JP2013107887A - Water-in-oil emulsion cosmetic and skin care method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-in-oil emulsion cosmetic extremely excellent in all of stability, the benefit of shielding the skin from external stimuli, and feel of skin after application.SOLUTION: The water-in-oil emulsion cosmetic includes the following ingredients (A) to (E): (A) 0.5-10 mass% silicone elastomer; (B) 0.2-10 mass% dimethylpolysiloxane of a degree of polymerization of 350-1,500; (C) 3-28 mass% dimethylpolysiloxane of a degree of polymerization of 1-6 and/or decamethylcyclopentasiloxane; (D) 0.5-25 mass% ethyl alcohol; and (E) water.

Description

  The present invention relates to a water-in-oil emulsified cosmetic and a skin care method.

In people's daily lives, the skin continues to be damaged due to external ultraviolet rays such as the sun's ultraviolet rays, exhaust from automobiles, air pollution caused by factories, smoking by other people, and makeup. In the present invention, the effect of protecting the skin from these external stimuli is defined as an isolation effect.
So far, research has been conducted on cosmetics that protect the skin from irritation such as the sun's ultraviolet rays, exhaust from automobiles, dust from factories, and cigarette smoke. Among these, what suppresses adhesion and penetration of stimulating substances by making a film on the skin surface has been studied (Patent Documents 1 to 4).

  Patent Document 1 proposes a high internal water phase water-in-oil emulsion cosmetic combining a silicone elastomer and a high molecular weight silicone as a cosmetic having no stickiness, good usability, and good stability. However, since the cosmetic uses a high molecular silicone, it is difficult to stretch when applied, there is a film residual feeling after application, a film with excellent feel cannot be obtained, and dirt is likely to adhere. Also, storage stability is not enough.

Patent Document 2 includes a combination of a silicone elastomer, an organic silicone resin, and an acrylic-silicone graft copolymer as a cosmetic with excellent water resistance and oil resistance, good adhesion to the skin, and excellent makeup effect durability. Water-in-oil base cosmetics have been proposed.
Patent Document 3 discloses a water-in-oil makeup that combines a silicone elastomer and an acrylic-silicone-based graft copolymer as a cosmetic material that has a long-lasting makeup, excellent makeup durability, excellent usability and stability over time. Fees have been proposed. However, these cosmetics have a heavy feeling due to a strong film residual feeling after application, and a refreshing feeling of use cannot be obtained.

  Patent Document 4 discloses a cosmetic that has excellent water resistance and durability of suncare effect, has a good feeling of use with reduced stickiness and sliminess, and has excellent stability. Silicone elastomer, oil-soluble UV absorber, Oil-in-water sun care cosmetics that combine water-soluble polymers have been proposed. However, since this cosmetic contains a water-soluble polymer, sufficient water repellency cannot be obtained, and its persistence is weak. Therefore, the effect of isolating external stimuli, particularly stimuli other than solar ultraviolet rays, is not sufficient.

JP 2001-2925 A Japanese Patent Laid-Open No. 10-236917 JP-A-11-180847 Japanese Patent Laid-Open No. 9-175777

As described above, in any of the conventional techniques, a polymer or silicone resin is often used to form a film, so that stickiness occurs at the time of application, and the skin after application is uncomfortable, such as a film feeling or a feeling of tension. There was a problem such as. In addition, an ideal effect cannot be achieved by combining stability, an isolation effect against external stimuli, and a refreshing feeling. Therefore, development of the skin care cosmetics which improved more about these points is desired.
The present invention relates to a water-in-oil emulsified cosmetic that is extremely excellent in stability, an isolation effect against external stimuli, and a refreshing feeling.

  The inventors use a specific silicone elastomer, a specific highly polymerized dimethylpolysiloxane, a specific low polymerized silicone oil and ethyl alcohol in a specific ratio in combination, stability, isolation effect against external stimuli, application It has been found that a water-in-oil emulsified cosmetic with good spreading at times, no film residual feeling after application, and a very refreshing feeling can be obtained.

The present invention includes the following components (A) to (E):
(A) Silicone elastomer 0.5-10 mass%,
The silicone elastomer has the following general formula (a-1):
R ¹ _a R ² _b H _c SiO _{(4-abc) / 2} (a-1)
And / or the following general formula (a-2):
R ¹ _j H _k SiO _{(4-jk) / 2} (a-2)
An organohydrogenpolysiloxane represented by:
The following general formula (a-3):
_{C m H 2m-1 O (} C 2 H 4 O) p (C 3 H 6 O) q C m H 2m-1 (a-3)
And / or the following general formula (a-4):
R ¹ _d R ³ _e SiO _{(4-de) / 2} (a-4)
A silicone elastomer having the component represented by the general formula (a-1) and / or the general formula (a-3) as an essential component, which is obtained by addition polymerization with an organopolysiloxane represented by the formula:
(In the formula, R ¹ is a substituted or unsubstituted alkyl group or aryl group each monovalent 1-18 carbon atoms, an aralkyl group or a halogenated hydrocarbon group having same or different, R ² is Formula - _{C n H 2n O (C 2} H 4 O) f (C 3 H 6 O) g R an organic group represented by ^4, R ³ is a monovalent hydrocarbon group having 2 to 10 carbon atoms having a terminal vinyl group, R ⁴ is a hydrogen atom, a saturated organic group having 1 to 10 carbon atoms or a group represented by R ⁵ — (CO) —, R ⁵ is a saturated organic group having 1 to ⁵ carbon atoms,
a, b, c, d, e, j and k are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1, 0.001 ≦ c ≦ 1, 1.0 ≦ d ≦ 3.0, respectively. 0.001 ≦ e ≦ 1.5, 1.0 ≦ j ≦ 3.0 and 0.001 ≦ k ≦ 1.5, f and p are integers of 2 to 200, and g and q are 0 to 200. ), F + g is 3 to 200, p + q is 3 to 200, and m and n are 2 to 6)
(B) 0.2-10 mass% of dimethylpolysiloxane whose degree of polymerization is 350 or more and 1500 or less,
(C) dimethylpolysiloxane and / or decamethylcyclopentasiloxane having a degree of polymerization of 1 or more and 6 or less, 3 to 28% by mass,
(D) 0.5-25% by mass of ethyl alcohol,
(E) It relates to a water-in-oil emulsified cosmetic containing water.

  The present invention also relates to a skin care method for using and holding the water-in-oil emulsified cosmetic on the skin.

  The water-in-oil emulsified cosmetic of the present invention is excellent in storage stability and the effect of sequestration to external stimuli, and also has good spreading at the time of application, and after application, there is no residual film feeling and is excellent in touch and refreshing. It is a thing.

In an Example, it is a figure which shows the dirt chamber used for the adhesion measurement of dirt.

  Hereinafter, each component used for the water-in-oil emulsified cosmetic of the present invention will be described in detail.

Component (A):
Component (A) is a silicone elastomer as described above.
Here, R ¹ is preferably the same or different substituted or unsubstituted monovalent alkyl group having 1 to 18 carbon atoms, preferably a methyl group or a lauryl group. In the general formula (a-3), m is preferably 3 to 6, and more preferably 3. Further, p is preferably 10 to 15, and q is preferably 0.
The component (A), together with the component (B) described later, spreads well when the water-in-oil type emulsified cosmetic of the present invention is applied to the skin. It has the function of forming a non-coated film. As a result, stimulation from the outside world can be blocked and a high isolation effect can be exhibited. Furthermore, the component (A) has a self-emulsifying ability and can stabilize the emulsification of the water-in-oil emulsified cosmetic.

Specifically, examples of the component (A) include (dimethicone / (PEG-10 / 15)) crosspolymer, (PEG-15 / lauryl dimethicone) crosspolymer, (PEG-10 / lauryl dimethicone) crosspolymer, and the like. It is done. These are usually marketed mixed with other oils. For example, there are KSG-210, KSG-240, KSG-310, KSG-320, KSG-330, KSG-340 (KSG series, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
Here, “KSG-210” is a mixture of 25% (dimethicone / (PEG-10 / 15)) crosspolymer and 75% dimethicone, and “KSG-240” is (dimethicone / (PEG-10 / 15). )) A mixture of 20% cross polymer and 80% cyclopentasiloxane, “KSG-310” is a mixture of 30% (PEG-15 / lauryl dimethicone) cross polymer and 70% mineral oil, “KSG-320 "Is a mixture of 25% (PEG-15 / lauryl dimethicone) crosspolymer and 75% isododecane, and" KSG-330 "is a mixture of 20% (PEG-15 / lauryl dimethicone) cross polymer and 80% triethylhexanoin. “KSG-340” is (PEG-10 / lauryl dimethicone) cloth Rimmer and (PEG-15 / lauryl dimethicone) is a mixture of 30% crosspolymer and squalane 70%.

  Component (A) can be used alone or in combination of two or more. From the viewpoint of a refreshing feeling and storage stability, the content of the component (A) is 0.5% by mass or more, preferably 0.625% by mass or more, more preferably 0.75% by mass or more in the total composition. It is 10 mass% or less, preferably 5 mass% or less, more preferably 2.5 mass% or less. Moreover, content of a component (A) is 0.5-10 mass% in the whole composition, 0.625-5 mass% is preferable, and 0.75-2.5 mass% is more preferable.

Ingredient (B):
Component (B) is dimethylpolysiloxane having a degree of polymerization of 350 or more and 1500 or less.
Component (B) is important for forming a flexible film on the skin surface together with component (A) and forming a natural film after application and drying. As a result, it helps to enhance the isolation effect against external stimuli.
From the viewpoint of film formation and isolation effect, the polymerization degree of the dimethylpolysiloxane of the component (B) is 350 or more, preferably 600 or more. The degree of polymerization is 1500 or less, and preferably 800 or less.
Here, the degree of polymerization is the molecular weight of dimethylpolysiloxane divided by 74.

Specific examples of the dimethylpolysiloxane having a polymerization degree of the component (B) of 350 or more and 1500 or less include KF-96A-1000cs, KF-96A-5000cs, KF-96A-10000cs, KF-96A-100000cs (Shin-Etsu). Commercial products such as Chemical Industry Co., Ltd.).
Component (B) can be used singly or in combination of two or more, and from the standpoint of sequestration effect and refreshing feeling, the content is 0.2% by mass or more in the total composition, preferably 0.8. 5 mass% or more, more preferably 1 mass% or more, 10 mass% or less, preferably 5 mass% or less, more preferably 3 mass% or less. Moreover, content of a component (B) is 0.2-10 mass% in the whole composition, 0.5-5 mass% is preferable, and 1-3 mass% is more preferable.

Component (C):
Component (C) is dimethylpolysiloxane and / or decamethylcyclopentasiloxane having a degree of polymerization of 1 to 6.
Component (C) acts as a plasticizer for component (A) and component (B) in the water-in-oil emulsified cosmetic of the present invention, improves the mixing of component (A) and component (B), and is applied. It spreads well and spreads evenly over the skin surface. As a result, a better film is formed, and the isolation effect against external stimuli is further improved.
Specific examples of the dimethylpolysiloxane having a degree of polymerization of component (C) of 1 or more and 6 or less include dimethylpolysiloxane (viscosity 1 cs), dimethylpolysiloxane (viscosity 2 cs), and the like, and decamethylcyclopentasiloxane. Etc.

Component (C) can be used alone or in combination of two or more.
Considering the easiness of extension at the time of application and storage stability, the content of the component (C) is 3% by mass or more, preferably 8% by mass or more, and 28% by mass or less in the total composition. Preferably it is 18 mass% or less, More preferably, it is 14 mass% or less. Moreover, content of a component (C) is 3-28 mass% in the whole composition, 8-18 mass% is preferable, and 8-14 mass% is more preferable.

  In the water-in-oil emulsified cosmetic of the present invention, the mass ratio (A) / ((A) of the content of the component (A) and the total content of the component (A), the component (B) and the component (C). ) + (B) + (C)) is preferably 0.03 or more, more preferably 0.04 or more, and still more preferably 0.06 or more, from the viewpoints of emulsion stability, film formation, and spreadability. 0.27 or less, more preferably 0.14 or less.

Component (D):
Component (D) is ethyl alcohol. It functions as a solvent in the water-in-oil emulsified cosmetic of the present invention, contributes to good spreadability during application, and can improve the storage stability of the system. In particular, when an oily component that does not mix with the components (A) and (B) such as the ultraviolet protective agent of the component (H) described later is blended, the separation of the oil is suppressed by the component (D).
The content of component (D) is 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and 25% by mass or less in the total composition from the viewpoint of storage stability. Preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less. Moreover, content of a component (D) is 0.5-25 mass% in the whole composition, 1-20 mass% is preferable, and 3-15 mass% is more preferable.

Ingredient (E):
Ingredient (E) is water. The water-in-oil emulsified cosmetic of the present invention can stably contain a large amount of water in the cosmetic. As a result, when applied, the skin surface is not sticky and gives a light feel. In addition, since the water-in-oil emulsified cosmetic of the present invention can form a highly occlusive film, water can be retained on the skin even after a long time, and even after application, it can be maintained continuously. A refreshing feeling can be given to the skin.
The water content of the component (E) is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more in the total composition from the viewpoint of a refreshing feeling and storage stability. is there. Moreover, 90 mass% or less is preferable, and 85 mass% or less is more preferable.

Ingredient (F):
The water-in-oil emulsified cosmetic of the present invention can further contain (F) a surfactant containing a silicone chain of less than HLB8.
The component (F) contributes to the improvement of the stability of the water-in-oil emulsified cosmetic of the present invention. In producing the emulsified cosmetic of the present invention, stirring by a homomixer may be added in order to realize long-term storage stability improvement of the emulsified cosmetic by making the particle size of the emulsified cosmetic uniform and fine. When the component (F) is contained, no separation occurs even when a strong shearing force such as a homomixer is applied.
In order to stabilize water-in-oil emulsification, the surfactant of component (F) preferably has an HLB of less than 8, more preferably HLB 3-5.

Here, HLB (Hydrophilic-Lypophilic Balance) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant, and is determined by the following formula.
HLB = 7 + 11.7 log (Mw / Mo) (I)
In the formula (I), Mw represents the molecular weight of the hydrophilic base, and Mo represents the molecular weight of the lipophilic base.

  In the present invention, since the oil phase is mainly composed of silicone, a silicone-based surfactant is preferably used as the component (F) surfactant. Specific examples include PEG-3 dimethicone (HLB4.5), PEG-10 dimethicone (HLB4.5), PEG-12 dimethicone (HLB6.0), PEG-9 polydimethylsiloxyethyl dimethicone (HLB4.0), lauryl. PEG-9 polydimethylsiloxyethyl dimethicone (HLB3.0) etc. are mentioned. Of these, PEG-3 dimethicone, PEG-10 dimethicone, and PEG-12 dimethicone are preferable, and PEG-10 dimethicone is more preferable.

  The surfactant of component (F) can be used by mixing one or more surfactants. The content of the component (F) is preferably 0.1% by mass or more, more preferably 0.33% by mass or more, and still more preferably 0% in the total composition from the viewpoints of feeling during use and stability during preparation. .66% by mass or more. Moreover, 3 mass% or less is preferable, More preferably, it is 2.5 mass% or less, More preferably, it is 2 mass% or less.

Ingredient (G):
The water-in-oil emulsified cosmetic of the present invention can further contain (G) inorganic salts. When the water-in-oil emulsified cosmetic of the present invention further contains an inorganic salt of component (G), the change in viscosity with time can be suppressed.
Specific examples of the inorganic salt of component (G) include chlorides such as sodium chloride, potassium chloride, calcium chloride and magnesium chloride; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate and aluminum sulfate; sodium carbonate and hydrogen carbonate Carbonates such as sodium; potassium hydroxide and the like. Sodium chloride, calcium chloride, magnesium sulfate and potassium hydroxide are preferred, and magnesium sulfate is more preferred.
The inorganic salts of component (G) can be used alone or in combination of two or more. The content of the component (G) is preferably 0.1% by mass or more, more preferably 0.33% by mass or more, further preferably 0.66 or more, in the total composition from the viewpoint of the rate of change in viscosity with time. is there. Moreover, 3 mass% or less is preferable, More preferably, it is 2 mass% or less.

Ingredient (H):
Furthermore, the water-in-oil emulsified cosmetic of the present invention can contain (H) a UV protection agent. In the water-in-oil emulsified cosmetic of the present invention, by further containing the ultraviolet protective agent of component (H), in the formation of a film composed of the components (A), (B) and (C), the component The ultraviolet protection effect of (H) is further enhanced.
The ultraviolet protective agent of component (H) includes an ultraviolet absorber and an ultraviolet scattering agent.

  Specific examples of the ultraviolet absorber include benzyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, Cinnamic acid-based UV absorbers such as isopropyl paramethoxycinnamate and diisopropyl cinnamate ester, hydroxymethoxybenzophenone, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, paradimethylaminoamyl amyl, paradimethyl Benzoic acid ester UV absorption such as octyl aminobenzoate, ethyl 4- [N, N-di (2-hydroxypropyl) amino] benzoate, hexyl 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoate Agent, ethylene glycol salicylate , Salicylic acid UV absorbers such as phenyl, salicylate, octyl salicylate, benzyl salicylate, p-tert-butylphenyl salicylate, homomenthyl salicylate, 2,4,6-trianilino-p- (carbo-2'-ethylhexyl-1'- And oil-soluble organic ultraviolet absorbers such as triazine ultraviolet absorbers such as (oxy) -1,3,5-triazine.

  Specific examples of ultraviolet scattering agents include metal oxides such as low-order titanium oxide, zinc oxide and cerium oxide, metal hydroxides such as iron hydroxide, metal flakes such as plate-like iron oxide and aluminum flakes, silicon carbide And powders of ceramics and the like. These powders are conventionally known surface treatments, for example, fluorine compound treatment (perfluoroalkyl phosphate treatment or perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment is preferred), Silicone treatment (methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, vapor phase tetramethyltetrahydrogencyclotetrasiloxane treatment is preferred), silicone resin treatment (trimethylsiloxysilicate treatment is preferred), pendant treatment (vapor phase method) A method of adding an alkyl chain or the like after the silicone treatment), a silane coupling agent, a titanium coupling agent treatment, a silane treatment (preferably an alkylsilane or an alkylsilazane treatment), an oil agent treatment, an N-acylated lysine treatment, It is preferable that the surface treatment is carried out by reacrylic acid treatment, metal soap treatment (preferably stearic acid or myristic acid salt), acrylic resin treatment, metal oxide treatment, etc., and more preferably these treatments are used in combination. Is preferred. For example, the surface of fine particle titanium oxide is coated with a metal oxide such as silane or alumina, and then surface-treated with alkylsilane. In addition, it is preferable that these powders having an ultraviolet protection effect have been subjected to water repellency treatment with an organosilicon compound. Examples of the organosilicon compound include silane coupling agents and silicone resins among the above treatment agents.

  Of these, preferable as ultraviolet absorbers are 2-ethylhexyl paramethoxycinnamate and hexyl 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoate, and preferable as a UV scattering agent is silicone-treated oxidation. Titanium, silicone-treated zinc oxide, methylhydrogenpolysiloxane-treated or octylsilyl-treated titanium oxide and zinc oxide.

  As the component (H), the ultraviolet protective agent can be used alone or in combination of two or more. The content of the ultraviolet protective agent of component (H) is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 8% by mass or less in the total composition from the viewpoint of stability.

Other ingredients:
The water-in-oil emulsified cosmetic of the present invention adjusts the skin feeling and improves the storage stability of the cosmetic, as long as the effects of the present invention are not affected, in addition to the components (A) to (H). For the purpose of making it, an oily component can be contained.
Examples of the oil component include mineral oil, vegetable oil, ester oil, low viscosity silicone oil other than components (B) and (C), and tocopherol. Specific examples of mineral oil include liquid paraffin, dodecane, polybutylene, polyisobutylene, and specific examples of vegetable oil include rapeseed oil, linseed oil, cottonseed oil, soybean oil, tea seed oil, rice bran oil, tung oil, and the like. Specific examples of low-viscosity silicone oils include dimethyl silicone oil having a viscosity of 6 cs (Silicone KF-96A-6cs, manufactured by Shin-Etsu Chemical Co., Ltd.), (dimethicone / vinyl dimethicone) crosspolymer (25% dimethicone 6cs dispersion) ( KSG-16, manufactured by Shin-Etsu Chemical Co., Ltd.).

  Moreover, you may mix | blend various other arbitrary components used for cosmetics, a pharmaceutical, etc. according to the objective in the range which does not affect the effect of this invention. Examples include humectants, powders, thickeners, thickeners, other surfactants, emulsifiers, flame retardants, antioxidants, pH adjusters, chelating agents, preservatives, dyes, fragrances, collagen, and the like. .

  Examples of the product form of the water-in-oil emulsified cosmetic of the present invention include gels, emulsions, creams, ointments and the like.

  When performing skin care using the water-in-oil emulsified cosmetic of the present invention, the water-in-oil emulsified cosmetic of the present invention may be used and held on the skin. Furthermore, when the water-in-oil emulsified cosmetic composition of the present invention is used on the skin, the emulsified cosmetic composition is immediately demulsified to form a refreshing film that is not sticky on the skin surface, and has an isolation effect on external stimuli. Is effective.

Example 1 and Comparative Examples 1-8
According to the following manufacturing method, the water-in-oil type emulsified cosmetics of Example 1 and Comparative Examples 1 to 8 having the compositions shown in Table 2 are manufactured, and have an isolation effect against external stimuli, storage stability, and spread at the time of application. Goodness, feel after application and drying, and refreshing feeling were evaluated. The results are shown in Table 1.

(Production method)
Components (A) to (D) are designated as phase I (oil phase) components, and component (E) is designated as phase II (water phase) component. Ingredients of Phase I were mixed uniformly at room temperature with propeller stirring (500 rpm) at room temperature, and dissolved and mixed Phase II was slowly added with stirring to emulsify, 300 g of water-in-oil emulsified cosmetic. Manufactured.

(Evaluation methods and standards)
Based on the following methods and criteria, the water-in-oil emulsified cosmetic is evaluated for its isolation effect against external stimuli, storage stability, good spreadability during application, feel after application and dryness, and refreshment.

(I) Evaluation of isolation effects on external stimuli:
The isolation effect against external stimuli is evaluated using contact angle, occlusion and dirt adhesion measurement. The specific evaluation method is as follows.
(A) Contact angle:
(1) Prepare artificial leather with an area of 5cm x 4cm (supplera / Idemitsu).
(2) Apply 0.04 mL of cosmetic material uniformly to the artificial leather and dry it indoors overnight.
(3) Install the artificial leather horizontally. Further, a camera is installed on the horizontal line of the artificial leather, and the horizontal surface of the dried sample on the artificial leather can be photographed by adjusting the height and distance of the camera.
(4) Using a microsyringe, 5 μL of pure water (water droplets) is slowly dropped onto the coated surface of the artificial leather on the dry sample surface.
(5) Take a picture after standing for 5 minutes.
(6) The contact angle θ is calculated from the photograph of the obtained water droplet using the following formula.
As the contact angle is larger, the wettability is lower and the external stimulus component is less likely to spread, which means that the isolation effect is higher.

(B) Occlusion:
Occlusion is measured by the cup method. That is, in a 40 mL vial bottle (Pierce vial CV-400 (manufactured by ASONE); a hole having a diameter of 17.3 mm is formed in the lid), φ = 22.0 mm Glass Microfiber Filter (Whatman GF / C) is placed on the bottle. Place on top and cover. The emulsified cosmetic 0.05 g was applied to the exposed filter part and dried for one day. Thereafter, 25 mL of water was added, and after standing for 3 days at 20 ° C. and a humidity of 40% (in a state where there was no mass fluctuation of the sample), the mass was measured (M1), and the mass after 24 hours was further measured (M2). The amount of water transpiration was determined from the equation.
Moisture transpiration (g) = M1-M2

Further, Placebo (water) was used instead of the emulsified cosmetic, and the amount of water transpiration was determined by the same treatment as above, and the obstructive property (%) was determined by the following formula. The higher the occlusion property, the higher the uniform film forming ability and the greater the isolation effect against external stimuli.
Occlusion property (%) = [1- (moisture transpiration of emulsified cosmetic / water transpiration of Placebo treatment)] × 100

(C) Dirt adhesion measurement:
Using 煤 as a model for air pollutants, the adhesion is examined using a dirt chamber.
(1) Prepare 5cm x 4cm white artificial leather (supplera, manufactured by Idemitsu).
(2) Uniformly apply 0.02 g of model sebum (model sebum composition is as shown in Table 1).

(3) Uniformly apply 0.04 mL of cosmetic material to the whole artificial leather.
(4) Dry overnight.
(5) The L * a * b * value is measured with a color difference meter (D-2500d, manufactured by Olympus).
(6) Prepare a dirt chamber (65 × 40 × 40 cm box type / with circulation fan (manufactured by Kao)) (FIG. 1).
(7) In the center of the chamber, install artificial leather coated with cosmetics according to the height of the exhaust port.
(8) Install a filter paper soaked in kerosene (φ = 22.0 mm Glass Microfiber Filter (Whatman GF / C)) in the combustion chamber and ignite.
(9) Circulate the smoke with a fan, leave it for 5 minutes, and then remove the artificial leather.
(10) Repeat this operation 5 times.
(11) After (10), a sample is taken out, L * a * b * value is measured by a color difference meter, and ΔE is obtained.
It means that the smaller the ΔE, the greater the effect of suppressing the adhesion of dirt, and the greater the effect of isolating against external stimuli.

(II) Evaluation for storage stability:
Each cosmetic is placed in a glass bottle (height 9.5 cm, inner diameter 4.5 cm), stored at 50 ° C. for 1 month, 2 weeks a day for 2 weeks and a temperature cycle of 40 ° C. to −30 ° C. for 2 weeks. And evaluated according to the following criteria.
(Evaluation criteria)
A: No change.
○: There is a slight change, but there is no division and there is no problem as a product.
Δ: Slightly divided.
X: Completely separated.

(III) Evaluation of good spread during application, feel after application and drying, and refreshing feeling:
Ten professional panelists apply and hold 0.2 g of each cosmetic on the face. The following criteria (1), criteria (2), and criteria (3) are used to evaluate the goodness of spreading at the time of application, the feel after application and drying, and the refreshing feeling. An average score is obtained from the evaluation of 10 professional panelists, and 3.6 or more is evaluated as ◎, 2.6 to less than 3.6 is evaluated as ◯, 1.6 to less than 2.6 is evaluated as Δ, and less than 1.6 is evaluated as ×.

Evaluation criteria (1)
4; It is very easy to extend.
3; Easy to extend.
2; It is easy to extend a little.
1; Hard to stretch.

Evaluation criteria (2)
4; There is no film residual feeling.
3: There is almost no residual film.
2; There is a little residual film.
1: There is a film residual feeling.

Evaluation criteria (3)
4; Very refreshing.
3; It is refreshing.
2; A little refreshing.
1; not refreshing.

  As is clear from the results in Table 2, the water-in-oil emulsified cosmetic of the present invention has a contact angle, occlusiveness, and dirt adhesion measurement as compared with those of Comparative Examples 1 to 8. Excellent results, excellent isolation effect against external stimuli, easy to spread during application, excellent film feel after coating and drying, and also achieves both storage stability and refreshing feeling. I understood it.

Examples 2-8
According to the production method of Example 1, water-in-oil type emulsified cosmetics of Examples 2 to 8 having the compositions shown in Table 3 were produced with a homomixer under stirring conditions of 4000 rpm, 7000 rpm, and 10,000 rpm. The aqueous phase separation after production and the rate of change in viscosity over time were evaluated. The results are shown in Table 3.

(Evaluation methods and standards)
Based on the following methods and criteria, the water phase separation after production of the water-in-oil emulsified cosmetic and the rate of change in viscosity over time are evaluated.

(IV) Aqueous phase separation after production (after shearing by stirring):
Each cosmetic is stirred with a propeller / homomixer to produce a cosmetic. The state of the cosmetic after production is visually observed and evaluated according to the following criteria.
(Evaluation criteria)
○: Not separated.
X: Separated.

(V) Viscosity change rate with time after production:
The cosmetics immediately after production are put into a glass bottle (height 9.5 cm, inner diameter 4.5 cm), and at 25 ° C., a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., BM type or TV-10 type), speed of 6 rpm The viscosity was measured. After the cosmetic was stored at room temperature for 1 month, the viscosity was measured again under the same conditions as described above, and the rate of change in viscosity over time was determined by the following formula. It means that the change in viscosity with time increases as the rate of change increases from 1.
Viscosity change rate with time = viscosity immediately after preparation / viscosity after 1 month storage at room temperature

  As is apparent from the results in Table 3, when a surfactant containing a silicone chain of less than HLB8 of component (F) is blended with the water-in-oil emulsified cosmetic of the present invention, water is used even if a homomixer is used. Phase separation was suppressed, and when the inorganic salt of component (G) was further blended, changes in viscosity with time were suppressed.

Examples 9-11 and Comparative Examples 9-11
According to the production method of Example 1, water-in-oil emulsified cosmetics of Examples 9 to 11 and Comparative Examples 9 to 11 having the compositions shown in Table 4 were produced, and SPF values of the cosmetics were measured. The results are shown in Table 4.

(Measuring method)
Based on the following method, the SPF value of the water-in-oil emulsified cosmetic was measured.
Each cosmetic is uniformly applied to a surgical tape on a quartz glass plate to 2 mg / cm ² , left to dry for 20 minutes or longer, and then dried using an SPF analyzer (Optometrics) to determine the SPF value of the cosmetic. It was measured.

  As is clear from the results in Table 4, the water-in-oil emulsified cosmetic of the present invention was able to form an excellent film and obtain a more excellent UV protection effect.

Examples 12-30
According to the production method of Example 1, the water-in-oil emulsified cosmetics of Examples 12 to 27 having the composition shown in Table 5 and Example 28 (moisturizing serum), Example 29 (sunscreen), and Example 30 (Balm cream) was produced.

  All of the water-in-oil emulsified cosmetics obtained in Examples 12 to 30 have good storage stability, a good feel during application and after application, a refreshing feeling, and an excellent isolation effect against external stimuli. It is a thing.

Claims (10)

The following components (A) to (E):
(A) Silicone elastomer 0.5-10 mass%,
The silicone elastomer has the following general formula (a-1):
R ¹ _a R ² _b H _c SiO _{(4-abc) / 2} (a-1)
And / or the following general formula (a-2):
R ¹ _j H _k SiO _{(4-jk) / 2} (a-2)
An organohydrogenpolysiloxane represented by:
The following general formula (a-3):
_{C m H 2m-1 O (} C 2 H 4 O) p (C 3 H 6 O) q C m H 2m-1 (a-3)
And / or the following general formula (a-4):
R ¹ _d R ³ _e SiO _{(4-de) / 2} (a-4)
A silicone elastomer having the component represented by the general formula (a-1) and / or the general formula (a-3) as an essential component, which is obtained by addition polymerization with an organopolysiloxane represented by the formula:
(In the formula, R ¹ is a substituted or unsubstituted alkyl group or aryl group each monovalent 1-18 carbon atoms, an aralkyl group or a halogenated hydrocarbon group having same or different, R ² is Formula - _{C n H 2n O (C 2} H 4 O) f (C 3 H 6 O) g R an organic group represented by ^4, R ³ is a monovalent hydrocarbon group having 2 to 10 carbon atoms having a terminal vinyl group, R ⁴ is a hydrogen atom, a saturated organic group having 1 to 10 carbon atoms or a group represented by R ⁵ — (CO) —, R ⁵ is a saturated organic group having 1 to ⁵ carbon atoms,
a, b, c, d, e, j and k are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1, 0.001 ≦ c ≦ 1, 1.0 ≦ d ≦ 3.0, respectively. 0.001 ≦ e ≦ 1.5, 1.0 ≦ j ≦ 3.0 and 0.001 ≦ k ≦ 1.5, f and p are integers of 2 to 200, and g and q are 0 to 200. ), F + g is 3 to 200, p + q is 3 to 200, and m and n are 2 to 6)
(B) 0.2-10 mass% of dimethylpolysiloxane whose degree of polymerization is 350 or more and 1500 or less,
(C) dimethylpolysiloxane and / or decamethylcyclopentasiloxane having a degree of polymerization of 1 or more and 6 or less, 3 to 28% by mass,
(D) 0.5-25% by mass of ethyl alcohol,
(E) A water-in-oil emulsified cosmetic containing water.   The mass ratio (A) / ((A) + (B) + (C)) of the content of component (A) and the total content of component (A), component (B) and component (C) is: It is 0.03-0.27, The water-in-oil type emulsified cosmetics of Claim 1 characterized by the above-mentioned.   The water-in-oil according to claim 1 or 2, wherein the silicone elastomer of component (A) is selected from (dimethicone / (PEG-10 / 15)) crosspolymer and (PEG-15 / lauryl dimethicone) crosspolymer. Type emulsified cosmetic.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the degree of polymerization of the component (B) dimethylpolysiloxane is 600 or more and 1500 or less.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 4, wherein the degree of polymerization of the component (B) dimethylpolysiloxane is 600 or more and 800 or less.   Content in a water-in-oil type emulsified cosmetics of a component (E) is 30-90 mass%, The water-in-oil type emulsified cosmetics of any one of Claims 1-5.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 6, further comprising (F) a surfactant containing a silicone chain having an HLB value of less than 8.   Furthermore, the water-in-oil type emulsified cosmetics of any one of Claims 1-7 containing (G) inorganic salt.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 8, further comprising (H) an ultraviolet protective agent.   A skin care method comprising using and holding the water-in-oil emulsified cosmetic according to any one of claims 1 to 9 on the skin.