JP5066372B2 - Aqueous two-layer cosmetic - Google Patents

Description

  The present invention relates to an aqueous two-layer separated cosmetic.

  The water-based two-layer separated cosmetic containing powder is characterized by separating into two layers of a transparent layer and a powder layer when allowed to stand, and showing a beautiful appearance. It has a fresh and refreshing feeling when applied.

  However, the two-layer separation type cosmetic containing such a powder has a problem that the powder is fixed during long-term storage and easily causes “caking” that cannot be easily redispersed even when shaken during use. There is. For this reason, various proposals have been made to solve this problem in powder-containing water-based two-layer separated cosmetics, for example, a mixture of hydrophobic powder and volatile oil and / or ester oil. (See Patent Document 1), gellan gum and powder (see Patent Document 2), water-swellable clay mineral, powder, electrolyte (see Patent Document 3), and a large amount of ethanol In addition, oil agents, phospholipids, alkylmethyl taurate salts, water-soluble polymers, electrolytes, powders (see Patent Document 4), and the like have been proposed. However, none of the techniques is sufficiently satisfactory in preventing the caking and improving the redispersibility.

  In addition, in order to improve the water and oil repellency of the coating film formed on the skin by application, fluorine oils are also added or the powder is hydrophobized. It is difficult to blend in an appropriate amount, and there are also problems such as poor water and oil repellency of the coating film, and the coating film after coating becomes bulky.

JP 7-267843 A JP 2002-249417 A JP 2003-277229 A Japanese Patent Laid-Open No. 2004-2283

  Therefore, the present invention is excellent in redispersibility without causing caking even when stored for a long period of time, quickly separating into two layers upon standing, presenting a beautiful appearance, giving the skin a refreshing and fresh feel, and repelling the coating film. An object of the present invention is to provide a water-based two-layer separated cosmetic that is excellent in water and oil repellency.

  The present inventors use a combination of a powder coated with an acrylic-silicone graft copolymer and a fluorinated oil agent to form oil droplets in which the coated powder is oriented at the interface of the fluorinated oil agent, It can be separated into two layers promptly upon standing, and an aqueous two-layer separation type cosmetic can be obtained that can be easily redispersed by lightly shaking without causing caking even after long-term storage. It has been found that when applied to the skin, a fresh refreshing feeling can be obtained and a coating film having excellent water and oil repellency can be formed.

The present invention provides an aqueous two-layer separated cosmetic containing components (A) to (D).
(A) Powder coated with acrylic-silicone graft copolymer (B) Fluorine oil (C) Water (D) Ethanol

  The aqueous two-layer separated cosmetic of the present invention does not cause caking over time, has excellent redispersibility, has a beautiful appearance, and is excellent in refreshing feeling, water and oil repellency, and moist feeling.

  In the powder coated with the acrylic-silicone graft copolymer of component (A), examples of the acryl-silicone graft copolymer for coating the powder include, for example, An organopolysiloxane compound (a1) having a radically polymerizable group at one end of a molecular chain and a radically polymerizable monomer (a2) mainly composed of acrylate and / or methacrylate described in JP-A-4-342513. Examples include copolymers obtained by polymerization.

  The organopolysiloxane compound (a1) having a radical polymerizable group at one end of a molecular chain used for the production of the acrylic-silicone graft copolymer is represented by, for example, the following general formula (1) ( And (meth) acrylate-substituted organopolysiloxane.

[Wherein, R ¹ represents a methyl group or a hydrogen atom, R ² represents a linear or branched divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be blocked by an ether bond, and a Indicates a number from 3 to 300. ]

In the general formula (1), specific examples of R ² include methylene, trimethylene, 2-methyltrimethylene, hexamethylene, octamethylene, decamethylene, —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH (CH ₃ ) CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — and the like can be mentioned. Moreover, as a, 5-100 are preferable.

  The (meth) acrylate-substituted organopolysiloxane can be synthesized, for example, by subjecting a (meth) acrylate-substituted chlorosilane compound and a terminal hydroxyl group-substituted dimethylpolysiloxane to a dehydrochlorination reaction according to a conventional method.

  The radical polymerizable monomer (a2) mainly composed of acrylate and / or methacrylate is preferably an alkyl (meth) acrylate having 1 to 30 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl. Alkyl (meth) acrylates such as (meth) acrylate and 2-ethylhexyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Examples thereof include (meth) acrylate having 10 perfluoroalkyl.

  In addition to the above acrylate and / or methacrylate, various polymerizable monomers can be used in combination with the radical polymerizable monomer (a2) as necessary. These polymerizable monomers include styrene, substituted styrene, vinyl acetate, (meth) acrylic acid, maleic anhydride, maleic ester, fumaric ester, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluoride. An olefin etc. can be illustrated.

  In the radical polymerizable monomer (a2), the ratio of acrylate and / or methacrylate is preferably 50% by mass or more based on the total amount of the radical polymerizable monomer in terms of prevention of stickiness of the resulting coated powder.

  The polymerization ratio (molar ratio) between the dimethylpolysiloxane compound (a1) having a radical polymerizable group at one end of the molecular chain and the radical polymerizable monomer (a2) mainly composed of acrylate and / or methacrylate is the component (A). From the viewpoint of sufficient water resistance and stickiness prevention of the coated powder of (a1) / (a2) = 1/19 to 1/1.

  Copolymerization of a dimethylpolysiloxane compound (a1) having a radically polymerizable group at one end of the molecular chain with a radically polymerizable monomer (a2) mainly composed of acrylate and / or methacrylate is carried out by benzoyl peroxide or lauroyl peroxide. , Can be carried out in the presence of a normal radical polymerization initiator such as azobisisobutyronitrile, and any of the solution polymerization method, emulsion polymerization method, suspension polymerization method and bulk polymerization method can be applied. . Among these, the solution polymerization method is a more preferable method because it is easy to adjust the molecular weight of the obtained graft copolymer to the optimum range. Solvents used include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and isobutyl acetate, and alcohols such as isopropanol and butanol, or 2 A mixture of seeds or more can be mentioned.

  The polymerization reaction can be usually carried out within a temperature range of 50 to 180 ° C., preferably 60 to 120 ° C., and can be completed in about 5 to 10 hours under these conditions. The acrylic-silicone graft copolymer thus produced preferably has a polystyrene-reduced weight average molecular weight in GPC in the range of about 3,000 to about 200,000, particularly about 5,000 to about 100,000, and −30 It preferably has a glass transition temperature in the range of ~ + 60 ° C.

  The acrylic-silicone graft copolymer obtained as described above is specifically known as Acrylates / Dimethicone Copolymer under the INCI name, and further, methyl methacrylate / butyl methacrylate / 2-ethylhexyl. Examples include acrylate / methyl polysiloxane alkyl acrylate.

  The powder coated with such an acrylic-silicone graft copolymer is not particularly limited as long as it is usually used in cosmetics, and inorganic powder, organic powder, pearl agent, and the like can be used. . Specific examples include talc, mica, kaolin, titanium oxide, aluminum silicate, anhydrous silicic acid, zinc oxide, calcium carbonate, magnesium carbonate, bengara, yellow iron oxide, black iron oxide, ultramarine, mica titanium, aluminum oxide, oxy Examples thereof include bismuth chloride, iron oxide mica, polyethylene, polystyrene, cellulose, nylon, acrylic, Teflon (registered trademark), and silk powder. These can be used alone or in combination of two or more.

  The coated powder of component (A) is produced by coating these powders with an acrylic-silicone graft copolymer. For example, a fluidized bed coating method, an acrylic-silicone graft copolymer in a volatile solvent. Is mixed with the powder to form a mixed dispersion slurry, which can be coated by a method of heating the mixture under reduced pressure to distill off the solvent.

  The volatile solvent used here is not particularly limited as long as it can uniformly dissolve the acrylic-silicone graft copolymer. For example, aromatic hydrocarbons such as benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone. Ketones such as ethyl acetate, esters such as isobutyl acetate, alcohols such as isopropanol and butanol, volatile silicone oils such as decamethylcyclopentasiloxane, and the like. These may be used alone or in combination of two or more. Can be used. Furthermore, a plasticizer, an activator, an oil agent, etc. can be used in the range which does not prevent the effect of this invention other than an acryl-silicone type graft copolymer in the case of a coating process.

  The powder surface of the coating powder of component (A) is preferably coated with an acrylic-silicone graft copolymer of 0.5 to 30% by mass, particularly 1 to 15% by mass of the powder mass.

  The content of the component (A) is preferably 2 to 30% by mass, more preferably 5 to 20% by mass, and particularly preferably 7 to 15% by mass of the cosmetic of the present invention from the viewpoint of redispersibility and usability.

  Preferred examples of the component (B) fluorine-based oil include fluorine-modified silicone and perfluoropolyether.

  Specifically, examples of the fluorine-modified silicone include those having one or more structural units represented by the following general formulas (2) to (5) and a structural unit represented by the following general formula (6). Can be mentioned.

[Wherein R ^f1 and R ^f2 are each independently a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms, or H (CF ₂ ) _h — (h is an integer of 1 to 20 R ³ , R ^6, and R ⁷ are each independently a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a ω-H-perfluoroalkyl group represented by Represents an alicyclic or aromatic hydrocarbon group having 5 to 10 carbon atoms; R ⁴ represents a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aliphatic group having 5 to 10 carbon atoms. cyclic or aromatic hydrocarbon group, a perfluoroalkyl group or the formula _H (CF _{2) h} having 1 to 20 carbon atoms - indicates in omega-H- perfluoroalkyl group represented; R ⁵ is the number of carbon atoms It shows a 2-6 divalent hydrocarbon radical; X ¹ and Y ¹ represents a single bond, -CO- or a divalent hydrocarbon group having 1 to 6 carbon atoms; b is a number of 2 to 16 And each c and d is a number of 1 to 16, e represents a number of 0 to 20, f represents a number of 1 to 200, g is a number of 0 to 200]

In the structural units represented by the general formulas (2) to (5), as the perfluoroalkyl group represented by R ^f1 and R ^f2 , both linear and branched ones can be used. _{3 -, C 2 F 5 -} , C 4 F 9 -, C 6 F 13 -, C 8 F 17 -, C 10 F 21 -, H (CF 2) 2 -, H (CF 2) 4 -, H _{(CF 2) 6 -, H} (CF 2) 8 - , and the like can be given _{-, (C 3 F 7)} C (CF 3) 2. Moreover, _H (CF _{2) h} - as h in the 6 to 20 is preferably an integer of.

Examples of the hydrocarbon group represented by R ³ , R ⁶ and R ⁷ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl groups. Chain alkyl group; branched chain alkyl group such as isopropyl group, s-butyl group, t-butyl group, neopentyl group, 1-ethylpropyl group, 2-ethylhexyl group; cyclic alkyl group such as cyclopentyl group, cyclohexyl group; phenyl group And aromatic hydrocarbon groups such as a naphthyl group. Moreover, as a bivalent hydrocarbon group shown by R < ⁵ >, a C2-C4 linear or branched alkylene group is preferable, and especially ethylene group and a propylene group are preferable.

  As the fluorine-modified silicone having such a structural unit, for example, the following general formula (7)

[In the formula, at least one of Z ¹ and Z ² represents a structural unit selected from the general formulas (2), (3), (4) and (5), the remainder represents a single bond, g, R ⁶ And R ⁷ has the same meaning as described above.
Represented by the following general formula (8)

[Wherein Z ³ represents a structural unit selected from the general formulas (2), (3), (4) and (5), and R ⁸ represents a linear or branched aliphatic group having 1 to 20 carbon atoms. A hydrocarbon group or an alicyclic or aromatic hydrocarbon group having 5 to 10 carbon atoms, i represents a number from 0 to 200, and g, R ⁶ and R ⁷ have the same meaning as described above.]
Can be mentioned.

The structural units represented by the general formulas (2) to (5) and the groups in the respective formulas in the fluorine-modified silicones represented by the general formulas (7) and (8) are considered in terms of prevention of cosmetic collapse and usability. In this case, the following are preferable. R ^f1 and R ^f2 are represented by a linear or branched perfluoroalkyl group having 6 to 20 carbon atoms or the following formula; H (CF ₂ ) _h1 — (h ¹ represents an integer of 6 to 20). The ω-H-perfluoroalkyl group is preferred. R ³ , R ⁶ and R ⁷ may be the same or different and are preferably a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms. R ⁴ is preferably a hydrogen atom, a C 6-20 perfluoroalkyl group, or an ω-H-perfluoroalkyl group represented by the formula H (CF ₂ ) _h1 —. R ⁶ is preferably a divalent hydrocarbon group having 2 to 4 carbon atoms. X ¹ and Y ¹ are preferably a single bond, —CO— or a divalent hydrocarbon group having 1 to 4 carbon atoms, b is preferably 2 to 10, particularly 2 to 5, and c and d are each 2-10, especially 1-6 are preferred, e is 0-20, especially 0-5, f is preferably 1-100, especially 1-10, g is 0-100, especially A number from 0 to 10 is preferred. The arrangement of the structural units of the fluorine-modified silicone represented by the general formula (8) may be alternating, block, or random.

  Preferred examples of the fluorine-modified silicone include a structural unit represented by the general formula (3) and a structural unit represented by the general formula (6). 200 fluorine-modified silicones, fluorine-modified silicones described in JP-A-6-184312, commercially available products FSL-300, FSL-400 from Asahi Glass Co., Ltd. X-22-819, X-22-820, X from Shin-Etsu Chemical Co., Ltd. -22-821, X-22-822 and FL-100, and FS1265 manufactured by Toray Dow Corning.

  Further, as perfluoropolyether, for example, the following general formula (9)

[Wherein R ⁹ , R ¹¹ , R ¹² and R ¹³ may be the same or different and each represents a fluorine atom, a perfluoroalkyl group or a perfluoroalkyloxy group, and R ¹⁰ represents a fluorine atom or a perfluoroalkyl group. And j, k, and l represent a number of 0 or more with a molecular weight of 500 to 100,000. However, j = k = l = 0 does not occur. ]
Can be mentioned. In the general formula (9), the perfluoro groups shown in parentheses need not be arranged in this order, and may be random or block polymerization. As for carbon number of a perfluoroalkyl group and a perfluoroalkyloxy group, 1-4 are preferable.

The perfluoropolyether, among those represented by the general formula (9), a viscosity of 5 to 5000 mm ² / s, in particular those of 5~1000mm ² / s like liquid preferably, for example, the following general formula (10 )

[In formula, m and n show the number from which an average molecular weight will be 500-100,000, and m / n is 0.2-2. ]
FOMBLIN HC-04 (average molecular weight 1500), HC-25 (3200), HC-R (6600) (above, Augmont), represented by the following general formula (11)

[In formula, o shows the number of 4-500. ]
Demnam S-20 (mass average molecular weight 25000), S-65 (4500), S-100 (5600), S-200 (8400) (above, Daikin Industries) be able to.

  The content of the component (B) fluorinated oil is preferably 5 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 10 to 35% by mass in the cosmetic of the present invention.

  The water content of the component (C) is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and particularly preferably 30 to 65% by mass in the cosmetic of the present invention.

  The content of the component (D) ethanol is preferably 5 to 20% by mass, more preferably 8 to 18% by mass, especially 10 to 15% by mass in the cosmetic of the present invention, from the viewpoint of redispersibility and refreshing feeling. Is preferred.

  The cosmetic composition of the present invention may further contain a small amount of surfactant, but from the viewpoint of high water repellency, it is 0.1% by mass or less, and further 0.05% by mass or less. It is preferable not to contain.

  The cosmetic of the present invention may further contain a salt. In particular, when fluorine-modified silicone is used as the component (B), it is preferable to contain a salt from the viewpoint of redispersibility and a beautiful appearance. Examples of the salt include inorganic salts such as magnesium sulfate, sodium sulfate, sodium chloride, magnesium chloride, calcium chloride and sodium phosphate, and organic acid salts such as sodium citrate, sodium lactate and sodium succinate. The salt content is preferably 0.01 to 1% by mass, more preferably 0.1 to 1% by mass, and particularly preferably 0.5 to 1% by mass.

  In addition to the above components, the cosmetics of the present invention can be blended with components that are blended in ordinary cosmetics depending on the purpose. For example, water-soluble polymers such as hydroxyethylcellulose, methylcellulose and carboxyvinyl polymer; moisturizers such as 1,3-butylene glycol, glycerin and sorbitol; other colorants such as organic dyes, preservatives, antioxidants, thickeners An agent, a pH adjuster, a fragrance, an ultraviolet absorber, a blood circulation promoter, a cooling agent, an antiperspirant, a disinfectant, a skin activator, and the like can be blended.

  The aqueous two-layer separated cosmetic of the present invention is obtained by mixing and dispersing the coating powder of component (A), the fluorinated oil of component (B), and ethanol of component (D) from the viewpoint of prevention of caking and redispersibility. It is preferable to produce by adding and mixing water of component (C). By doing in this way, the oil droplet in which the coating powder orientated can be formed in the interface of a fluorine-type oil agent.

Examples 1-8 and Comparative Examples 1-5
A liquid foundation having the composition shown in Table 1 was prepared and evaluated.
(Production method)
1. Using a disper, ethanol [component (D)] and oil agent [component (B), squalane, chain dimethylpolysiloxane] and a salt are uniformly mixed.
2. Add powder [component (A), silicone-treated powder, untreated powder] to 2.1 and disperse uniformly.
Add purified water (component (C)) and water-soluble components to 3.2 and mix.

(Evaluation method)
・ Beauty of appearance after use and after use Lightly shake cosmetics up and down, and the appearance after standing for one day was judged according to the following criteria.
：: Dispersed uniformly when shaken, and after standing, the upper layer was a transparent water layer, and the lower layer was formed into two layers in which oil and powder were granulated and dispersed.
○: Dispersed uniformly when shaken, and after standing, the upper layer was a transparent water layer, and the lower layer was formed into two layers in which oil and powder became coarse granules and dispersed.
X: When shaken, the mixed layer of oil and powder was dispersed as droplets, and after standing, the upper layer was separated into a transparent aqueous phase, and the mixed layer of oil and powder was combined with the lower layer.

-Storage stability After leaving the cosmetic at room temperature for half a year, the appearance when the cosmetic was shaken lightly up and down was judged according to the following criteria.
A: Dispersed uniformly by shaking within 10 times.
○: Uniformly dispersed by shaking 11-25 times.
X: It is not uniformly dispersed by shaking within 25 times.

・ Usage
Ten professional panelists used the cosmetics to make a sensory evaluation of the “cool feeling” and judged the following criteria.
○: Seven or more people evaluated it as good.
(Triangle | delta): Four to six persons evaluated it as favorable.
X: Three or less people evaluated it as favorable.

-Water repellency Cosmetics are evenly applied to an artificial leather sheet made of polyurethane at 3 mg / cm ² and dried at room temperature for 2 hours. Thereafter, ion-exchanged water was dropped from the tip of the microsyringe onto the sample surface, the contact angle after 1 minute was measured, and judged according to the following criteria.
◎: Contact angle 90 ° or more ○: Contact angle 70 to less than 90 ° △: Contact angle 40 to less than 70 ° ×: Contact angle less than 40 °

・ Oil repellency Cosmetics are evenly applied to polyurethane artificial leather sheet at 3mg / cm ² and dried at room temperature for 2 hours. Thereafter, squalane was dropped from the tip of the microsyringe onto the sample surface, the contact angle after 1 minute was measured, and the determination was made according to the following criteria.
◎: Contact angle 50 ° or more ○: Contact angle 30 to less than 50 ° △: Contact angle 10 to less than 30 ° ×: Contact angle less than 10 °

Example 9
A makeup base having the composition shown in Table 2 was prepared and evaluated according to the same method and criteria as described above. The results are shown in Table 2.

Claims (3)

An aqueous two-layer separated cosmetic containing components (A) to (D) and no surfactant .
(A) Acrylic polymer obtained by copolymerizing (meth) acrylate-substituted organopolysiloxane (a1) represented by the following general formula (1) and alkyl (meth) acrylate (a2) having 1 to 30 carbon atoms Powder coated with silicone-based graft copolymer : 2 to 15% by mass

[Wherein, R ¹ represents a methyl group or a hydrogen atom, R ² represents a linear or branched divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be blocked by an ether bond, and a Indicates a number from 3 to 300. ]
(B) Fluorine- based oil selected from fluorine-modified silicone and perfluoropolyether : 10 to 40% by mass
(C) Water : 30-65% by mass
(D) Ethanol : 5-15% by mass Furthermore, aqueous two-layer separation type cosmetic composition of claim 1, wherein those containing salt 0.01% by mass. The aqueous two-layer separated cosmetic according to claim 1 or 2, which is produced by adding and mixing the component (C) after mixing and dispersing the components (A), (B) and (D).