JP7022422B2 - Water-in-oil emulsification composition - Google Patents

Description

The present invention relates to a water-in-oil emulsified composition having excellent storage stability, spreading on the skin, and having a good feeling of use without stickiness or stickiness.

The emulsified composition is roughly divided into an oil-in-water emulsified composition in which the outer phase is water and a water-in-oil emulsified composition in which the outer phase is oil, and they are used properly according to the required function and usability. While the oil-in-water emulsified composition is characterized by a fresh feeling of use, the water-in-oil emulsified composition has a high emollient effect and moisturizing effect, and is easy to impart water resistance, so it is mainly used as a foundation or a makeup base. , Is often used in sunscreen cosmetics.

In general, the water-in-oil emulsified composition often has a problem of storage stability as compared with the oil-in-water emulsified composition. For example, since the water-in-oil emulsified composition has no electric charge, it is not possible to prevent the particles from coalescing due to electrostatic repulsion between the emulsified particles, and separation or precipitation is likely to occur. There is also a problem that the oil phase, which is a continuous phase, is separated, and oil accumulates on the surface or voids of the composition and seeps out. In particular, when metal oxides such as titanium oxide, zinc oxide, and iron oxide are contained, when a volatile oil agent is contained to improve the usability, or when the ratio of water in the aqueous phase is low, the storage stability is significantly deteriorated. There is a tendency.

Conventionally, various studies have been made to improve the storage stability of the water-in-oil emulsified composition. For example, stability is improved by thickening the oil phase by blending a solid oil having a high melting point such as wax (Patent Documents 1 and 2) and blending an oil gelling agent (Patent Documents 3 and 4). The technology to make it is disclosed. However, these techniques tend to make the spread heavy at the time of application and give stickiness after application, resulting in poor usability. Further, in order to achieve both good storage stability and a fresh and non-greasy feel, techniques using a water-soluble polymer (Patent Documents 5 and 6) are also disclosed. However, depending on the type and content of the water-soluble polymer, there are problems such as slippage during coating and the presence or absence of an electrolyte greatly affects the storage stability.

Japanese Unexamined Patent Publication No. 2008-24630 Japanese Unexamined Patent Publication No. 2002-255738 Japanese Unexamined Patent Publication No. 2011-219425 Japanese Unexamined Patent Publication No. 5-70336 Japanese Unexamined Patent Publication No. 2010-235469 Japanese Unexamined Patent Publication No. 2002-348210

It is an object of the present invention to provide a water-in-oil emulsified composition which is excellent in storage stability, is also excellent in spreading on the skin and freshness, and has a good feeling of use without stickiness and stickiness. ..

In view of such circumstances, as a result of diligent research, the inventor of the present application has found that the component (A) dipolyhydroxystearate PEG-30, the component (B) a semi-solid ester oil at 25 ° C., the component (C) diglycerin and the component ( D) The water-in-oil emulsified composition containing water and having the content of the component (D) in a weight ratio of 0.1 to 0.5 with respect to the total amount of the aqueous phase is excellent in storage stability and further. Has completed the invention of the present application by finding that it has excellent spreadability and freshness on the skin, and has a good feeling of use without stickiness or stickiness.

That is, the present invention has the following components (A) to (D);
(A) PEG-30 dipolyhydroxystearate
(B) Contains semi-solid ester oil (C) diglycerin (D) water at 25 ° C., and the content of component (D) is 0.1 to 0.5 by weight with respect to the total amount of the aqueous phase. It is a water-in-oil emulsified composition characterized by being.

Further, the present invention is a water-in-oil emulsified composition characterized by containing the component (E) sugar alcohol.

The water-in-oil emulsified composition of the present invention has excellent storage stability, spreads on the skin, and has excellent freshness, and has a good feeling of use without stickiness or stickiness. Hereinafter, each component will be described in detail.

The component (A) dipolyhydroxystearic acid PEG-30 used in the present invention is a diester of poly (12-hydroxystearic acid) of polyethylene glycol (average molecular weight 1500), and the average molecular weight thereof is about 5000. Specific examples of commercially available products include Croda Japan's Sysrol DPHS.

The content of the component (A) PEG-30 dipolyhydroxystearate is not particularly limited, but is preferably 0.1 to 4.0% by weight, more preferably 0.5 to 2.0% by weight in the composition. If the content is less than 0.1% by weight, the storage stability may be deteriorated, and if it is more than 4.0% by weight, the feeling of use such as stickiness may be deteriorated after application.

The semi-solid ester oil at 25 ° C. of the component (B) used in the present invention is distinguished from liquid ester oil and solid ester oil in that it has a melting point of 25 to 70 ° C. and does not completely solidify in this range. Ester oil. For example, a dimer acid ester, a pentaerythrit fatty acid ester, a cholesterol fatty acid ester, and a phytosterol fatty acid ester are mentioned, preferably a dimer acid ester, and more preferably a dimer linoleic acid ester. The dimer dilinoleic acid ester is an ester of dimer acid obtained by polymerizing mainly 2 to 3 molecules of linoleic acid, and is, for example, dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl) and dimer dilinole. Examples thereof include acid dimer dilinoleyl bis (behenyl / isostearyl / phytosteryl). Specific examples of commercially available products include PLANDOOL-S, PLANDOOL-H, and PLANDOOL-G manufactured by Nippon Fine Chemical Co., Ltd.

The content of the semi-solid ester oil at 25 ° C. of the component (B) is not particularly limited, but is preferably 0.5 to 5.0% by weight, more preferably 1.0 to 3.0% by weight in the composition. .. If the content is less than 0.5% by weight, the storage stability may be deteriorated, and if it is more than 5.0% by weight, the spreadability at the time of application may be heavy and the usability may be deteriorated.

The component (C) diglycerin used in the present invention is not particularly limited as long as it is usually used for cosmetics, and any of them can be used. Specific examples of commercially available products include diglycerin 801 manufactured by Sakamoto Pharmaceutical Co., Ltd.

The content of the component (C) diglycerin is not particularly limited, but is preferably 3.0 to 12.0% by weight, more preferably 5.0 to 10.0% by weight in the composition. If the content is less than 3.0% by weight, the storage stability may be deteriorated, and if it is more than 12.0% by weight, the feeling of use such as stickiness may be deteriorated after application.

The content of the component (D) water used in the present invention is 0.1 to 0.5 by weight with respect to the total amount of the aqueous phase, more preferably 0.2 to 0.35. Within this range, excellent effects can be expected in both storage stability and usability.

The component (E) sugar alcohol used in the present invention is not particularly limited, and examples thereof include sorbitol, maltitol, mannitol, xylitol, and erythritol, and sorbitol is preferable. Specific examples of commercially available products include sorbitol D-70 (sorbitol 70% by weight aqueous solution) manufactured by Mitsubishi Corporation Food Tech.

The content of the component (E) sugar alcohol is not particularly limited, but is preferably 0.5 to 10.0% by weight, more preferably 2.0 to 7.0% by weight in the composition. Within this range, excellent effects can be expected in both storage stability and usability.

The water-in-oil emulsified composition of the present invention contains various components other than the above-mentioned components, for example, ultraviolet rays, which are usually used for external skin preparations such as cosmetics and pharmaceuticals, as needed, within the range not impairing the effects of the present invention. Absorbents, pH regulators, oils, moisturizers, aqueous ingredients, surfactants, antioxidants, beauty ingredients, preservatives, water-soluble polymers, film-forming agents, anti-fading agents, defoamers, fragrances, etc. Can be contained.

Hereinafter, the present invention will be described in more detail with reference to examples. The invention of the present application is not limited to the following examples. Further, the content in the following examples and the like indicates% by weight unless otherwise specified.

Prior to the examples, the effect test method used in the present invention will be described.

[Storage stability]
(1) Emulsified particles The water-in-oil emulsified composition of each example was filled in a plastic container and stored in a constant temperature bath at 4 ° C. and 40 ° C. for 3 months. The emulsified particles were observed under a microscope and judged according to the following criteria.
(Evaluation criteria)
⊚: No difference is observed from the initial state.
◯: The emulsified particles are slightly larger, but the emulsified state is maintained.
X: The emulsified particles are clearly larger.

(2) Oil exudation The water-in-oil emulsified composition of each example was filled in a plastic container and stored in a constant temperature bath at 4 ° C. and 40 ° C. for 3 months. The oil seepage was visually confirmed, and the judgment was made according to the following criteria.
(Evaluation criteria)
⊚: There is no oil seepage and no difference is observed from the initial state.
◯: Slight oil seepage is seen.
X: A large amount of oil seeps out.

[Usage]
(1) Good spreadability A 20-person expert panel conducted a usage test on the spreadability of the water-in-oil emulsified composition of each example when applied to the skin, and judged from the results of the questionnaire according to the following criteria.
(Evaluation criteria)
⊚: Of the 20 people, 15 or more answered that they had good growth.
◯: Of the 20 respondents, 10 to 14 responded that the spread was good.
Δ: 5 to 9 out of 20 responded that the spread was good.
×: Of the 20 respondents, 4 or less answered that the spread was good.

(2) No slipperiness A 20-person expert panel conducted a usage test on the non-slipperiness of the water-in-oil emulsified composition of each example when applied to the skin, and judged from the results of the questionnaire according to the following criteria.
(Evaluation criteria)
⊚: Of the 20 people, 15 or more answered that they were not sly.
◯: Of the 20 respondents, 10 to 14 responded that there was no slippage.
Δ: 5 to 9 out of 20 responded that there was no slippage.
×: Of the 20 respondents, 4 or less responded that there was no slippage.

(3) Freshness A water-in-oil emulsified composition of each example was subjected to a usage test for freshness after being applied to the skin by 20 specialist panels, and the results of the questionnaire were judged according to the following criteria.
(Evaluation criteria)
⊚: Of the 20 people, 15 or more answered that they felt freshness.
◯: Of the 20 respondents, 10 to 14 responded that they felt freshness.
Δ: 5 to 9 out of 20 responded that they felt freshness.
×: Of the 20 respondents, 4 or less answered that they felt freshness.

(4) Non-stickiness The water-in-oil emulsified composition of each example was tested for non-stickiness after being applied to the skin by 20 specialist panels, and the results of the questionnaire were judged according to the following criteria.
(Evaluation criteria)
⊚: Of the 20 people, 15 or more answered that they were not sticky.
◯: Of the 20 respondents, 10 to 14 responded that they were not sticky.
Δ: 5 to 9 out of 20 responded that they were not sticky.
×: Of the 20 respondents, 4 or less answered that they were not sticky.

The water-in-oil emulsified compositions of the formulations shown in Tables 1 to 3 were prepared, and the storage stability and usability were evaluated according to the above criteria.

The water-in-oil emulsified compositions obtained by the formulations shown in Tables 1 to 3 were prepared by the production methods shown below.
(Examples 1 to 23 and Comparative Examples 1 to 7, 10, 11)
After the oil phase a part was heated and mixed, the b part was added and uniformly dispersed. The uniformly dissolved aqueous phase was gradually added to the oil phase while stirring, and the homomixer was operated at 5000 rpm for 10 minutes at room temperature to emulsify. After emulsification, defoaming was performed to obtain a water-in-oil emulsified composition of each example.
(Comparative Examples 8 and 9)
After the oil phase a part was heated and mixed, the b part was added and uniformly dispersed. In the aqueous phase, xanthan gum or a carboxyvinyl polymer was dispersed in water, and then other components were added and mixed. The aqueous phase was gradually added to the oil phase with stirring, and the homomixer was operated at 5000 rpm for 10 minutes at room temperature to emulsify. After emulsification, defoaming was performed to obtain a water-in-oil emulsified composition of each example.

From the results shown in Table 1, the component (A) dipolyhydroxystearate PEG-30, the component (B) semi-solid ester oil at 25 ° C., the component (C) diglycerin and the component (D) water were contained. Moreover, the water-in-oil emulsified compositions (Examples 1 to 9) in which the content of the component (D) is 0.1 to 0.5 by weight with respect to the total amount of the aqueous phase are all excellent in storage stability. It was also good in all the usability evaluation items. In particular, the component (A) PEG-30 dipolyhydroxystearate is 0.5 to 2.0% by weight, and the component (B) dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl) is 1.0 to 2.0. The water-in-oil emulsified composition containing 3.0% by weight (Examples 2, 3, 6 and 7) had remarkably excellent evaluation results in all the evaluation items. On the other hand, instead of the water-in-oil emulsified composition (Comparative Examples 1 and 2) and the component (B) containing no component (A) or component (B), a semi-solid hydrocarbon oil or solid at 25 ° C. The water-in-oil emulsified composition (Comparative Examples 3 to 6) using the oil having a shape did not provide sufficient storage stability and a satisfactory usability.

From the results shown in Table 2, the component (A) dipolyhydroxystearate PEG-30, the component (B) semi-solid ester oil at 25 ° C., the component (C) diglycerin and the component (D) water were contained. Moreover, the water-in-oil emulsified compositions (Examples 10 to 17) in which the content of the component (D) is 0.1 to 0.5 by weight with respect to the total amount of the aqueous phase are all excellent in storage stability. It was also good in all the usability evaluation items. In particular, water-in-oil emulsification in which the component (C) diglycerin is 5.0 to 10.0% by weight and the content of the component (D) is 0.2 to 0.35 by weight with respect to the total amount of the aqueous phase. The composition (Examples 11, 12, 15, 16) was a remarkably excellent evaluation result in all the evaluation items. On the other hand, the content of the water-in-oil emulsified composition (Comparative Examples 7 to 9) containing no component (C) and the content of the component (D) is 0.1 to 0.5 by weight with respect to the total amount of the aqueous phase. The water-in-oil emulsified compositions (Comparative Examples 10 and 11) that did not have sufficient storage stability and satisfactory usability could not be obtained.

From the results shown in Table 3, the component (A) dipolyhydroxystearate PEG-30, the component (B) semi-solid ester oil at 25 ° C., the component (C) diglycerin, and the component (D) water were contained. Moreover, the water-in-oil emulsified compositions (Examples 18 to 23) in which the content of the component (D) is 0.1 to 0.5 by weight with respect to the total amount of the aqueous phase are all excellent in storage stability. It was also good in all the usability evaluation items. Further, the water-in-oil emulsified composition (Examples 19 and 20) containing 2.0 to 7.0% by weight of sorbitol as the component (E) sugar alcohol was a remarkably excellent evaluation result in all the evaluation items. rice field.

Hereinafter, the invention of the present application will be described with reference to examples in order to explain in detail. In addition, both Examples 24 and 25 were excellent in storage stability, and were also good in all the usability evaluation items.

Example 24: Makeup base (water-in-oil type)
Ingredient content (% by weight)
Oil phase (1) Dipolyhydroxystearate PEG-30 * 1 1.00
(2) Dimer dilinoleic acid (phytosteryl / isostearyl)
/ Cetyl / Stearyl / Behenil) * 2 2.00
(3) Isotridecyl isononanoate 7.00
(4) Didimethylpolysiloxane (10cs) 8.00
(5) Ethylhexyl methoxycinnamate 4.00
(6) PEG-9 Methyl Ether Dimethicone 1.00
(7) Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 2.50
(8) Trimethylsiloxysilicic acid 1.50
(9) Hydrophobicized silica * 14 2.00
(10) Tocopherol 0.05
(11) Decamethyltetrasiloxane * 15 Remaining amount (12) Silicone-treated fine particles Titanium oxide * 16 3.00
(13) Silicone-treated titanium oxide * 8 5.00
(14) Silicone treated Bengala * 17 0.12
(15) Silicone-treated iron oxide * 18 0.36
(16) Silicone-treated black iron oxide * 19 0.06
Aqueous phase (17) Purified water 15.00
(18) 1,3-butylene glycol 15.00
(19) Glycerin * 20 7.00
(20) Diglycerin * 9 9.00
(21) Magnesium sulfate 0.30
(22) Methyl paraoxybenzoate 0.20

After the oil phases (1) to (11) were heated and mixed, (12) to (16) were added and uniformly dispersed. The uniformly dissolved aqueous phases (17) to (22) were gradually added while stirring, and the homomixer was operated at 5000 rpm for 10 minutes at room temperature to obtain the makeup base of Example 24.

Example 25: Foundation (water-in-oil type)
Ingredient content (% by weight)
Oil phase (1) Dipolyhydroxystearate PEG-30 * 1 1.00
(2) Dimer dilinoleic acid (phytosteryl / isostearyl)
/ Cetyl / Stearyl / Behenil) * 2 2.00
(3) Octyldodecyl myristate 5.00
(4) Ethylhexyl methoxycinnamate 4.00
(5) PEG-9 Dimethicone 1.00
(6) Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 2.50
(7) Trimethylsiloxysilicic acid 1.50
(8) Gisteardimonium hectorite 0.50
(9) Hydrophobicized silica * 14 2.00
(10) Tocopherol 0.05
(11) Cyclopentasiloxane remaining amount (12) Silicone-treated fine particles Titanium oxide * 16 4.00
(13) Silicone-treated titanium oxide * 8 10.00
(14) Silicone treated Bengala * 17 0.40
(15) Silicone-treated iron oxide * 18 1.60
(16) Silicone-treated black iron oxide * 19 0.20
Aqueous phase (17) Purified water 14.00
(18) 1,3-butylene glycol 12.00
(19) Glycerin * 20 5.00
(20) Sorbitol (70% by weight aqueous solution) * 10 5.00
(21) Diglycerin * 9 9.00
(22) Magnesium sulfate 0.30
(23) Xanthan gum * 11 0.05
(24) Sodium hyaluronate 0.01
(25) Methyl paraoxybenzoate 0.20

After the oil phases (1) to (11) were heated and mixed, (12) to (16) were added and uniformly dispersed. In the aqueous phase (17) to (25), (23) and (24) were dispersed in (17), and then other components were added and mixed. The aqueous phase was gradually added to the oil phase with stirring, and the homomixer was operated at 5000 rpm for 10 minutes at room temperature to obtain the foundation of Example 25.

* 1: Sysroll DPHS: Made by Croda Japan * 2: Plandool-H: Made by Nippon Seika Co., Ltd. * 3: Cosmall 168ARV: Made by Nisshin Oillio Group * 4: CROLATUM V: Made by Croda Japan * 5: BEES WAX- S: Made by Croda Japan * 6: Paraffin WAX 130: Made by Nippon Seiro * 7: BEHENYL ALCOHOL: Made by Higher Alcohol Industry Co., Ltd. * 8: SA-Titanium MP-1133 (AL2.5 wt% hydroxide, 2 weight dimethicon) %process)
: Made by Miyoshi Kasei, Inc. * 9: Diglycerin 801: Made by Sakamoto Pharmaceutical Co., Ltd. * 10: Sorbitol D-70 (70% by weight of sorbitol, 30% by weight of water): Made by Mitsubishi Corporation Food Tech Co., Ltd. * 11: Echo gum: DSP Gokyo Food & Chemical Co., Ltd. * 12: Hibiswaco 104: Wako Pure Chemical Industries, Ltd. * 13: D-Mannitol: Kao Co., Ltd. * 14: AEROSIL R976: Japan Aerosil Co., Ltd. * 15: KF-96L-1.5cs: Shin-Etsu Chemical Industry Co., Ltd. * 16: MTY-700BS (hydrogen dimethicone 2% by weight treatment): Teika Co., Ltd. * 17: SAS-Red R516-PS (100%) (dimethicone 3% by weight, hydrogen dimethicone 0.5% by weight treatment) ): Manufactured by Miyoshi Kasei, Inc. * 18: SAS-Yellow LL-100P (100%) (treated with 3% by weight of dimethicone, 0.5% by weight of hydrogen dimethicone): manufactured by Miyoshi Kasei, Inc. * 19: SAS-Black BL-100P (100%) 100%) (3% by weight of dimethicone, 0.5% by weight of hydrogen dimethicone): manufactured by Miyoshi Kasei, Inc. * 20: glycerin RG, co, P: manufactured by Nichiyu Co., Ltd.

It is possible to provide a water-in-oil emulsified composition which is excellent in storage stability, is also excellent in spreading on the skin and freshness, and has a good feeling of use without stickiness or stickiness.

Claims (2)

The following components (A) to (D);
(A) Dipolyhydroxystearate PEG-30 0.5-2% by weight
(B) Dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl) 1 to 3% by weight
(C) Diglycerin 5-10% by weight
(D) A water-in-oil emulsified composition containing water and having a content of component (D) of 0.2 to 0.35 by weight with respect to the total amount of the aqueous phase. The water-in-oil emulsified composition according to claim 1, which contains a sugar alcohol as the component (E).