JP6395448B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

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

Conventionally, cosmetics containing various organopolysiloxanes, cross-linked methylpolysiloxanes, and powders are known to be effective for makeup paste, makeup retention, and makeup.
For example, in Patent Document 1, a cosmetic material containing organopolysiloxane having a specific structure, cross-linked methylpolysiloxane, plate-like powder, or spherical powder repairs the skin surface such as desquamation, and adheres to the skin. It is described that it is excellent in the makeup and the makeup lasting time. Patent Document 2 discloses that a cross-linked polyether-modified silicone, an organopolysiloxane having a specific structure, and a water-in-oil emulsified cosmetic containing a powder have a good touch on the skin and are excellent in use feeling. It is described that since the powder is uniformly dispersed, the skin can be brightened, and powdering and makeup due to drying are not noticeable.

JP2013-103895A JP 2013-43847 A

  Conventional cosmetics have a problem that when applied to the skin or when a powder foundation is overlaid, the color tends to fade when rubbed with hands, cloth, or tissue paper.

  The inventor obtains a combination of poly (N-acylalkylenimine) -modified organopolysiloxane having a specific modification rate, volatile silicone oil, specific cross-linked polyether-modified silicone, and spherical organic powder having a specific particle size. The water-in-oil emulsified cosmetics form a firm and uniform film on the skin crevice and hills, so it is difficult to rub off with hands or cloth, and even when powder foundation is overlaid I found it difficult to fall.

The present invention includes the following components (A), (B), (C) and (D):
(A) At least two of the organopolysiloxane segments constituting the main chain, through an alkylene group containing a hetero atom, the following general formula (1);

(Wherein R ¹ 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 weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1000-40000,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 15000 to 200000,
Organopolysiloxane having a mass ratio (a / b) of 65/35 to 90/10 of the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkyleneimine) segment (b). 1-10% by mass,
(B) Volatile silicone oil 1-40% by mass,
(C) The following general formula (5)

(In the formula, each R represents a methyl group or a phenyl group, each R ′ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R ″ represents an alkyl group having 1 to 30 carbon atoms or An acyl group or a siloxane group having a silicon atom of 1 to 30. d represents a number of 1 to 20, e and f represent a number of 0 to 200, and e and f are not simultaneously 0. g Represents a number from 0 to 30, h represents a number from 1 to 100, i represents a number from 10 to 2000, j represents a number from 1 to 1000, and k represents a number from 1 to 1000)
0.1 to 20% by mass of a crosslinked polyether-modified silicone represented by
(D) Spherical organic powder having a particle diameter of 10 to 50 μm 0.05 to 10% by mass
The present invention relates to a water-in-oil emulsified cosmetic containing

  The water-in-oil emulsified cosmetic of the present invention has excellent adhesion to the skin and forms a firm and uniform film on the skin's skin crevice and skin hill, so it can be removed even when rubbed with hands, cloth, tissue paper, etc. In addition, even when a powder foundation is overlaid, it has excellent adhesion, forms a uniform film, and is difficult to fall off. Moreover, these effects last for a long time.

  In the component (A) used in the present invention, the poly (N-acylalkylenimine) 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 (A) is a graft polymer having a poly (N-acylalkylenimine) segment composed of at least two or more repeating units represented by the general formula (1) 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 (1), the alkyl group having 1 to 3 carbon atoms in R ¹ is, for example, a straight chain having 1 to 3 carbon atoms. Examples thereof include a chain alkyl group or a branched 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 (1), 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 65/35 to 90/10, has excellent adhesion to the skin, and forms a firm and uniform film on the skin's skin grooves and hills. 68/32 to 80/20 are preferable, and 72/28 to 78/22 are more preferable from the viewpoint of suppressing color fading even when rubbed with a cloth, tissue paper or the like.
In this specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of component (A) 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 (A), the weight average molecular weight of the organopolysiloxane segment between the adjacent poly (N-acylalkyleneimine) segments (hereinafter also simply referred to as “MWg”) is in the range of 1000 to 40000, From the point of the softness | flexibility of the film | membrane of cosmetics, 10000-35000 are preferable and 15000-32000 are more preferable.

In the present specification, the “organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments” means an organopolysiloxane of a poly (N-acylalkylenimine) segment as shown in the following formula (2). 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 ² SiO units, one R ³ , and y + 1 (R ² ) ₂ SiO units. The “poly (N-acylalkylenimine) segment” refers to —Z—R ⁴ bonded to R ³ .

In the general formula (2), R ² independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group, R ³ represents an alkylene group containing a hetero atom, and —Z—R ⁴ represents poly (N— An acylalkylenimine) segment, R ⁴ 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 (2), but is understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly (N-acylalkylenimine) 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 molecular weight of the poly (N-acylalkylenimine) segment can be calculated from the molecular weight of the N-acylalkyleneimine unit and the degree of polymerization, or can be measured by gel permeation chromatography (hereinafter also simply referred to as “GPC”) measurement method. it can. 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. MNox is preferably in the range of 500 to 4000, more preferably 800 to 3500, and even more preferably 1000 to 3000, from the viewpoint of enhancing the flexibility of the cosmetic film and the solubility in a solvent.

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 organopolysiloxane segment constituting the main chain has a weight average molecular weight (hereinafter also simply referred to as “MWsi”) of 15,000 to 200,000, and preferably 50,000 to 170000 from the viewpoint of flexibility of the cosmetic and adhesion to the skin. More preferably, it is 70000-150,000. The organopolysiloxane of component (A) 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 simply referred to as “MWt”) of the organopolysiloxane of component (A) is preferably 15000 to 200000, more preferably 50000 to 170000, and still more preferably, from the viewpoint of excellent adhesion to the skin. 70000-150,000. MWt is a value measured by GPC under the measurement conditions described later and converted to polystyrene.

  In addition to the high elastic modulus and a large deformable amount, the organopolysiloxane of component (A) becomes extremely soft when heated to a temperature range of 50 to 220 ° C., 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 (A) is, for example, the following general formula (3)

(Wherein R ² represents the same meaning as described above, and R ⁵ and R ⁶ each represent the same group as R ² , or the following formulas (viii) to (xiii)

R ⁷ 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 (4)

(Wherein R ¹ 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 (4) (hereinafter also simply referred to as “cyclic imino ether (4)”). 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 sulfates are 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 (4).

  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 (4), poly (N-acylethyleneimine) of t = 2 in the general formula (1) is obtained, and 2-substituted-dihydro When 2-oxazine is used, in the above general formula (1), poly (N-acylpropyleneimine) having t = 3 is obtained.

  Poly (N-acylalkylenimine) obtained by living polymerization of cyclic iminoether (4) 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 (3) By reacting, the organopolysiloxane of component (A) can be obtained.

  In the production method by the living polymerization, the degree of polymerization can be easily controlled by the use amount of the cyclic imino ether (4) and the polymerization initiator as in the theoretical formula (II) shown below, 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 (4) used and the amount of polymerization initiator used is preferably such that MNi in formula (II) is 500-4000, more preferably 800-3500, The amount is more preferably 1000 to 3000.

  The weight average molecular weight of the modified organopolysiloxane represented by the general formula (3) is preferably 15000 to 220,000 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 50000-190000, More preferably, it is 70000-170000.

Further, the functional group equivalent of the modified organopolysiloxane represented by the general formula (3) has an upper limit to satisfy the mass ratio (a / b) and MWg of the organopolysiloxane of the component (A). From this viewpoint and the viewpoint of imparting appropriate hydrophobicity to the main chain, the functional group equivalent is preferably 1000 to 40000, more preferably 10,000 to 35000, and still more preferably 15000 to 32000. Here, the functional group equivalent of the modified organopolysiloxane represented by the general formula (3) is the weight average molecular weight of the modified organopolysiloxane represented by the general formula (3). This is the value divided by the average value of the number of R ^{7 around} .

  The amount of the modified organopolysiloxane represented by the general formula (3) and the terminal reactive poly (N-acylalkyleneimine) is the mass ratio (modified organopolysiloxane / terminal reactive poly (N-acylalkylene). The imine)) is preferably in the range of 65/35 to 90/10 from the viewpoint of the elastic modulus and deformable amount of the resulting organopolysiloxane, excellent in adhesion to the skin, 68/32 to 80/20 is more preferable from the viewpoint of forming a firm and uniform film on the skin and suppressing discoloration even when rubbed with hands, cloth, tissue paper, etc., and 72/28 to 78 / 22 is 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 (manufactured by 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
・ Accumulation count: 8 times Confirmation peak around 0ppm: Polydimethylsiloxane methyl group,
Around 3.4ppm: Methylene part of ethyleneimine.
The ratio of silicone to poly (N-propionylethyleneimine) was calculated from each integrated value.

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

  The component (A) can be used alone or in combination of two or more thereof, and the content thereof is excellent in adhesion to the skin, and forms a firm and uniform film on the skin crevice and hill, From the viewpoint of suppressing discoloration even when rubbed with hands, cloth, tissue paper, etc., it is 0.1% by mass or more in the total composition, preferably 0.4% by mass or more, and 0.6% by mass or more. More preferably, 1.0 mass% or more is more preferable, 10 mass% or less, 3 mass% or less is preferable, 1.8 mass% or less is more preferable, and 1.6 mass% or less is further more preferable. Moreover, content of a component (A) is 0.1-10 mass% in the whole composition, 0.4-3 mass% is preferable, 0.6-1.8 mass% is more preferable, 1. 0-1.6 mass% is further more preferable.

In the volatile silicone oil of the component (B), volatile is one having a flash point of 35 to 87 ° C.
Examples of the volatile silicone oil of component (B) include linear dimethylpolysiloxanes such as dimethylpolysiloxane (1.5cs) and dimethylpolysiloxane (2cs); tris (trimethylsilyl) methylsilane, tetrakis (trimethylsilyl) silane, and the like. And branched siloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

  Ingredient (B) can be used alone or in combination of two or more thereof, and its content is excellent in the solubility / dispersibility of ingredient (A) and adhesion to the skin, and firmly in the skin's skin crevice and dermis. And 1% by mass or more in the total composition, preferably 10% by mass or more, from the viewpoint of suppressing discoloration even when rubbed with hands, cloth, tissue paper or the like. % By mass or more is more preferable, 17% by mass or more is more preferable, 40% by mass or less is preferable, 30% by mass or less is preferable, 25% by mass or less is more preferable, and 22% by mass or less is more preferable. Moreover, content of a component (B) is 1-40 mass% in the whole composition, 10-30 mass% is preferable, 14-25 mass% is more preferable, 17-22 mass% is further more preferable.

  In the present invention, the mass ratio (A) / (B) of the components (A) and (B) is excellent in adhesion to the skin, and forms a firm and uniform film on the skin crevice and skin mound. Suppresses discoloration even when rubbed with hands, cloth, tissue paper, etc., and also has excellent adhesion to the skin, forms a uniform film, and is difficult to fall off even when powder foundation is overlaid Moreover, 0.01 or more is preferable, 0.02 or more is more preferable, 0.03 or more is further more preferable, 0.045 or more is further more preferable, and 1 or less is preferable from the point that these effects last for a long time. Is preferably 0.2 or less, more preferably 0.1 or less, and even more preferably 0.09 or less. Moreover, 0.01-1 are preferable, as for mass ratio (A) / (B) of a component (A) and (B), 0.02-0.2 are more preferable, and 0.03-0.1 are further Preferably, 0.045 to 0.09 is even more preferable.

The crosslinked polyether-modified silicone of component (C) used in the present invention is represented by the general formula (5).
In the formula, R ″ is preferably an alkyl group having 1 to 15 carbon atoms. Further, g is a number of 0 to 15, h is a number of 1 to 40, i is a number of 10 to 200, and j is 1 to 50. The number k is preferably a number from 1 to 50.

The crosslinked polyether-modified silicone of component (C) can be produced, for example, by the method described in JP-A-4-72932.
The crosslinked polyether-modified silicone of component (C) is preferably diluted or dispersed in volatile hydrocarbon oil, and polyisobutene is more preferable as the volatile hydrocarbon oil.

  Examples of the component (C) include KSG-210, KSG-240 (dimethicone / (PEG-10 / 15)) crosspolymer); KSG-310, KSG-320, KSG-330 ((PEG-15 / lauryl dimethicone). Commercially available products such as KSG-340 ((PEG-10 / lauryl dimethicone) cross polymer and (PEG-15 / lauryl dimethicone) cross polymer) (above, Shin-Etsu Chemical Co., Ltd.) can be used.

  Component (C) can be used alone or in combination of two or more, and the content thereof is excellent in the adhesion of the water-in-oil emulsified cosmetic to the skin, and even when the powder foundation is overlaid, From the point of forming a uniform film with excellent adhesion to the resin, it is 0.1% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, and more preferably 2% by mass or more. Is more preferably 20% by mass or less, preferably 10% by mass or less, more preferably 4% by mass, and even more preferably 3.3% by mass or less. Moreover, content of a component (C) is 0.1-20 mass% in all the compositions, 1-10 mass% is preferable, 1.5-4 mass% is more preferable, 2-3.3 mass % Is more preferable.

  In the present invention, the mass proportions (A) / (C) of the components (A) and (C) are excellent in adhesion to the skin, and form a firm and uniform film on the skin crevice and hill. In addition, it suppresses discoloration even by rubbing with hands, cloth, tissue paper, etc., and even when powder foundation is overlaid, it has excellent adhesion, forms a uniform film, and is hard to fall off, Moreover, from the point that these effects last for a long time, 0.02 or more is preferable, 0.1 or more is more preferable, 0.3 or more is more preferable, 0.4 or more is more preferable, 2 or less is preferable, 1 or less is more preferable, 0.8 or less is more preferable, and 0.6 or less is more preferable. Moreover, 0.02-2 are preferable, as for mass ratio (A) / (C) of component (A) and (C), 0.1-1 are more preferable, 0.3-0.8 are more preferable, 0.4 to 0.6 is even more preferable.

The spherical organic powder of the component (D) has a particle size of 10 to 50 μm, and preferably has a particle size of 20 to 40 μm from the viewpoint of suppressing pore conspicuousness and excellent usability. The shape may be a spherical powder or the like including a true sphere, a substantially spherical shape, and a spheroid, and having irregularities on the surface.
The particle diameter of the powder is measured by a particle size distribution measuring machine using a laser diffraction / scattering method. Specifically, 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.

The spherical organic powder of component (D) may be any spherical organic powder as long as it is used in ordinary cosmetics. Color pigments, pigments, dyes, metal ions, etc. are added to these spherical organic powders by a conventional method. It may be coated, encapsulated and colored.
Examples of the spherical organic powder include a spherical polyamide resin, a spherical polymethyl methacrylate resin, a spherical polyurethane resin, a spherical silicone resin, a spherical polyethylene resin, a spherical polystyrene resin, a spherical cellulose resin, and the like. Methyl resin, spherical polyurethane resin, and spherical silicone resin are preferred.

Among the components (D), spherical organic powders having rubber elasticity are preferable from the viewpoint of suppressing pore conspicuousness, excellent usability, and excellent adhesion to the skin. More preferably, rubber elasticity of 20 to 75 is even more preferable. Here, the rubber elasticity is measured by the durometer A according to JIS K 7215.
Of the component (D), the spherical organic powder having such rubber elasticity is preferably a spherical silicone resin or a spherical polyurethane resin. Examples of spherical silicone resins include silicone KSP-101 (Shin-Etsu Chemical Co., Ltd .; particle diameter 7-20 μm, rubber elasticity 30), silicone KSP-102 (Shin-Etsu Chemical Co., Ltd .; particle diameter 10-50 μm, rubber elasticity 30), and the like; As the spherical polyurethane resin, commercially available products such as Dymic Beads UCN-8150CM Clear (Daiichi Seika Kogyo Co., Ltd .; particle diameter 15 μm, rubber elasticity 74) can be used.

  The component (D) can be used alone or in combination of two or more, and the content thereof is excellent in the adhesion to the skin of the water-in-oil emulsified cosmetic, and even when the powder foundation is overlaid, From the point of excellent adhesion to the film and forming a uniform film, the total composition is 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass. % Or more is more preferable, it is 10 mass% or less, 6 mass% or less is preferable, 4 mass% or less is more preferable, and 3 mass% or less is further more preferable. Moreover, content of a component (D) is 0.05-10 mass% in the whole composition, 0.1-6 mass% is preferable, 0.5-4 mass% is more preferable, 1-3 mass % Is more preferable.

  In the present invention, the mass ratio (A) / (D) of the components (A) and (D) is excellent in the adhesion to the skin of the water-in-oil emulsified cosmetic, and is firmly attached to the skin crevice and skin hill. Forms a uniform film that suppresses discoloration even when rubbed with hands, cloth, tissue paper, etc., and even when powder foundation is overlaid, it has excellent adhesion to the skin and a uniform film. In view of the long-lasting effect of these effects, it is preferably 0.05 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and 0.4 or more. More preferably, 10 or less is preferable, 5 or less is more preferable, 2.5 or less is further preferable, and 2 or less is more preferable. Moreover, 0.05-10 are preferable, as for the mass ratio (A) / (D) of component (A) and (D), 0.2-5 are more preferable, 0.3-2.5 are more preferable, 0.4-2 are still more preferable.

The water-in-oil emulsified cosmetic of the present invention can further contain (E) a non-volatile oil, and can improve the feeling of use and makeup sustainability.
Here, the term “nonvolatile” means that 1 g of an oil agent is spread on a glass petri dish having a diameter of 48 mm and the mass reduction rate after being left at 25 ° C. and normal pressure for 24 hours is 1% or less.
The non-volatile oil of component (E) may be any as long as it is used in ordinary cosmetics, and examples thereof include ester oils, higher alcohols, hydrocarbon oils, and silicone oils.

  The ester oil is preferably liquid at 25 ° C., for example, octyldodecyl myristate, isopropyl myristate, isopropyl isostearate, isononyl isononanoate, isotridecyl isononanoate, butyl stearate, 2-ethylhexyl palmitate, octyl oleate Dodecyl, oleyl oleate, octyldodecyl ricinoleate, neopentyl glycol dicaprate, diisostearyl malate, octyldodecyl erucate, octyl hydroxystearate, octyl paramethoxycinnamate, macadamia nut oil, olive oil, castor oil, jojoba oil , Avocado oil, sunflower oil, polyglyceryl diisostearate, polyglyceryl triisostearate, glyceryl diisostearate, triisostearate Glyceryl phosphate, tri (caprylic-capric acid) glyceryl, glyceryl tri-2-ethylhexanoate, tetraethylene octanoate pentaerythrityl the like.

Examples of the higher alcohol include branched or unsaturated higher alcohols such as 2-octyldodecanol, isostearyl alcohol, and oleyl alcohol, and higher alcohols having 16 to 24 carbon atoms are preferable.
Examples of the hydrocarbon oil include squalane, liquid paraffin, liquid isoparaffin, polybutene, hydrogenated polyisobutene, hydrogenated polydecene, and petroleum jelly.
Examples of the silicone oil include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified silicone, acrylic-modified silicone, and fluorine-modified silicone.

  As the component (E), octyl paramethoxycinnamate, dimethylpolysiloxane, and fluorine-modified silicone are preferable from the viewpoint of excellent usability and makeup sustainability.

  Component (E) can be used singly or in combination of two or more, and the content thereof is preferably 0% by mass or more, preferably 0.1% by mass in the total composition, from the viewpoint of excellent feeling of use and makeup sustainability. The above is more preferable, 1% by mass or more is more preferable, 20% by mass or less is preferable, 15% by mass or less is more preferable, and 10% by mass or less is more preferable. Moreover, 0-20 mass% is preferable in the whole composition, as for content of a component (E), 0.1-15 mass% is more preferable, and 1-10 mass% is further more preferable.

  In the present invention, the mass ratio (B) / ((B) + (E)) of the component (B) to the total mass of the components (B) and (E) is excellent in adhesion to the skin, and the skin's skin groove And 0.4 or more, more preferably 0.5 or more from the viewpoint of forming a firm and uniform film on the hill and suppressing discoloration even when rubbed with hands, cloth, tissue paper, etc. 0.6 or more is more preferable, 1 or less is preferable, 0.95 or less is more preferable, and 0.9 or less is more preferable. The mass ratio (B) / ((B) + (E)) of the component (B) to the total mass of the components (B) and (E) is preferably 0.4 to 1, and preferably 0.5 to 0.00. 95 is more preferable, and 0.6 to 0.9 is even more preferable.

The water-in-oil emulsified cosmetic of the present invention can further contain (F) a spherical powder having a particle diameter of less than 1 to 10 μm, preferably 2 to 8 μm, and is excellent in slipping property during application. be able to. The shape may be a spherical powder or the like including a true sphere, a substantially spherical shape, and a spheroid, and having irregularities on the surface.
The particle diameter of the powder is measured in the same manner as in the component (D).

The spherical powder of component (F) may be either an inorganic spherical powder or an organic spherical powder as long as it is used in ordinary cosmetics, and these spherical powders are colored by a usual method. A pigment, pigment, dye, metal ion or the like may be coated, encapsulated, and colored.
Examples of the spherical powder include inorganic spherical powders such as spherical silica, spherical alumina, and spherical titania; spherical polyamide resin, spherical polymethyl methacrylate resin, spherical polyurethane resin, spherical silicone resin, spherical polyethylene resin, and spherical polystyrene resin. And organic spherical powders such as spherical cellulose-based resins; and those obtained by granulating extender pigments, colored pigments and the like into spheres by a conventional method. Among these spherical powders, spherical silica, spherical alumina, spherical polyamide resin, spherical polymethyl methacrylate resin, and spherical silicone resin are preferable from the viewpoint of feeling of use.

  Component (F) can be used singly or in combination of two or more, and its content is preferably 0.1% by weight or more, more preferably 0.5% by weight or more in the total composition from the point of use feeling. Preferably, 1% by mass or more is more preferable, 20% by mass or less is preferable, 10% by mass or less is more preferable, and 7% by mass or less is more preferable. Moreover, 0.1-20 mass% is preferable in the whole composition, as for content of a component (F), 0.5-10 mass% is more preferable, and 1-7 mass% is further more preferable.

  In the present invention, the mass ratio (D) / ((D) + (F)) of the component (D) to the total mass of the components (D) and (F) is the adhesion of the water-in-oil emulsified cosmetic to the skin. 0.02 or more is preferable from the viewpoint of excellent properties, forming a firm and uniform film on the skin crevice and cuticle, and suppressing discoloration even when rubbed with hands, cloth, tissue paper, etc. 0.05 or more is more preferable, 0.1 or more is more preferable, 1 or less is preferable, 0.8 or less is more preferable, and 0.6 or less is more preferable. In addition, the mass ratio (D) / ((D) + (F)) of the component (D) to the total mass of the components (D) and (F) is preferably 0.02-1, and 0.05-0. 8 is more preferable, and 0.1 to 0.6 is more preferable.

  In this invention, it is preferable to contain water 1-80 mass% in the whole composition from the point of a finish, 10-70 mass% is more preferable, and 20-60 mass% is further more preferable.

  Further, the water-in-oil emulsified cosmetic of the present invention includes, in addition to the above components, components used in ordinary cosmetics, for example, oily components other than those described above, powders other than those described above, surfactants, perfumes, and moisturizers. Agents, cosmetic ingredients, medicinal ingredients, ultraviolet absorbers, thickeners, bactericides, pH adjusters, antioxidants, preservatives, and the like.

Any of the powders used in the present invention can be used as it is, and further, one or two or more of these powders which have been subjected to a hydrophobic treatment can be used.
The hydrophobizing treatment is not limited as long as it is a treatment applied to normal cosmetic powders. Silicone treatment, fatty acid treatment, lauroyllysine treatment, lecithin treatment, N-acylamino acid treatment, metal soap treatment, fluorine Compound treatment and the like can be mentioned. Of these, silicone treatment is preferred.

The water-in-oil emulsified cosmetic of the present invention can be produced by a usual method, and is suitable as a skin cosmetic such as emulsion, cream, foundation, makeup base, concealer, lip balm, blusher, eye shadow, mascara and the like. is there.
This invention discloses the following compositions further regarding embodiment mentioned above.

<1> The following components (A), (B), (C) and (D):
(A) At least two of the organopolysiloxane segments constituting the main chain, through an alkylene group containing a hetero atom, the following general formula (1);

(Wherein R ¹ 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 weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1000-40000,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 15000 to 200000,
Organopolysiloxane having a mass ratio (a / b) of 65/35 to 90/10 of the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkyleneimine) segment (b). 1-10% by mass,
(B) Volatile silicone oil 1-40% by mass,
(C) The following general formula (5)

(In the formula, each R represents a methyl group or a phenyl group, each R ′ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R ″ represents an alkyl group having 1 to 30 carbon atoms or An acyl group or a siloxane group having a silicon atom of 1 to 30. d represents a number of 1 to 20, e and f represent a number of 0 to 200, and e and f are not simultaneously 0. g Represents a number from 0 to 30, h represents a number from 1 to 100, i represents a number from 10 to 2000, j represents a number from 1 to 1000, and k represents a number from 1 to 1000)
0.1 to 20% by mass of a crosslinked polyether-modified silicone represented by
(D) Spherical organic powder having a particle diameter of 10 to 50 μm 0.05 to 10% by mass
Water-in-oil emulsified cosmetic containing

<2> In the component (A), the mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is preferably 68. The water-in-oil emulsified cosmetic according to <1>, wherein / 32 to 80/20 is more preferable and 72/28 to 78/22 is more preferable.
<3> In the component (A), the weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is preferably 10,000 to 35,000, and more preferably 15,000 to 32,000. The water-in-oil emulsified cosmetic according to 1> or <2>.
<4> In the component (A), the number average molecular weight of the poly (N-acylalkyleneimine) segment is preferably 800 to 3500, more preferably 1000 to 3000, and any of the above <1> to <3> The water-in-oil emulsified cosmetic according to claim 1.
<5> In the component (A), the weight average molecular weight of the organopolysiloxane segment constituting the main chain is preferably 50000 to 170000, and more preferably 70000 to 150,000. The water-in-oil emulsified cosmetic according to claim 1.

<6> The organopolysiloxane of component (A) is preferably poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, or poly (N-propionylethyleneimine) organosiloxane. The water-in-oil emulsion cosmetic according to any one of <1> to <5>.
The content of <7> component (A) is preferably 0.4% by mass or more, more preferably 0.6% by mass or more, further preferably 1.0% by mass or more, in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <6>, preferably at most mass%, more preferably at most 1.8 mass%, further preferably at most 1.6 mass%.
<8> The water-in-oil emulsified cosmetic according to any one of <1> to <7>, wherein the volatile silicone oil of component (B) is preferably one having a flash point of 35 to 87 ° C.
It has a flash point.
The content of <9> component (B) is preferably 10% by mass or more in the total composition, more preferably 14% by mass or more, further preferably 17% by mass or more, and preferably 30% by mass or less, The water-in-oil emulsified cosmetic according to any one of <1> to <8>, more preferably 25% by mass or less, and further preferably 22% by mass or less.

<10> The mass ratio (A) / (B) of the components (A) and (B) is preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.03 or more, 0.045 or more is more preferable, 1 or less is preferable, 0.2 or less is more preferable, 0.1 or less is more preferable, and 0.09 or less is still more preferable any one of said <1>-<9> The water-in-oil emulsified cosmetic described.
<11> The crosslinked polyether-modified silicone of component (C) is preferably diluted or dispersed in volatile hydrocarbon oil, and more preferably diluted or dispersed in polyisobutene <1> The water-in-oil emulsified cosmetic according to any one of to <10>.
The content of the <12> component (C) is preferably 1% by mass or more in the total composition, more preferably 1.5% by mass or more, further preferably 2% by mass or more, and 10% by mass or less. The water-in-oil emulsified cosmetic according to any one of <1> to <11>, preferably 4% by mass, more preferably 3.3% by mass or less.

<13> The mass ratio (A) / (C) of the components (A) and (C) is preferably 0.02 or more, more preferably 0.1 or more, still more preferably 0.3 or more, 0.4 or more is still more preferable, 2 or less is preferable, 1 or less is more preferable, 0.8 or less is more preferable, and 0.6 or less is still more preferable, Any one of said <1>-<12> Water-in-oil emulsified cosmetic.
<14> The water-in-oil emulsified cosmetic according to any one of <1> to <13>, wherein the spherical organic powder of component (D) preferably has a particle diameter of 20 to 40 μm.
<15> The spherical organic powder of component (D) is preferably a spherical organic powder having rubber elasticity, more preferably rubber elasticity 5 to 80, and further preferably rubber elasticity 20 to 75. <1> The water-in-oil emulsified cosmetic according to any one of ~ <14>.
The content of <16> component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and 6% by mass in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <15>, preferably 4% by mass or less, more preferably 3% by mass or less.

<17> The mass ratio (A) / (D) of the components (A) and (D) is preferably 0.05 or more, more preferably 0.2 or more, further preferably 0.3 or more, 0 4 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, 2.5 or less is more preferable, and 2 or less is more preferable, and water in oil in any one of said <1>-<16> Type emulsified cosmetic.
<18> Further, (E) can contain non-volatile oil, preferably contains ester oil, higher alcohol, hydrocarbon oil, silicone oil, octyl paramethoxycinnamate, dimethylpolysiloxane, fluorine-modified The water-in-oil emulsified cosmetic according to any one of <1> to <17>, wherein silicone is more preferable.
The content of <19> component (E) is preferably 0% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, and more preferably 20% by mass or less in the total composition. Preferably, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable, The water-in-oil type emulsion cosmetic as described in said <18>.

<20> The mass ratio (B) / ((B) + (E)) of the component (B) to the total mass of the components (B) and (E) is preferably 0.4 or more, and 5 or more is more preferable, 0.6 or more is further preferable, 1 or less is preferable, 0.95 or less is more preferable, and 0.9 or less is more preferable. The water-in-oil emulsion makeup according to the above <18> or <19> Fee.
<21> Further, (F) a spherical powder having a particle diameter of 1 to less than 10 μm can be contained, preferably any of the above <1> to <20> containing a spherical powder having a particle diameter of 2 to 8 μm The water-in-oil emulsified cosmetic according to claim 1.
The content of the <22> component (F) is preferably 0.1% by mass or more in the total composition, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and 20% by mass. The water-in-oil emulsified cosmetic according to the above <21>, preferably 10% by mass or less, more preferably 7% by mass or less.

<23> The mass ratio (D) / ((D) + (F)) of the component (D) to the total mass of the components (D) and (F) is preferably 0.02 or more, and 05 or more is more preferable, 0.1 or more is more preferable, 1 or less is preferable, 0.8 or less is more preferable, and 0.6 or less is still more preferable. Fee.
<24> The water content is preferably 1 to 80% by mass in the total composition, more preferably 10 to 70% by mass, and further preferably 20 to 60% by mass <1> to <23>. The water-in-oil emulsified cosmetic according to any one of the above.

Synthesis Example 1 (Production of poly (N-propionylethyleneimine) -modified silicone)
Dissolve 19.0 g (0.12 mol) of diethyl sulfate and 81.0 g (0.82 mol) of 2-ethyl-2-oxazoline in 203.0 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. Reactive poly (N-propionylethyleneimine) was synthesized. The number average molecular weight measured by GPC was 1100. A 33% ethyl acetate solution of 300 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 2000) was added all at once and heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (390 g, yield 97%). The content of the organopolysiloxane segment in the final product was 75% by mass, and the weight average molecular weight was 40000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that about 20 mol% of amino groups remained.

Synthesis Example 2 (Production of poly (N-propionylethyleneimine) -modified silicone)
From 3.2 g (0.021 mol) of diethyl sulfate, 92.8 g (0.98 mol) of 2-ethyl-2-oxazoline and 205 g of dehydrated ethyl acetate, poly (N-propionylethyleneimine) having a number average molecular weight of 5200 was obtained. Obtained. Further, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 50000, amine equivalent 3800) was used to convert N-propionylethyleneimine-dimethylsiloxane copolymer into a pale yellow rubber-like solid (188 g, yield 96%). ). The content of the organopolysiloxane segment in the final product was 51% by mass, and the weight average molecular weight was 98,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that about 24 mol% of amino groups remained.

Synthesis Example 3 (Production of poly (N-propionylethyleneimine) -modified silicone)
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 content of the organopolysiloxane segment in the final product was 96% by mass, and the weight average molecular weight was 104,000.

Synthesis Example 4 (Production of dimethylsiloxane methyl (undecylglyceryl ether) siloxane copolymer)
(1) STEP-1: Synthesis of tetramethyldisiloxane having an alkyl group different from other alkyl groups in the silicone chain at both ends of the silicone chain:
1,4,8 g of 1,1,3,3-tetramethyldisiloxane and 1.0 g of Spiers catalyst (2-propanol solution of 2 mass% chloroplatinic acid) were added to a three-necked flask and heated to 70 ° C. At 70 ° C. under a nitrogen atmosphere, 174.2 g of α-olefin (“Dialene 168” manufactured by Mitsubishi Chemical Corporation, 1/1 (mass ratio) mixture of carbon numbers 16 and 18)) was added dropwise, followed by stirring for 2 hours. It was. After cooling, the reaction system was neutralized with an aqueous sodium hydroxide solution, and purified by distillation under reduced pressure. From the ¹ H-NMR spectrum (400 MHz) of the obtained product, the obtained product is a 1,1,3,3-tetramethyldisiloxane derivative having an alkyl group having 16 and 18 carbon atoms at both ends. (22.1 g, yield; 85%).

(2) STEP-2: Synthesis of an organohydrogenpolysiloxane having an alkyl group different from other alkyl groups in the silicone chain at both ends of the silicone chain and having a silicon-hydrogen bond in the silicone chain:
4,4.8 g of a 1,1,3,3-tetramethyldisiloxane derivative having an alkyl group having 16 and 18 carbon atoms at both ends synthesized in (1), 78.6 g of decamethylcyclopentasiloxane, 1,3 , 5,7-tetramethylcyclotetrasiloxane 19.8 g, n-heptane 50 g, and activated clay 5 g were added to a three-necked flask and refluxed for 12 hours. After cooling, distillation purification was performed under reduced pressure. From the ¹ H-NMR spectrum of the obtained product, the obtained product was a dimethylsiloxane / methylsiloxane copolymer having an alkyl group having 16 and 18 carbon atoms at both ends (the following formula; p = 23, q = 4) (132.8 g, yield; 95%).

(3) STEP-3: Synthesis of polysiloxane in which both ends are substituted with alkyl groups and side chains are graft-modified with alkyl glyceryl ether groups:
50.0 g of a dimethylsiloxane / methylsiloxane copolymer having an alkyl group having 16 and 18 carbon atoms at both ends synthesized in (2), 61.0 g of 10-undecenyl glyceryl ether, 5% by mass platinum-supporting carbon 0.25 g of catalyst was added to a three-necked flask and stirred at 70 ° C. for 3 hours. After cooling, distillation purification was performed under reduced pressure. From the ¹ H-NMR spectrum of the obtained product, the obtained product was a dimethylsiloxane methyl (undecyl glyceryl ether) siloxane copolymer having an alkyl group having 16 carbon atoms and 18 carbon atoms at both ends (described below). P = 23, q = 4) (63.0 g, yield; 95%).

Synthesis Example 5 (Production of fluorine-modified silicone)

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 condenser 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 (Compound B1) (yield 89%).

Examples 1-10 and Comparative Examples 1-5
Producing water-in-oil emulsified cosmetics having the composition shown in Table 1, adhesion to the skin, homogeneity of the cosmetic coating film on the skin, difficulty in conspicuous pores, difficulty in dropping when rubbed with fingers, In addition, the adhesion to the skin after application of the powder foundation, the homogeneity of the cosmetic coating on the skin and the difficulty of falling off when rubbed with a finger, and the rubbing with a finger after 4 hours of application of the powder foundation The difficulty of falling was evaluated. The results are also shown in Table 1.

(Production method)
About Examples 1-10 and Comparative Examples 1-5, the whole quantity is measured with a scale of 100 g. The oil phase (including the active agent) containing the components (A), (B), (C) and (E) is preliminarily dispersed using a disper (1500 r / min, 5 minutes). Next, the powder phase containing the components (D) and (F) is dispersed in the oil phase (2000 r / min, 5 minutes) to confirm that the powder phase is uniformly dispersed. Using an oil phase in which the powder phase has become uniform, the aqueous phase is gradually added with emulsification while stirring with a disper (3000 r / min, 5 minutes), emulsified and retained, and then the viscosity is adjusted with a homomixer (5800 r / Min, 5 minutes) and defoaming to obtain a water-in-oil emulsified cosmetic.

(Evaluation method)
(1) Adhesion to skin:
Five professional panelists performed sensory evaluation on the following criteria for the adhesion to the skin when each cosmetic was applied to the face. The result was shown as an integrated value of 5 persons.
5; Very good adhesion to skin.
4; Good adhesion to skin.
3; Slightly good adhesion to skin.
2; Adhesion to skin is not so good.
1; Adhesion to skin is not good.

(2) Homogeneity of the cosmetic film on the skin:
When five specialist panelists applied each cosmetic to the face, the homogeneity of the cosmetic coating film on the skin was subjected to sensory evaluation according to the following criteria. The result was shown as an integrated value of 5 persons.
5: A decorative coating film having no powder agglomeration and uniform uniformity.
4: A cosmetic coating film with less powder aggregation and uniform uniformity.
3; A slightly non-uniform decorative coating film with powder agglomeration.
2: It is a non-uniform coating film with powder aggregation.
1; Clearly powder agglomeration, unevenness is conspicuous, and the coating film is uneven.

(3) Hard to notice pores:
Five expert panelists performed sensory evaluation on the following criteria for the difficulty of conspicuous pores when each cosmetic was applied to the face. The result was shown as an integrated value of 5 persons.
5: Pore is not conspicuous.
4; The pores are hardly noticeable.
3; pores are not very noticeable.
2; The pores are slightly noticeable.
1; pores are conspicuous.

(4) Difficult to fall off when rubbed with fingers:
For each cosmetic, a decorative coating film was prepared on a black artificial leather with a coater of 0.152 mm and dried for 12 hours. Then, when 5 expert panelists rubbed the said cosmetic coating film lightly using one right hand middle finger, it evaluated by the following references | standards whether a cosmetic coating film could not be rubbed. The result was shown as an integrated value of 5 persons.
5: Even if rubbed, the decorative coating cannot be removed.
4; Even if rubbed, the decorative coating film is hardly removed.
3; When it is rubbed, a slight cosmetic film can be removed.
2; When rubbed, a decorative coating can be removed.
1; When rubbed, the decorative coating peels off.

(5) Adhesion to the skin after applying the powder foundation:
Five specialist panelists applied each cosmetic to the face, and then applied a powder foundation, and then sensoryly evaluated the adhesion to the skin according to the following criteria. The result was shown as an integrated value of 5 persons.
5; Very good adhesion to skin.
4; Good adhesion to skin.
3; Slightly good adhesion to skin.
2; Adhesion to skin is not so good.
1; Adhesion to skin is not good.

(6) Homogeneity of the cosmetic coating film on the skin after applying the powder foundation:
Five professional panelists applied each cosmetic material to the face, and then overlaid with a powder foundation, and then sensory-evaluated the homogeneity of the cosmetic coating film on the skin according to the following criteria. The result was shown as an integrated value of 5 persons.
5: A decorative coating film having no powder agglomeration and uniform uniformity.
4: A cosmetic coating film with less powder aggregation and uniform uniformity.
3; A slightly non-uniform decorative coating film with powder agglomeration.
2: It is a non-uniform coating film with powder aggregation.
1; Clearly powder agglomeration, unevenness is conspicuous, and the coating film is uneven.

(7) Difficult to fall off when rubbed with fingers after applying powder foundation:
When five specialist panelists apply each cosmetic on their face, and then apply a powder foundation, and then gently rub the cosmetic film with one middle finger on their right hand, the cosmetic film is rubbed off. The following criteria were used to assess whether there was any. The result was shown as an integrated value of 5 persons.
5: Even if rubbed, the decorative coating cannot be removed.
4; Even if rubbed, the decorative coating film is hardly removed.
3; When it is rubbed, a slight cosmetic film can be removed.
2; When rubbed, a decorative coating can be removed.
1; When rubbed, the decorative coating peels off.

(8) Difficult to fall off when rubbed with fingers after 4 hours of powder foundation application:
Five professional panelists applied each cosmetic to the face and then overlaid with powder foundation. After the lapse of 4 hours, whether or not the decorative coating film was rubbed when it was lightly rubbed with one middle finger on the right hand was evaluated according to the following criteria. The result was shown as an integrated value of 5 persons.
5: Even if rubbed, the decorative coating cannot be removed.
4; Even if rubbed, the decorative coating film is hardly removed.
3; When it is rubbed, a slight cosmetic film can be removed.
2; When rubbed, a decorative coating can be removed.
1; When rubbed, the decorative coating peels off.

Claims (8)

The following components (A), (B), (C) and (D):
(A) At least two of the organopolysiloxane segments constituting the main chain, through an alkylene group containing a hetero atom, the following general formula (1);
(Wherein R ¹ 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 weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1000-40000,
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 15000 to 200000,
Organopolysiloxane having a mass ratio (a / b) of 72/28 to 78/22 of the organopolysiloxane segment (a) constituting the main chain and the poly (N- acylalkyleneimine ) segment (b) 1-10% by mass,
(B) Volatile silicone oil 1-40% by mass,
(C) The following general formula (5)
(In the formula, each R represents a methyl group or a phenyl group, each R ′ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R ″ represents an alkyl group having 1 to 30 carbon atoms or An acyl group or a siloxane group having a silicon atom of 1 to 30. d represents a number of 1 to 20, e and f represent a number of 0 to 200, and e and f are not simultaneously 0. g Represents a number from 0 to 30, h represents a number from 1 to 100, i represents a number from 10 to 2000, j represents a number from 1 to 1000, and k represents a number from 1 to 1000)
0.1 to 20% by mass of a crosslinked polyether-modified silicone represented by
(D) Spherical organic powder having a particle diameter of 10 to 50 μm 0.05 to 10% by mass
Water-in-oil emulsified cosmetic containing   The water-in-oil emulsified cosmetic according to claim 1, wherein the component (B) has a flash point of 35 to 87 ° C.   The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein the mass ratio (A) / (C) of the components (A) and (C) is 0.02 to 2.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the mass ratio (A) / (D) of the components (A) and (D) is 0.05 to 10.   Furthermore, the water-in-oil type emulsified cosmetics of any one of Claims 1-4 containing 0-20 mass% of (E) non-volatile oil.   The water-in-oil mold according to claim 5, wherein the mass ratio (B) / ((B) + (E)) of component (B) to the total mass of components (B) and (E) is 0.4 to 1. Emulsified cosmetic.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 6, further comprising (F) 0.1 to 20% by mass of a spherical powder having a particle size of less than 1 to 10 µm.   The water-in-oil type according to claim 7, wherein the mass ratio (D) / ((D) + (F)) of component (D) to the total mass of components (D) and (F) is 0.02-1. Emulsified cosmetic.