JP5956837B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

  The present invention relates to a water-in-oil emulsified cosmetic.

Conventionally, in order to obtain a cosmetic with excellent makeup durability, use of various water / oil repellency compounds has been studied.
For example, Patent Document 1 describes a cosmetic containing a fluorine-modified silicone resin having a silanol group in the molecule and having a specific structure, is difficult to collapse, has high water resistance, and has a long-lasting cosmetic effect. It has been proposed to be superior.

Japanese Patent Laid-Open No. 9-12431

The present inventor has found that the cosmetic described in Patent Document 1 is uniform in the skin dermis when the texture is rough and the skin has rough texture with aging, etc. It has been found that there is a problem in that it cannot be adhered to the surface, resulting in uneven color and a natural finish cannot be obtained.
An object of the present invention is to provide a cosmetic that can be uniformly adhered to the skin, does not cause color unevenness, and has a natural finish.

  The inventor has solved the above problems by using a combination of a specific fluorine-modified silicone resin, a specific fluorine compound-treated powder, and a specific poly (N-acylalkyleneimine) -modified organopolysiloxane. It has been found that an emulsified cosmetic can be obtained.

The present invention includes the following components (A), (B) and (C):
(A) The following general formula (1)
R ¹ _a SiO _{(4-a) / 2} (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ² —Rf (R ² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8, which is arbitrarily selected from a functional group having a hydroxyl group and a general formula —R ² —Rf as essential, and a is an average number of 1.0 ≦ a ≦ 1. 8)
0.01 to 10% by mass of a fluorine-modified silicone resin having a structure represented by
(B) Powder surface-treated with tridecafluorooctyltriethoxysilane,
(C) At least two silicon atoms of the organopolysiloxane segment constituting the main chain, via an alkylene group containing a hetero atom, the following general formula (2);

(Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3)
An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 4000,
The mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is 80/20 to 98/2,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 10,000 to 40,000,
It contains an organopolysiloxane having a weight average molecular weight of 50,000 to 170000, and the mass ratio of components (A) and (C) is (A) / (C) = 0.01. The water-in-oil emulsified cosmetic composition of 10 to 10 is provided.

  The water-in-oil emulsified cosmetic of the present invention can be uniformly adhered to the skin, suppresses color unevenness, and provides a natural finish. In particular, in the case of skin with a rough texture due to aging or the like, the cosmetics are difficult to adhere to the smooth skin and difficult to uniformly apply, but the water-in-oil emulsion makeup of the present invention Even in such a case, the material can uniformly adhere to the crevice and the cuticle. In addition, sliding during application is good.

The component (A) fluorine-modified silicone resin used in the present invention has a structure represented by the general formula (1).
The fluorine-modified silicone resin has a silanol group in the molecule from the viewpoint of adhesion to skin and powder, and the ratio of the OH group in the silanol group is 0.1 to 5% by mass with respect to the resin mass. Of 0.5 to 5% by mass is more preferable.

  The fluorine-modified silicone resin is solid at 25 ° C. For this reason, it is preferable to use it by dissolving in cyclic silicone, dimethylpolysiloxane or the like. The cyclic silicone is preferably used by dissolving in one or more selected from octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5).

  As such a fluorine-modified silicone resin, INCI names “Trifluoropropyldimethyl / Trimethylsiloxysilicate”, XS66-B8226, XS66-C1191, XS66-B8636 (above, Momentive Performance Materials) Commercially available products such as those manufactured by the company) can be used.

Component (A) can be used singly or in combination of two or more, and can be uniformly attached to rough skin, suppress uneven color, and provide a natural finish. The lower limit with respect to the whole is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.25% by mass or more, still more preferably 0.4% by mass or more, and the upper limit is 10%. 7% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less. Moreover, content of a component (A) is 0.01-10 mass%, 0.1-7 mass% is preferable, 0.25-5 mass% is more preferable, 0.4-3 mass% is Further preferred.
Here, the natural finish means that the cosmetic does not look thick because the skin is thinly and evenly attached to the skin dermis and skin groove.

The powder of component (B) used in the present invention has been surface-treated with tridecafluorooctyltriethoxysilane represented by the following formula.
F ₃ C— (CF ₂ ) ₅ — (CH ₂ ) ₂ —Si— (OCH ₂ CH ₃ ) ₃
Of the fluorine compounds that surface-treat the powder, the powder surface-treated with tridecafluorooctyltriethoxysilane can be used in combination with component (A) to evenly adhere to the skin and suppress color unevenness. And can improve the texture of the skin. As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.

  The powder to be treated is not particularly limited as long as it is an extender pigment or a color pigment used in ordinary cosmetics, for example, silicic acid, silicic anhydride, magnesium silicate, talc, sericite, mica, kaolin, Bengala, clay, bentonite, titanium coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, titanium oxide, zinc oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, oxidation Inorganic powders such as chromium, chromium hydroxide, calamine and carbon black, and composites thereof; polyamide, polyester, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, acrylic resin, melamine Resin, Epoxy Organic powders such as resins, polycarbonate resins, divinylbenzene / styrene copolymers, silk powder, cellulose, long-chain alkyl phosphate metal salts, N-mono long-chain alkyl acyl basic amino acids, and complexes thereof; A composite powder of inorganic powder and organic powder can be used.

As a method of surface-treating the powder with tridecafluorooctyltriethoxysilane, for example, tridecafluorooctyltriethoxysilane is dropped or added in a mixer and mixed with the powder, followed by heat treatment, and if necessary And a method in which an organic solvent liquid in which tridecafluorooctyltriethoxysilane is dissolved or dispersed and a powder are mixed, the organic solvent is removed, and the mixture is crushed after drying.
Among them, tridecafluorooctyltriethoxysilane is dissolved or dispersed in an organic solvent, and while mixing the powder and the mixer in the mixer, the mixer is heated under reduced pressure to remove the organic solvent. A production method for crushing is preferred. Examples of the organic solvent used here include polar organic solvents such as methanol, ethanol, isopropyl alcohol, isobutanol, acetone, ethyl acetate, butyl acetate, methyl ethyl ketone, dichloromethane, and chloroform, and normal hexane, toluene, and xylene. Hydrocarbon organic solvents are suitable.

  The treatment amount of tridecafluorooctyltriethoxysilane varies depending on the powder, but the lower limit is preferably 0.05% by mass or more and more preferably 0.1% by mass or more with respect to the powder mass of the component (B). The upper limit is preferably 50% by mass or less, and more preferably 20% by mass or less. Moreover, it is preferable that the processing amount of tridecafluorooctyltriethoxysilane is 0.05-50 mass% with respect to the powder mass of a component (B), and 0.1-20 mass% is processed. Is more preferable. This treatment amount is preferable because water repellency and oil repellency are sufficiently exhibited, and feel and fluidity are good.

Component (B) preferably has an average particle size of 0.1 to 20 μm, more preferably 0.1 to 10 μm, from the standpoint of powderiness and finish at the time of application.
In the present invention, the particle diameter of the component (B) is measured with an electron microscope observation and a particle size distribution measuring device by a laser diffraction / scattering method. Specifically, in the case of the laser diffraction / scattering method, measurement is performed with a laser diffraction / scattering particle size distribution analyzer (for example, LA-920, manufactured by Horiba, Ltd.) using ethanol as a dispersion medium.

  Component (B) can be used singly or in combination of two or more, can be uniformly attached to rough skin, suppress uneven color, obtain a natural finish, and slip during application From the viewpoint of good, the lower limit is preferably 0.01% by mass or more, more preferably 1% by mass or more, further preferably 7% by mass or more, and the upper limit is preferably 40% by mass or less with respect to the entire cosmetic. 30 mass% or less is more preferable, and 15 mass% or less is further more preferable. Moreover, 0.01-40 mass% is preferable, as for content of a component (B), 1-30 mass% is more preferable, and 7-15 mass% is further more preferable.

  In the present invention, the mass ratios (A) / (B) of the components (A) and (B) can be uniformly attached to the roughened skin, and color unevenness is suppressed and a natural finish is obtained. The lower limit is preferably 0.001 or more, more preferably 0.02 or more, further preferably 0.04 or more, and the upper limit is preferably 1 or less, and 0.5 or less from the viewpoint of good slippage during application. More preferred is 0.3 or less. Moreover, it is preferable that mass ratio (A) / (B) is 0.001-1, 0.02-0.5 is more preferable, It is further more preferable that it is 0.04-0.3.

  Component (C) used in the present invention is represented by the following general formula (2) via an alkylene group containing a hetero atom in at least two silicon atoms of the organopolysiloxane segment constituting the main chain;

(Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3)
An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 4000,
The mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is 80/20 to 98/2,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 10,000 to 40,000,
It is an organopolysiloxane having a weight average molecular weight of 50,000 to 170000 of the organopolysiloxane segment constituting the main chain, and by using this component, more excellent stability can be obtained.

  The poly (N-acylalkyleneimine) segment is bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a hetero atom. Further, it is preferably bonded to one or more silicon atoms excluding both ends of the organopolysiloxane segment via the alkylene group, and bonded to two or more silicon atoms excluding both ends via the alkylene group. More preferably. That is, the organopolysiloxane of component (C) is a graft polymer having a poly (N-acylalkyleneimine) segment composed of at least two or more repeating units represented by the general formula (2) as a side chain. is there.

The alkylene group containing a hetero atom functions as a linking group for the poly (N-acylalkylenimine) segment. Examples of the alkylene group include C2-C20 alkylene groups containing 1 to 3 nitrogen atoms, oxygen atoms or sulfur atoms, and are represented by any of the following formulas (i) to (vii). A group represented by the following formula (i) or (ii) is more preferred, and a group represented by the following formula (i) is more preferred. In the formula, An ⁻ represents a counter ion of a quaternary ammonium salt, for example, ethyl sulfate ion, methyl sulfate ion, chloride ion, iodide ion, sulfate ion, p-toluenesulfonate ion, perchlorate ion. Is exemplified.

In the N-acylalkyleneimine unit constituting the poly (N-acylalkylenimine) segment, in the general formula (2), examples of the alkyl group having 1 to 3 carbon atoms in R ² include straight chain having 1 to 3 carbon atoms. Examples include a chain alkyl group or a branched or alkyl group having 3 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  In the general formula (2), t represents a number of 2 or 3, and is preferably 2 from the viewpoint of obtaining raw materials when producing the organopolysiloxane.

The mass ratio (a / b) is in the range of 80/20 to 98/2, and is preferably 83/17 to 96/4, more preferably 85/15 from the viewpoint of excellent adhesion to the skin and emulsification. ~ 94/6.
In the present specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of component (C) in deuterated chloroform and analyzing it by nuclear magnetic resonance ( ¹ H-NMR) analysis. The value obtained from the integral ratio of the alkyl group or phenyl group in the segment and the methylene group in the poly (N-acylalkylenimine) segment.

  In the organopolysiloxane of component (C), the weight average molecular weight of the organopolysiloxane segment between the adjacent poly (N-acylalkylenimine) segments (hereinafter also simply referred to as “MWg”) is in the range of 10,000 to 40,000. From the point of the softness | flexibility of a film | membrane and the orientation to an oil-water interface, More preferably, it is 15000-35000, More preferably, it is 18000-32000.

In the present specification, the “organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments” is an organopolysiloxane of a poly (N-acylalkylenimine) segment as shown in the following formula (3). A portion surrounded by a broken line between two points from a bonding point to the segment (bonding point A) to a bonding point (bonding point B) of the poly (N-acylalkyleneimine) segment adjacent thereto, A segment composed of R ³ SiO units, one R ⁴ , and y + 1 (R ³ ) ₂ SiO units. The “poly (N-acylalkylenimine) segment” refers to —Z—R ⁵ bonded to R ⁴ .

In the general formula (3), R ³ independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group, R ⁴ represents an alkylene group containing a hetero atom, and —Z—R ⁵ represents poly (N— Acylalkylenimine) segment, R ⁵ represents a residue of a polymerization initiator, and y represents a positive number.

  MWg is the molecular weight of the portion surrounded by the broken line in the above general formula (3), but is understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly (N-acylalkyleneimine) segment. Can do. In addition, when the functional group of the modified organopolysiloxane that is the raw material compound is 100% substituted with poly (N-acylalkyleneimine), it matches the functional group equivalent (g / mol) of the modified organopolysiloxane.

  The poly (N-acylalkylenimine) segment is represented by a number average molecular weight, and is calculated from the molecular weight of N-acylalkyleneimine units and the degree of polymerization, or gel permeation chromatography (hereinafter also simply referred to as “GPC”). ) It can be measured by the measuring method. In the present invention, the polystyrene-equivalent number average molecular weight (hereinafter, also simply referred to as “MNox”) measured by GPC measurement performed under the measurement conditions described later is used. When the MNox is in the range of 500 to 4000, the flexibility of the film and the solubility in the solvent can be increased. From this viewpoint, the MNox is preferably 800 to 3500, more preferably 1000 to 3000.

The MWg can be obtained by the following formula (I) using the content (mass%) of the organopolysiloxane segment constituting the main chain (hereinafter also simply referred to as “Csi”).
MWg = Csi × MNox / (100−Csi) (I)

  The weight average molecular weight (hereinafter also simply referred to as “MWsi”) of the organopolysiloxane segment constituting the main chain is 50,000 to 170000, preferably from 70000 to 160000, more preferably from the viewpoint of flexibility and adhesion to the skin. 80,000 to 150,000. Further, the organopolysiloxane of component (C) can be easily blended into various products by dissolving in a polar solvent such as water. Since the organopolysiloxane segment constituting the main chain has a common skeleton with the modified organopolysiloxane that is the raw material compound, MWsi is substantially the same as the weight average molecular weight of the modified organopolysiloxane that is the raw material compound. In addition, the weight average molecular weight of the modified organopolysiloxane which is a raw material compound is measured by GPC under the measurement conditions described later, and is converted to polystyrene.

  The weight average molecular weight (hereinafter also referred to simply as “MWt”) of the organopolysiloxane of component (C) is preferably 50,000 to 170000, more preferably 70000 to the viewpoint of achieving both adhesion to the skin and emulsion stability. It is 160000, More preferably, it is 80000-150,000. MWt is a value measured by GPC under the measurement conditions described later and converted to polystyrene.

  The organopolysiloxane of component (C), when heated to a temperature range of 50 to 220 ° C. in addition to a high elastic modulus and a large deformable amount, becomes extremely soft and soft, and immediately after the heating is stopped and it returns to room temperature. It has a characteristic thermoplasticity that regains elasticity.

  The organopolysiloxane of component (C) is, for example, the following general formula (4)

(In the formula, R ³ has the same meaning as described above, and R ⁶ and R ⁷ each represent the same group as R ³ , or the following formulas (viii) to (xiii)

R ⁸ represents a monovalent group represented by the above formulas (viii) to (xiii), and d represents a number from 91.5 to 1255.0. E represents a number of 2.0 to 62.5]
Modified organopolysiloxane represented by the following general formula (5)

(Wherein R ² and t have the same meaning as described above)
Is produced by reacting with a terminal reactive poly (N-acylalkyleneimine) obtained by ring-opening polymerization.

  A polymerization initiator can be used for the ring-opening polymerization of the cyclic imino ether represented by the general formula (5) (hereinafter also simply referred to as “cyclic imino ether (5)”). As the polymerization initiator, a compound having strong electrophilic reactivity, for example, a strong acid such as benzenesulfonic acid alkyl ester, p-toluenesulfonic acid alkyl ester, trifluoromethanesulfonic acid alkyl ester, trifluoroacetic acid alkyl ester, sulfuric acid dialkyl ester, etc. Alkyl esters can be used, and among them, dialkyl sulfate is preferably used.

  Examples of the polymerization solvent include acetates such as ethyl acetate and propyl acetate, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogen solvents such as chloroform and methylene chloride, acetonitrile. , Nitrile solvents such as benzonitrile, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, etc., among which acetates are preferred Is done. The usage-amount of a solvent is 20-2000 mass parts normally with respect to 100 mass parts of cyclic imino ether (5).

  The polymerization temperature is usually from 30 to 170 ° C., preferably from 40 to 150 ° C., and the polymerization time is not uniform depending on the polymerization temperature or the like, but is usually from 1 to 60 hours.

  When, for example, 2-substituted-2-oxazoline is used as the cyclic imino ether (5), poly (N-acylethyleneimine) of t = 2 in the general formula (2) is obtained, and 2-substituted-dihydro When 2-oxazine is used, poly (N-acylpropyleneimine) having t = 3 in the general formula (2) is obtained.

  Poly (N-acylalkylenimine) obtained by living polymerization of cyclic iminoether (5) has a reactive group at the terminal. Therefore, the reactive group at the terminal of the poly (N-acylalkylenimine) and the reactive group represented by the above (viii) to (xiii) of the modified organopolysiloxane represented by the general formula (4) By reacting, the organopolysiloxane of component (C) can be obtained.

  The production method by the living polymerization can easily control the degree of polymerization by using the amount of the cyclic imino ether (5) and the polymerization initiator as in the following theoretical formula (II), and moreover than the normal radical polymerization. This is effective in that a substantially monodispersed poly (N-acylalkylenimine) having a narrow molecular weight distribution can be obtained.

  The amount of cyclic iminoether (5) and the amount of polymerization initiator used are preferably such that MNi in formula (II) is 500 to 4000, more preferably 800 to 3500, The amount is more preferably 1000 to 3000.

  The weight average molecular weight of the modified organopolysiloxane represented by the general formula (4) is preferably 50000 to 170000 from the viewpoint of solubility of the obtained organopolysiloxane in a polar solvent such as water and ease of handling after dissolution, More preferably, it is 70000-160000, More preferably, it is 80000-150,000.

Further, the functional group equivalent of the modified organopolysiloxane represented by the general formula (4) has an upper limit in order to satisfy the mass ratio (a / b) and MWg of the organopolysiloxane of the component (C). From this viewpoint and the viewpoint of imparting appropriate hydrophobicity to the main chain, the functional group equivalent is preferably 10,000 to 40,000, more preferably 15,000 to 35,000, and still more preferably 18,000 to 32,000. Here, the functional group equivalent of the modified organopolysiloxane represented by the general formula (4) is the weight average molecular weight of the modified organopolysiloxane represented by the general formula (4). The value divided by the average value of the number of R ⁸ per unit.

  The amount of the modified organopolysiloxane represented by the general formula (4) and the terminal reactive poly (N-acylalkyleneimine) is the mass ratio (modified organopolysiloxane / terminal reactive poly (N-acylalkylene). The imine)) is preferably set to a value in the range of 80/20 to 98/2 from the viewpoint of the elastic modulus and the deformable amount of the resulting organopolysiloxane. From the same viewpoint, 83/17 to 96/4 is more preferable. Preferably, 85/15 to 94/6 are more preferable.

  In the present invention, in the synthesis of each organopolysiloxane, various molecular weights were measured according to the following measurement conditions.

<Measurement conditions of weight average molecular weight of modified organopolysiloxane>
Column: Super HZ4000 + Super HZ2000 (Tosoh Corporation)
Eluent: 1 mM triethylamine / THF
Flow rate: 0.35mL / min
Column temperature: 40 ° C
Detector: UV
Sample: 50 μL

<Measurement conditions for MNox and MWt>
Column: Two K-804L (Tosoh Corporation) are connected in series.
Eluent: 1 mM dimethyldodecylamine / chloroform Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Sample: 50 μL

Further, ¹ H-NMR measurement for calculating the mass ratio (a / b) was performed under the following conditions.
^<1 H-NMR measurement conditions>
The composition of the obtained polymer was confirmed by ¹ H-NMR (manufactured by 400 MHz Varian).
A sample amount of 0.5 g dissolved in 2 g of a measurement solvent (deuterated chloroform) was measured.
PULSE SEQUENCE
・ Relax.delay: 30 seconds ・ Pulse: 45degrees ・ Number of integration: 8 times Confirmation peak around 0ppm: Polydimethylsiloxane methyl group, around 3.4ppm:
The methylene part of ethyleneimine.
The ratio of silicone to poly (N-propionylethyleneimine) was calculated from each integrated value.

  Examples of the component (C) organopolysiloxane include poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, and poly (N-propionylethyleneimine) organosiloxane.

  Component (C) can be used alone or in combination of two or more, can be uniformly attached to rough skin, suppress color unevenness, obtain a natural finish, and slip during application However, the lower limit is preferably 0.01% by mass or more, more preferably 0.2% by mass or more, further preferably 0.4% by mass or more, and the upper limit is 10% by mass with respect to the entire cosmetic. The following is preferable, 3 mass% or less is more preferable, and 2.5 mass% or less is further more preferable. Moreover, 0.01-10 mass% is preferable, as for content of a component (C), 0.2-3 mass% is more preferable, and 0.4-2.5 mass% is further more preferable.

  In the present invention, the mass proportions (A) / (C) of the components (A) and (C) can be uniformly attached to the roughened skin, suppress uneven color, and obtain a natural finish. The lower limit is 0.01 or more, preferably 0.1 or more, more preferably 0.3 or more, and the upper limit is 10 or less, preferably 5 or less, from the viewpoint of good slippage during application. 4 or less is more preferable. Moreover, mass ratio (A) / (C) is 0.01-10, 0.1-5 are preferable and 0.3-4 are more preferable.

  In addition, the mass ratio (B) / (C) of the components (B) and (C) is preferably 1 or more, more preferably 3 or more, from the viewpoint that the feeling during use and slipping during coating are good. More preferably, the upper limit is preferably 500 or less, more preferably 50 or less, and even more preferably 30 or less. Moreover, 1-500 are preferable, as for mass ratio (B) / (C), 3-50 are more preferable, and 5-30 are more preferable.

  In addition, the content of water used in the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and the upper limit is from the viewpoint of usability and storage stability, with respect to the entire cosmetic. 60% or less is preferable and 50 mass% or less is more preferable. Moreover, 10-60 mass% is preferable and, as for content of water, 20-50 mass% is more preferable.

In addition, the oil used in the present invention may be liquid at 20 ° C. When a solid or paste oil is used, it is preferably used after being dissolved in another oil or solvent.
Examples of the oil used in the present invention include silicone oils, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils (including fats and oils), ether oils, mineral oils, etc. Ester oil is more preferable, and silicone oil is more preferable. Of these, dimethylpolysiloxane and cyclopolysiloxane are more preferable.
These oil agents can be used alone or in combination of two or more.
Moreover, as for content of the oil agent used for this invention, 10 mass% or more is preferable with respect to the whole cosmetics, 20 mass% or more is more preferable, and an upper limit is 50 mass% or less, 40 mass is preferable. % Or less is more preferable. Moreover, 10-50 mass% is preferable, and, as for content of an oil agent, 20-40 mass% is more preferable from the point of use feeling and storage stability.

Examples of the surfactant used in the present invention include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Among these, nonionic surfactants are preferable, and polyether-modified silicones are more preferable. From the viewpoint of stably emulsifying the components (A), (B), and (C), the HLB value is preferably 1 or more and 7 or less, and the HLB value is more preferably 2 or more and 6 or less.
The content of the surfactant is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and the upper limit is preferably 6% by mass or less, and 3% by mass with respect to the entire cosmetic. The following is more preferable. Moreover, 0.1-6 mass% is preferable and, as for content of surfactant, it is more preferable to contain 0.2-3 mass%.

Here, HLB (hydrophilic-lipophilic balance <Hydrophilic-Lypophilic Balance>) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant. For nonionic surfactants, Griffin ( Griffin).
The HLB of the mixed surfactant composed of two or more kinds of nonionic surfactants is obtained as follows. The HLB of the mixed surfactant is obtained by averaging the HLB values of the nonionic surfactants based on the blending ratio.

Mixed HLB = Σ (HLBx × Wx) / ΣWx
HLBx indicates the HLB value of the nonionic surfactant X.
Wx indicates the weight (g) of the nonionic surfactant X having a value of HLBx.

  In the water-in-oil emulsified cosmetic of the present invention, the following general formulas (11) and (12)

(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R ¹¹ , R ¹² and R ¹³ are the same or different and each represents a straight-chain or branched chain having 1 to 6 carbon atoms. A hydrocarbon group, m is a number from 2 to 6, n is a number from 1 to 6, p is a number from 3 to 50, and s is a number from 1 to 5)
Fluorine-modified silicone oil having a polysiloxane unit represented by the formula (1) can be contained, and the cosmetic durability of the water-in-oil emulsified cosmetic can be improved. Such fluorine-modified silicone oil is liquid at 25 ° C.

In the formula, examples of the hydrocarbon group represented by R ¹¹ , R ¹² and R ¹³ include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; isopropyl group, sec -Branched alkyl groups such as butyl group, tert-butyl group, neopentyl group and 1-ethylpropyl group; and cyclic alkyl groups such as cyclopentyl and cyclohexyl.

Moreover, m shows the number of 2-6, Preferably it is 2-5, More preferably, it is 3. n shows the number of 1-6, Preferably it is 1-4, More preferably, it is 2.
p shows the number of 3-50, Preferably it is 3-10, More preferably, it is 3-6. s shows the number of 1-5, Preferably it is 1-3, More preferably, it is 1.

  The ratio of p and s, that is, the modification rate of the polysiloxane unit p represented by the general formula (11) with respect to the total p + s of the polysiloxane units represented by the general formulas (11) and (12) 0.66 ≦ p / (p + s) ≦ 0.9 is preferable, and 0.75 ≦ p / (p + s) ≦ 0.83 because it is excellent in durability and can be uniformly attached to rough skin. Is more preferable.

Such a fluorine-modified silicone oil can be produced, for example, according to the method described in JP-A-6-184212.
Moreover, as a fluorine-modified silicone oil, what is represented by following General formula (13) is preferable.

(Wherein p and s have the same meaning as described above, and q represents a number of 5)

  Fluorine-modified silicone oil can be used alone or in combination of two or more, and it has excellent makeup and can be uniformly attached to rough skin. 0.01 mass% or more is preferable, 0.1 mass% or more is more preferable, 1 mass% or more is more preferable, and the upper limit is preferably 30 mass% or less, more preferably 20 mass% or less, and more preferably 5 mass% or less. Further preferred. Moreover, 0.01-30 mass% is preferable, as for content of fluorine-modified silicone oil, 0.1-20 mass% is more preferable, and 1-5 mass% is further more preferable.

  The cosmetic of the present invention is a component used in normal cosmetics in addition to the above components, for example, solid oils such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax; water-soluble and oil-soluble polymers; Powders other than the above components: ethanol, polyhydric alcohol, preservatives, antioxidants, dyes, thickeners, pH adjusters, fragrances, ultraviolet absorbers, moisturizers, blood circulation promoters, cooling sensates, antiperspirants , Fungicides, skin activators and the like.

  The cosmetic of the present invention can be produced according to a usual method and is a water-in-oil emulsified cosmetic. Furthermore, examples of the dosage form include liquid, emulsion, cream, and gel, and emulsion is preferred.

  The cosmetics of the present invention can be makeup cosmetics such as foundations, lipsticks, blushers, and eye shadows; UV protective cosmetics such as sunscreen emulsions and sunscreen creams, and foundations are preferred.

Synthesis Example 1 (Synthesis of Compound C1)
12.9 g (0.13 mol) of 2-ethyl-2-oxazoline and 27.7 g of ethyl acetate were mixed, and the mixture was 2.0 g of molecular sieve (Zeoram A-4, manufactured by Tosoh Corporation) at 28 ° C. 15 Time dehydration was performed.
Also, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8015, manufactured by Shin-Etsu Silicone Co., Ltd., weight average molecular weight 100000, amine equivalent 20000) and ethyl acetate 203 g were mixed, and the mixture was 15.2 g of molecular sieve. Dehydration was performed at 28 ° C. for 15 hours.
To the above ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline was added 0.77 g (0.005 mol) of diethyl sulfate, and the mixture was heated to reflux at 80 ° C. for 8 hours under a nitrogen atmosphere, and terminal reactive poly (N-propionyl). Ethyleneimine) was synthesized. The number average molecular weight measured by GPC was 2700.
To this terminal-reactive poly (N-propionylethyleneimine) solution, the dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution was added all at once and heated to reflux at 80 ° C. for 10 hours.
The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine-dimethylsiloxane copolymer as a white rubbery solid (108 g). The mass ratio of the organopolysiloxane segment in the final product was 0.87, and the weight average molecular weight of the final product was 115,000.

Synthesis Example 2 (Synthesis of Compound C2)
3.63 g (0.036 mol) of 2-ethyl-2-oxazoline and 8.46 g of ethyl acetate were mixed, and the mixture was 0.6 g of molecular sieve (Zeoram A-4, manufactured by Tosoh Corporation) at 28 ° C. 15 Time dehydration was performed.
Also, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8015, manufactured by Shin-Etsu Silicone Co., Ltd., weight average molecular weight 100000, amine equivalent 20000) and ethyl acetate 203 g were mixed, and the mixture was 15.2 g of molecular sieve. Dehydration was performed at 28 ° C. for 15 hours.
Diethyl sulfate (0.54 g, 0.0035 mol) was added to the above-mentioned dehydrated 2-ethyl-2-oxazoline in ethyl acetate, heated to reflux at 80 ° C. for 8 hours under a nitrogen atmosphere, and terminal reactive poly (N-propionyl). Ethyleneimine) was synthesized. The number average molecular weight measured by GPC was 1200.
To this terminal-reactive poly (N-propionylethyleneimine) solution, the dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution was added all at once and heated to reflux at 80 ° C. for 10 hours.
The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a white rubbery solid (102 g). The mass ratio of the organopolysiloxane segment in the final product was 0.96, and the weight average molecular weight of the final product was 104,000.

Synthesis Example 3 (Synthesis of fluorine-modified silicone oil)

Synthesis of _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2:
To a 2 L four-necked flask equipped with a thermometer and a cooling tube, 800 g (2.2 mol) of FA-6 (Unimatec) and 175.78 g (4.4 mol) of granular NaOH (Wako Pure Chemical Industries) were added. It was. While stirring at 200 rpm with a 12 cm crescent stirring blade made of Teflon (registered trademark) in a nitrogen atmosphere, the temperature in the flask was adjusted to 60 ° C. Thereto, 398.73 g (3.3 mol) of allyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 70 ° C. for 1 hour and at 80 ° C. for 1 hour. Thereafter, the temperature was raised to 130 ° C. to remove excess allyl bromide. After cooling to 60 ° C., 800 g of ion-exchanged water was added, stirred for 30 minutes, and then allowed to stand to separate the layers. The upper aqueous layer was extracted, and 800 g of ion-exchanged water was further added, followed by stirring, standing still, and removal of the aqueous layer. Dried at 60 ℃ / 5KPa, 100 ℃ / distilled at 2 KPa, as a fraction, to obtain a _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2 774.9g ( yield: 88 %).

  To a 300 mL four-necked flask equipped with a thermometer, 52.89 g (111 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2% by mass of chloroplatinic acid hexahydrate / isopropyl alcohol 0.66 g was added, and the temperature was raised to 110 ° C.

C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 197.11 g (488 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 25.07 g of 0.1% NaOH solution was added and stirred for 2 hours. After dehydration at 60 ° C./5 KPa, 2.51 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature, and the mixture was stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 62.5 g of water to obtain 206.3 g of the target compound (yield 89%).

Examples 1-8, Comparative Examples 1-4
A water-in-oil type emulsion foundation having the composition shown in Table 2 was produced, “adhesion state immediately after application”, “hardness of color unevenness immediately after application”, “natural finish immediately after application”, and “ The “goodness of sliding during application” was evaluated. The results are also shown in Table 2.

(Production method)
About Examples 1-8 and Comparative Examples 1-4, the whole quantity is measured with a scale of 100 g. The oil phase (containing the active agent) containing the component (A) is preliminarily dispersed using a disper (500 r / min, 5 minutes). Next, the powder phase containing the component (B) is dispersed in the oil phase (1500 r / min, 10 minutes), and it is confirmed that the powder phase is uniformly dispersed. The ethanol phase containing the component (C) is added to the oil phase in which the powder phase has become uniform and stirred with a disper (450 r / min, 10 minutes). Next, the aqueous phase was gradually added while stirring with a disper (500 r / min), emulsified, and after emulsification, the viscosity was adjusted with a homomixer (3000 r / min), defoamed, A water-type emulsified liquid foundation was obtained.

(Evaluation method)
Five specialist panelists apply each water-in-oil emulsified foundation with a sponge to the skin of a woman whose texture has become rough due to aging, and “adhesion state” immediately after application, “difficult to notice uneven color” The “natural finish” and the “slippery” during application were evaluated according to the following criteria. A result is shown by the integrated value of 5 persons.

(1) Adhesion state immediately after application:
5: Cosmetics adhere uniformly.
4; Cosmetics adhere almost uniformly.
3; Cosmetics are slightly attached to the mottle.
2; Cosmetics adhere to mottle.
1; Cosmetics are considerably mottled.

(2) Difficult to notice uneven color immediately after application:
5: Color unevenness is not noticeable.
4; Color unevenness is not so noticeable.
3; Color unevenness is slightly noticeable.
2: Color unevenness is conspicuous.
1; Color unevenness is considerably conspicuous.

(3) Natural finish immediately after application:
5; I don't want to be thick.
4; I don't want to be too thick.
3; Slightly thick.
2;
1;

(4) Good sliding during application:
5; Sliding is quite good.
4; Good sliding.
3; Slip is slightly good.
2; Sliding is not so good.
1; Sliding is bad.

Example 9: Sunscreen emulsion A sunscreen emulsion having the composition shown in Table 3 was produced.

(Production method)
After roughly mixing the components (1) to (3), the components are mixed and pulverized using an atomizer pulverizer (Fuji Powder Co., Ltd.). Components (4) to (9) are mixed with stirring, and then components (10) and (11) are added and mixed with stirring. Add the ground ingredients and disperse using a disper. Components (12) and (13) were added and mixed with stirring to obtain a sunscreen emulsion.

  The sunscreen emulsion obtained as described above can evenly adhere to rough skin, suppress uneven color, give a natural finish, and have good slippage during application. I found out.

Claims (3)

The following components (A), (B) and (C):
(A) The following general formula (1)
R ¹ _a SiO _{(4-a) / 2} (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ² —Rf (R ² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8, which is arbitrarily selected from a functional group having a hydroxyl group and a general formula —R ² —Rf as essential, and a is an average number of 1.0 ≦ a ≦ 1. 8)
0.01 to 10% by mass of a fluorine-modified silicone resin having a structure represented by
(B) 0.01-40% by mass of powder surface-treated with tridecafluorooctyltriethoxysilane ,
(C) At least two silicon atoms of the organopolysiloxane segment constituting the main chain, via an alkylene group containing a hetero atom, the following general formula (2);

(Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3)
An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 4000,
The mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is 80/20 to 98/2,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 10,000 to 40,000,
0.01-10 mass% of organopolysiloxane whose weight average molecular weight of the organopolysiloxane segment which comprises a principal chain is 50000-170000
A water-in-oil emulsified cosmetic in which the mass ratio of components (A) and (C) is (A) / (C) = 0.1-10 . The water-in-oil emulsified cosmetic according to claim 1, wherein the mass ratio of the components (B) and (C) is (B) / (C) = 1 to 500. The water-in-oil emulsified cosmetic according to claim 1 or 2 , wherein the mass ratio of the components (A) and (B) is (A) / (B) = 0.001-1.