiloxane;
Chain or cyclic siloxane solution of high polymerization degree gum-like dimethylpolysiloxane, gum-like dimethylsiloxane / methylphenylsiloxane copolymer, gum-like dimethylpolysiloxane; trimethylsiloxysilicic acid etc .; trimethylsiloxysilicic acid chain Or a cyclic siloxane solution; and modified silicone oils such as diorganopolysiloxane having an alkyl group having 6 to 50 carbon atoms, amino-modified silicone, alkyl-modified silicone, and fluorine-modified silicone.

In the two-layer water-in-oil emulsion composition of the present invention, the amount of the silicone oil is 5.0 to 80.0% by weight, preferably 30.0% by weight, based on the total weight of the emulsion composition.
６60.0% by weight. If the blending amount of the silicone oil is less than 5.0% by weight, water is separated from the emulsified product even after shaking or mixing, and a stable emulsified product cannot be obtained.
When the content exceeds 0% by weight, an oily feeling becomes remarkable and exceeds an allowable range.

The amount of (c) water used in the present invention is 3.0 to 30.0% by weight, particularly 5.0 to 20.0% by weight.
Is preferred.

According to the present invention, the above (a) to
(D) a lower alcohol in addition to the component (c);
(E) There is provided a two-layer water-in-oil emulsion composition containing at least one polyhydric alcohol. By blending a lower alcohol and a polyhydric alcohol, a water-in-oil emulsion composition having a transparent appearance is obtained by shaking and mixing, and after a certain period of time, the oil-water interface is stably divided into two layers. Thus, a two-layer water-in-oil emulsion composition is obtained.

The type of the lower alcohol (d) used in the present invention is not particularly limited, but methanol or ethanol is preferred, and ethanol is particularly preferred in view of safety. In addition, i-propanol, n-propanol, t-butanol, s-butanol, etc. are too hydrophobic and are difficult to emulsify.

The amount of the lower alcohol used in the present invention is not particularly limited, but is preferably 1.0 to 30.0% by weight, more preferably 5.0 to 20.0% by weight based on the total weight of the emulsion composition. % Range. If the blending amount of the lower alcohol is less than 1.0% by weight, a transparent appearance cannot be obtained even when shaken or mixed, and if it exceeds 30.0% by weight, a stable emulsified composition can be obtained even if shaken. May not be obtained.

The type of the polyhydric alcohol (e) used in the present invention is not particularly limited, but a polyhydric alcohol having 3 to 8 carbon atoms is preferable.

The amount of the polyhydric alcohol used in the present invention is not particularly limited, but is preferably from 1.0 to 40.0% by weight, more preferably from 5.0 to 30.0% by weight based on the total weight of the emulsion composition. % By weight. If the blending amount of the polyhydric alcohol is less than 1.0% by weight, a transparent appearance cannot be obtained even if the mixture is shaken or mixed, and if it exceeds 40.0% by weight, safety is not preferred.

In the two-layer water-in-oil emulsion composition of the present invention, in addition to the above-mentioned components, if necessary, a humectant, an ultraviolet absorber, a fragrance, an antioxidant, an antiseptic and a sunscreen, an extender pigment,
Components commonly used in cosmetics, such as coloring pigments, can be blended within a range that does not impair the effects of the present invention.

The use of the emulsified composition of the present invention is not limited, but it is used as an emulsified cosmetic, preferably a skin cosmetic.

[0028]

EXAMPLES Next, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited thereby. All amounts are by weight.

Examples 1 to 3 and Comparative Examples 1 to 6 Two-layer water-in-oil emulsion compositions were prepared according to the formulations shown in Tables 1 and 2 below, and the resulting emulsion compositions were shaken. Stability test at the oil-water interface and a female expert panel (10
E) was evaluated by a practical use test. The results of the stability test were determined by shaking the emulsified composition left at 50 ° C. for one month to determine the appearance after a certain period of time, and the actual use test to determine the preference during use according to the following evaluation criteria. The results are shown in Tables 1 and 2.

(1) Stability Evaluation Criteria ：: After a certain period of time after shaking, the oil-water interface is clearly separated. Δ: After a certain period of time after shaking, the oil-water interface is almost separated. ×: After a certain period of time after shaking, the oil-water interface is not separated.

(2) Evaluation criteria for transparency after shaking ○: Transparent after shaking. Δ: Almost transparent after shaking. X: After shaking, it does not become transparent.

(3) Evaluation Criteria for Usability ：: At least 7 people were moist and dry but not sticky and judged good usability. Δ: 3 or more and less than 7 people were moist and dry but not sticky and judged good in usability. ×: Not more than 2 people were moist and dry but not sticky and judged good in usability.

[0033]

[Table 1]

[0034]

[Table 2] 比較 Comparative example ───────── ────────── 1 2 3 4 5 6 ────────────────────────────────── (1) Squalane 3.0 3.0 3.0 52.0 3.0 3.0 (2) Decamethylcyclopentasiloxane 50.0 50.0 50.0 1.0-50.0 (3) Dimethylpolysiloxane 2.0 2.0 2.0 2.0-2.0 (4) Dimethylsiloxane-methylphenylsiloxane copolymer 1.0 1.0 1.0 1.0 − 1.0 (5) Liquid paraffin − − − − 53.0 − (6) Cetyl 2-ethylhexanoate 0.5 0.5 0.5 0.5 0.5 0.5 (7) Polyether-modified silicone ^{* 1} − − 1.0 0.1 0.1 − (8) Polyether Modified silicone ^{* 2} − − − − − − 0.1 (9) Dynamite glycerin 10.0 10.0 10.0 10.0 10.0 10.0 (10) 1,3-butylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 (11 ) Ethanol − 25.0 10.0 10.0 10.0 10.0 (12) Deionized water 28.4 3.4 17.5 18.4 18.4 18.4 ────────────────────────────── ───── Stability × × × × × △ Transparency after shaking × × × × × × Usability ○ △ ○ × × △ ────────────────── ─────────────────

* 1: A compound represented by the following formula (2) (molecular weight: 55000, polyoxyalkylene group content: 45)
%) Was used.

[0036]

Embedded image

* 2: Compound represented by the following formula (3) (molecular weight: 6000, polyoxyalkylene group content: 20%)
) Was used.

[0038]

Embedded image

Example 4 Double-Layer Water-in-Oil Emulsion Composition (1) Squalane 3.0% by weight (2) Decamethylcyclopentasiloxane 50.0 (3) Dimethylpolysiloxane 2.0 (4) Dimethylsiloxane -Methylphenylsiloxane copolymer 1.0 (5) Cetyl 2-ethylhexanoate 0.5 (6) Polyether-modified silicone 0.1 (compound represented by the formula (2)) (7) Dynamite glycerin 10 0.0 (8) 1,3-butylene glycol 5.0 (9) Residual ion-exchanged water (10) Suitable amount of paraben (11) Suitable amount of antioxidant (12) Suitable amount of fragrance (Production method) (1) to (6), ( 12) is mixed and dispersed, and an oil phase is prepared in advance. Next, the aqueous phase in which (7) to (11) were dissolved was added to the oil phase while gradually stirring at room temperature using a stirrer to obtain a target emulsified composition. As in Examples 1 to 3, the emulsified composition has a usability of 、, that is, when applied to the skin, it is moist but dry, non-greasy, and has good stability (○). Was.

Example 5 Transparent two-layer water-in-oil emulsion composition (1) Squalane 3.0% by weight (2) Decamethylcyclopentasiloxane 50.0 (3) Dimethylpolysiloxane 2.0 (4) Tri Glyceryl 2-ethylhexanoate 0.5 (5) Pentaerythritol tetra-2-ethylhexanoate 0.5 (6) Polyether-modified silicone 0.05 (compound represented by the formula (2)) (7) Dynamite Glycerin 10.0 (8) Dipropylene glycol 5.0 (9) Sorbitol 2.0 (10) Ethanol 10.0 (11) Residual ion-exchanged water (12) Paraben proper amount (13) Antioxidant proper amount (14) Fragrance Appropriate amount (Preparation method) (1) to (6) and (14) are mixed and dispersed to prepare an oil phase in advance. Next, the aqueous phase in which (7) to (13) were dissolved was added to the oil phase while gradually stirring at room temperature using a stirrer to obtain a target transparent emulsion composition. The present transparent emulsion composition was prepared in Examples 1 to
Similar to 5, the usability was good, that is, when applied to the skin, it was moist but dry, non-greasy, and had good stability (good).

[0041]

As described above, according to the first aspect of the present invention,
According to the invention, a water-in-oil type emulsion composition is obtained by using only a silicone polymer as an emulsifier without using a surfactant together and shaking and mixing, and after a certain period of time, the oil-water A two-layer type water-in-oil emulsion composition in which the interface is stably divided into two layers can be obtained. Further, according to the invention of claim 2 of the present invention, after shaking and mixing, it is possible to obtain a two-layer water-in-oil emulsion composition in which an oil-water interface having a transparent appearance is stably divided into two layers. it can.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4C083 AB051 AC022 AC101 AC102 AC111 AC122 AC132 AC352 AC352 AC482 AD042 AD151 AD152 AD161 AD172 CC02 DD01 DD05 DD32 FF05

Claims (4)

[Claims] (1) 0.01 to 0.5% by weight, based on the total amount of an emulsified composition, of (a) one or more polyether-modified silicones represented by the following general formula (1): (b) silicone A two-layer type water-in-oil type emulsion composition comprising an oil content of 5.0 to 80.0% by weight and (c) water. Embedded image [In the formula, A represents a methyl group, a phenyl group or a later-described B, B has the general _{formula: -C 3 H 6 O (C} 2 H 4 O) a (C 3 H 6
O) bR ′ (wherein, R ′ is a group selected from the group consisting of a hydrogen atom, an acyl group, and an alkyl group having 1 to 4 carbon atoms, a is an integer of 5 to 50, and b is 5 Is an integer of from 50 to 50), R is a methyl group or a phenyl group, and m is from 50 to 50.
It is an integer of 1000, and n is an integer of 1 to 40. However, at least one has a polyoxyalkylene group in the molecule. Further, the polyoxyalkylene group is contained in the molecule in an amount of 40% by weight or more, and the molecular weight of the polyether-modified silicone is 30,000 or more. ] 2. A method according to claim 1, further comprising: (d) a lower alcohol;
2. A composition comprising at least one polyhydric alcohol.
The two-layer water-in-oil emulsion composition according to the above. 3. The two-layer water-in-oil emulsion composition according to claim 2, wherein the composition has a transparent appearance when shaken and mixed. 4. The two-layer water-in-oil emulsion composition according to claim 1, wherein the emulsion composition is a skin cosmetic.