JP6875122B2 - Solid powder cosmetics - Google Patents

Description

The present invention relates to solid powder cosmetics.

Solid powder cosmetics are produced by a press manufacturing method in which a powder component is the main component, an oily component is added and mixed as a binder, the container is filled, and then compressed and solidified. General solid powder cosmetics are molded with a high press pressure, and the obtained molded product is generally hard, and powder removal and feel are poor. Therefore, various studies have been conducted.
For example, Patent Document 1 describes that a solid powder cosmetic containing a powder, an oil agent, a non-volatile liquid water-soluble component, and a film-forming polymer has a soft, smooth, moist feel, and moisturizing property. There is.

Japanese Unexamined Patent Publication No. 2008-214264

According to the present inventor, when a spherical elastic powder is blended with a solid powder cosmetic, the smoothness and spreadability are good and a smooth feeling can be obtained, but when the blending amount is large, molding becomes difficult and the film forming property is high. By using the molecule together, it is excellent in spreading, sticking, and glossiness, but since the molded product becomes brittle, it is necessary to increase the molding pressure, the cosmetic becomes hard, and the powder removal is poor.

The present inventor uses a combination of poly (N-acylalkyleneimine) -modified organopolysiloxane and synthetic mica in a specific ratio together with a spherical silicone resin elastic powder to mold even if the molding pressure is lower than usual. It has been found that a solid powder cosmetic having excellent properties, softness, and good powder removal can be obtained.

In the present invention, the following components (A), (B) and (C):
(A) Spherical silicone resin elastic powder 11-70% by mass,
(B) The following general formula (1);

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3).
It is an organopolysiloxane formed by binding poly (N-acylalkyleneimine) segments consisting of repeating units represented by.
The poly (N-acylalkyleneimine) segment has a number average molecular weight of 500 to 4000 and
The mass average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is 1000-40,000.
The mass average molecular weight of the organopolysiloxane segment constituting the main chain is 1500 to 20000.
Organopolysiloxane 1 to the mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkyleneimine) segment (b) is 65/35 to 95/5. 6% by mass
(C) Synthetic phlogopite selected from synthetic phlogopite and iron-containing phlogopite 1 to 25% by mass
The present invention relates to a solid powder cosmetic containing, and the mass ratio (B) / (C) of the component (B) to the component (C) is 0.1 to 0.7.

The solid powder cosmetic of the present invention is excellent in moldability even when the molding pressure is lower than usual. Further, the solid powder cosmetic of the present invention is soft, has excellent powder removal, and gives a smooth and smooth feeling at the time of application.

The component (A) used in the present invention is a spherical silicone resin elastic powder.
The spherical shape may include a true sphere, a substantially spherical shape, a spheroid, and a spherical powder having an uneven surface.

The elastic powder of the silicone resin preferably has a rubber elasticity in the range of 5 to 80, more preferably 10 to 50. Rubber elasticity is measured by a durometer A according to JIS K 7215.
The silicone resin spherical elastic powder may be a silicone rubber elastic powder or a composite spherical powder having a silicone rubber elastic powder as a mother powder, and examples thereof include silicone resin-coated silicone rubber elastic powder.

The silicone rubber elastic powder is in the form of particles obtained by pulverizing silicone rubber having a structure in which linear dimethyl silicone is crosslinked, and a (dimethicone / vinyldimethicone) crosspolymer is preferable. Examples of commercially available products include Trefil E506S (average particle size 4 μm, rubber elasticity 30) and Trefil E508 (average particle size 4 μm, rubber elasticity 17) (all manufactured by Toray Downeening Co., Ltd.).
Silicone resin-coated silicone rubber elastic powder is a silicone rubber powder whose surface is coated with silsesquioxane resin, and is a (vinyldimethicone / methicone silsesquioxane) crosspolymer, (diphenyldimethicone / vinyldiphenyldimethicone /). Silicone skioxane) crosspolymer is preferred. Commercially available products include KSP-100 (average particle diameter 5 μm, rubber elasticity 30), KSP-101 (average particle diameter 12 μm, rubber elasticity 30), KSP-102 (average particle diameter 30 μm, rubber elasticity 30), KSP-105. (Average particle size 2 μm, rubber elasticity 75), KSP-300 (average particle size 5 μm, rubber elasticity 40) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be mentioned.

As the spherical silicone resin elastic powder of the component (A), a silicone resin-coated silicone rubber elastic powder is preferable from the viewpoint of being soft and excellent in powder removal.
In addition, the spherical silicone resin elastic powder of the component (A) has an average particle size of 1 to 50 μm because it is soft when pressed with a finger and is excellent in powder removal while maintaining the shape retention of the solid powder cosmetic. Is preferable, and 4 to 40 μm is more preferable.
The particle size of the powder is measured by a particle size distribution measuring machine by a laser diffraction / scattering method. Specifically, it is measured with a laser diffraction / scattering type particle size distribution measuring device (for example, LA-920 manufactured by HORIBA, Ltd.) using ethanol as a dispersion medium.
When the spherical silicone resin elastic powder is added, it can also be prepared by adding a solvent. Specifically, volatile and non-volatile silicones are useful.

As the component (A), one type or two or more types can be used, and the content is soft when pressed with a finger while maintaining the shape retention of the solid powder cosmetic, and is excellent in powder removal. The total composition is 11% by mass or more, preferably 25% by mass or more, more preferably 38% by mass or more, 70% by mass or less, preferably 65% by mass or less, and more preferably 60% by mass. The content of the component (A) is 11 to 70% by mass, preferably 25 to 65% by mass, and more preferably 38 to 60% by mass in the total composition.

The component (B) used in the present invention has the following general formula (1);

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3).
It is an organopolysiloxane formed by binding poly (N-acylalkyleneimine) segments consisting of repeating units represented by.
The poly (N-acylalkyleneimine) segment has a number average molecular weight of 500 to 4000 and
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is 1000-40,000.
The weight average molecular weight of the organopolysiloxane segment constituting the main chain is 1500 to 20000.
It is an organopolysiloxane having a mass ratio (a / b) of 65/35 to 95/5 of the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkyleneimine) segment (b). By using the component, it is possible to produce a solid powder cosmetic having excellent moldability and elasticity.

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 preferable that the organopolysiloxane segment is bonded to one or more silicon atoms excluding both ends via the alkylene group, and is bonded to two or more silicon atoms excluding both ends via the alkylene group. Is more preferable. That is, the organopolysiloxane of the component (B) is a graft polymer having a poly (N-acylalkyleneimine) segment consisting of at least two or more repeating units represented by the general formula (1) as a side chain. is there.

The alkylene group containing the heteroatom functions as a linking group for the poly (N-acylalkyleneimine) segment. Examples of such an alkylene group include an alkylene group having 1 to 2 carbon atoms containing 1 to 3 nitrogen atoms, oxygen atoms or sulfur atoms, and among them, they are represented by any of the following formulas (i) to (vii). The group represented by the following formula (i) or (ii) is more preferable, and the group represented by the following formula (i) is more preferable. In the formula, An ^- represents a counter ion of the quaternary ammonium salts, 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-acylalkyleneimine) segment, in the general formula (1), ^{the alkyl group having 1 to 3 carbon atoms in R 1} is, for example, a direct group having 1 to 3 carbon atoms. Examples thereof include a chain alkyl group and a branched alkyl group having 3 carbon atoms, and specific examples thereof 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 a raw material at the time of producing an organopolysiloxane.

The mass ratio (a / b) is in the range of 65/35 to 95/5, and is preferably 73/27 to 95/5, more preferably 73/27 to 95/5, from the viewpoint of producing a solid cosmetic having excellent moldability and elasticity. Is 80/20 to 93/7.
In the present specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of the component (B) in heavy chloroform and ^{analyzing the organopolysiloxane by nuclear magnetic resonance (1} H-NMR) analysis. A value obtained from the integral ratio of the alkyl group or phenyl group in the segment and the methylene group in the poly (N-acylalkyleneimine) segment.

In the organopolysiloxane of the component (B), the weight average molecular weight (hereinafter, also simply referred to as “MWg”) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is in the range of 1000 to 40,000. From the viewpoint of the flexibility of the cosmetic film, 1000 to 35000 is preferable, and 1500 to 32000 is more preferable.

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

In the above general formula (2), R ² independently represents an alkyl group or a phenyl group having 1 to 22 carbon atoms, R ³ represents an alkylene group containing a heteroatom, and -Z-R ⁴ represents a poly (N-). (Acylalkyleneimine) segment, R ⁴ indicates the residue of the polymerization initiator, and y indicates a positive number. The plurality of R ² , R ³ , and R ⁴ may be the same or different.

MWg is the molecular weight of the portion surrounded by a broken line in the above general formula (2), but can be understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly (N-acylalkyleneimine) segment. Can be done. When the functional group of the modified organopolysiloxane, which is a 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-acylalkyleneimine) segment can be calculated from the molecular weight and degree of polymerization of the N-acylalkyleneimine unit, or measured by gel permeation chromatography (hereinafter, also simply referred to as “GPC”). it can. In the present invention, it refers to a polystyrene-equivalent number average molecular weight (hereinafter, also simply referred to as “MNox”) measured by GPC measurement performed under the measurement conditions described below. 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 producing a solid cosmetic having excellent moldability and elasticity.

Further, the MWg can be determined 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 x MNox / (100-Csi) (I)

The weight average molecular weight of the organopolysiloxane segment constituting the main chain (hereinafter, also simply referred to as “MWsi”) is 1500 to 20000, and is preferably 50,000 to 170000 from the viewpoint of the flexibility of the cosmetic and the adhesion to the skin. , More preferably 70,000 to 150,000. Further, the organopolysiloxane of the component (B) can be easily blended into various products by dissolving it in a polar solvent such as water. Since the organopolysiloxane segment constituting the main chain has the same skeleton as the modified organopolysiloxane which is the raw material compound, MWsi is substantially the same as the weight average molecular weight of the modified organopolysiloxane which is the raw material compound. The weight average molecular weight of the modified organopolysiloxane, which is a raw material compound, is measured by GPC under the measurement conditions described below and converted to polystyrene.

The weight average molecular weight of the organopolysiloxane of the component (B) (hereinafter, also simply referred to as “MWt”) is preferably 1500 to 20000, more preferably 50,000 to 170000, and even more preferably, from the viewpoint of excellent adhesion to the skin. It is 70,000 to 150,000. MWt is a value measured by gel permeation chromatography (GPC) under the measurement conditions described below and converted into polystyrene.

In addition to its high elastic modulus and large deformable amount, the organopolysiloxane component (B) significantly improves its plasticity and becomes soft when heated to a temperature range of 50 to 220 ° C. In the process of stopping heating and returning to room temperature. It has a characteristic thermoplasticity that immediately regains elasticity.

The organopolysiloxane of the component (B) is, for example, the following general formula (3).

(In the formula, R ² has the same meaning as described above, and R ⁵ and R ⁶ each ^{have the same group as R 2} , or the following formulas (viii) to (xiii).

Indicates a monovalent group represented by any ^{of the above, R 7} represents a monovalent group represented by the above formulas (viii) to (xiii), and d represents a number of 91.5 to 1255.0. , E indicates a number from 2.0 to 62.5]
Modified organopolysiloxane represented by and the following general formula (4)

(In the formula, R ¹ and t have the same meaning as above)
It is produced by reacting a cyclic imino ether represented by (N) with a terminal reactive poly (N-acylalkyleneimine) obtained by ring-opening polymerization.

A polymerization initiator can be used for ring-opening polymerization of the cyclic imino ether represented by the general formula (4) (hereinafter, also simply referred to as “cyclic imino ether (4)”). Examples of the polymerization initiator include compounds having a strong electrophobetic reactivity, for example, strong acids such as benzenesulfonic acid alkyl ester, p-toluenesulfonic acid alkyl ester, trifluoromethanesulfonic acid alkyl ester, trifluoroacetate alkyl ester, and sulfuric acid dialkyl ester. Alkyl esters can be used, and among them, sulfuric acid dialkyl esters are preferably used.

Examples of the polymerization solvent include acetate esters 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, and acetonitrile. , A nitrile solvent such as benzonitrile, an aprotonic polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, and dimethylsulfoxide can be used, and among them, acetate esters are preferably used. Will be done. The amount of the solvent used is usually 20 to 2000 parts by mass with respect to 100 parts by mass of the cyclic imino ether (4).

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

When, for example, 2-substituted-2-oxazoline is used as the cyclic imino ether (4), poly (N-acylethyleneimine) having t = 2 is obtained in the general formula (1), and 2-substituted-dihydro is obtained. When -2-oxazine is used, poly (N-acylpropyleneimine) having t = 3 can be obtained in the above general formula (1).

The poly (N-acylalkyleneimine) obtained by living polymerization of the cyclic imino ether (4) has a reactive group at the terminal. Therefore, the reactive group at the terminal of this poly (N-acylalkyleneimine) and the reactive group represented by (viii) to (xiii) of the modified organopolysiloxane represented by the general formula (3) are separated. By reacting, the organopolysiloxane of the component (B) can be obtained.

In the above-mentioned production method by living polymerization, the degree of polymerization can be easily controlled by the amount of the cyclic imino ether (4) and the polymerization initiator used, as in the theoretical formula (II) shown below, and moreover than ordinary radical polymerization. It is effective in that a substantially monodisperse poly (N-acylalkyleneimine) having a narrow molecular weight distribution can be obtained.

The amount of the cyclic imino ether (4) used and the amount of the polymerization initiator used are preferably 500 to 4000 in MNi in the formula (II), more preferably 800 to 3500. It is more preferable that the amount is 1000 to 3000.

The weight average molecular weight of the modified organopolysiloxane represented by the general formula (3) is preferably 1500 to 220,000 from the viewpoint of the solubility of the obtained organopolysiloxane in a polar solvent such as water and the ease of handling after dissolution. , More preferably 50,000 to 190000, and even more preferably 70,000 to 170,000.

Further, the functional group equivalent of the modified organopolysiloxane represented by the general formula (3) has an upper limit in order to satisfy the mass ratio (a / b) and MWg of the organopolysiloxane of the component (A). From this viewpoint and from the viewpoint of imparting appropriate hydrophobicity to the main chain, the functional group equivalent is preferably 5000 to 40,000, more preferably 1000 to 35000, and further preferably 1500 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), and the modified organopolysiloxane is one molecule. It refers to a value obtained by dividing the average number of R ⁷ with per.

The amount of the modified organopolysiloxane represented by the general formula (3) and the terminal-reactive poly (N-acylalkyleneimine) used is the mass ratio (modified organopolysiloxane / terminal-reactive poly (N-acylalkyleneimine)). It is preferable that imine)) has a value in the range of 65/35 to 95/5 from the viewpoint of the elastic modulus and the deformable amount of the obtained organopolysiloxane, and a solid cosmetic having excellent moldability and elasticity can be obtained. From the point of view of making, 73/27 to 95/5 is more preferable, and 80/20 to 93/7 is even more preferable.

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

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

<Measurement conditions for MNox and MWt>
Column: K-804L (manufactured by Tosoh Co., Ltd.) Used by connecting two 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 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 measuring solvent (deuterated chloroform) was measured.
PULSE SEQUENCE
・ Relax.delay: 30 seconds ・ Pulse: 45degrees
・ Number of integrations: 8 times Confirmation peak around 0ppm: Methyl group of polydimethylsiloxane,
Around 3.4ppm: Methylene portion of ethyleneimine.
The ratio of silicone to poly (N-propionylethyleneimine) was calculated from each integral value.

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

As the component (B), a premix composition diluted with a solvent is preferable, and water is more preferable, from the viewpoints of improvement of workability, moldability of solid powder cosmetics, and impact resistance.
As the component (B), one type or two or more types can be used, and the content is such that the molding pressure is lower than usual even though the spherical elastic powder is blended in the solid powder cosmetics. A molded product having a uniform pressed surface can be obtained, and the produced solid powder cosmetics are soft, excellent in powder removal, and have a smooth and smooth feeling at the time of application. Therefore, 1% by mass or more in the total composition. It is preferably 2% by mass or more, 6% by mass or less, 5% by mass or less, and more preferably 4% by mass or less. The content of the component (B) is 1 to 6% by mass, preferably 2 to 5% by mass, and more preferably 2 to 4% by mass in the total composition.

In the present invention, the mass ratio (A) / (B) of the component (A) to the component (B) has a higher molding pressure than usual even though the spherical elastic powder is blended in the solid powder cosmetic. Even if it is low, a molded product having a uniform pressed surface can be obtained, and the produced solid powder cosmetics are soft, excellent in powder removal, and a smooth and smooth feeling can be obtained at the time of application, so 8 or more is preferable. 10 or more is more preferable, 11 or more is further preferable, 80 or less is more preferable, 50 or less is more preferable, and 30 or less is further preferable. The mass ratio (A) / (B) of the component (A) to the component (B) is preferably 8 to 80, more preferably 10 to 50, and even more preferably 11 to 30.

The component (C) used in the present invention is a synthetic phlogopite selected from synthetic phlogopite and iron-containing synthetic phlogopite.
Examples of synthetic phlogopite include those obtained by mixing and melting silicic acid anhydride, aluminum oxide, magnesium oxide, and potassium silicate, crystallizing crystals, pulverizing, and heat-treating. Iron-containing synthetic phlogopite. Examples thereof include those obtained by mixing and melting silicic acid anhydride, aluminum oxide, magnesium oxide, potassium fluoride, and iron oxide, crystallizing crystals, pulverizing, and heat-treating.
The iron-containing synthetic phlogopite preferably has an iron content of 0.5 to 10% by mass in terms of iron oxide, from the viewpoint of giving a highly transparent finish.

The shape is preferably plate-like, and the average particle size is 5 to 100 μm because it is excellent in moldability even when the molding pressure is lower than usual, and the produced solid powder cosmetic is soft and excellent in powder removal. It is preferably 5 to 40 μm, more preferably 10 to 30 μm, and the aspect ratio is preferably 15 to 100, more preferably 20 to 80, and even more preferably 40 to 70.

In the present invention, the average particle size is measured by an electron microscope observation and a particle size distribution measuring machine by a laser diffraction / scattering method. Specifically, in the case of the laser diffraction / scattering method, measurement is performed with a laser diffraction / scattering type particle size distribution measuring device (for example, LA-920 manufactured by HORIBA, Ltd.) using ethanol as a dispersion medium, and the average particle diameter is 50% median. The diameter. For the thickness, the difference from the reference plane is measured with an atomic force microscope, and the arithmetic mean is taken as the average thickness.
The aspect ratio is calculated by the ratio of the average particle size to the average thickness, and is defined by the aspect ratio = (average particle size / average thickness).

The synthetic phlogopite can be produced and used by the above-mentioned production method, or a commercially available product can also be used. Commercially available products include, for example, PDM-1000 (average particle size 12 μm, aspect ratio 20), PDM-10L (average particle size 12 μm, aspect ratio 60), PDM-20L (average particle size 20 μm, aspect ratio) manufactured by Topy Industries, Ltd. Ratio 70), PDM-40L (average particle size 40 μm, aspect ratio 80), PDM-NFES (average particle size 5 μm, aspect ratio 40) and the like can be used.

As the component (C), one type or two or more types can be used, and the content is excellent in moldability even when the molding pressure is lower than usual, and the produced solid powder cosmetic is soft and excellent in powder removal. From the viewpoint of feeling smooth and smooth at the time of application, the total composition is 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and 25% by mass or less. 20% by mass or less is preferable, 15% by mass or less is more preferable, and 14% by mass or less is further preferable. The content of the component (C) is 1 to 25% by mass, preferably 3 to 20% by mass, more preferably 5 to 15% by mass, and even more preferably 8 to 14% by mass in the total composition.

In the present invention, the mass ratio (B) / (C) of the component (B) to the component (C) has a higher molding pressure than usual even though the spherical elastic powder is blended in the solid powder cosmetic. Even if it is low, a molded product with a uniform press surface can be obtained, and the produced solid powder cosmetics are soft, excellent in powder removal, and give a smooth and smooth feeling at the time of application. Yes, 0.15 or more is preferable, 0.18 or more is more preferable, 0.7 or less, 0.6 or less is preferable, and 0.5 or less is more preferable. The mass ratio (B) / (C) of the component (B) to the component (C) is 0.1 to 0.7, preferably 0.15 to 0.6, and 0.18 to 0.5. Is more preferable.

In the present invention, the mass ratio (A) / (C) of the component (A) to the component (C) suppresses the swelling of the solid powder cosmetic, is soft, is excellent in powder removal, and gives a smooth and smooth feeling at the time of application. From this point of view, 1 or more is preferable, 2 or more is more preferable, 3 or more is further preferable, 40 or less is more preferable, 20 or less is more preferable, 8 or less is further preferable, and 6 or less is further preferable. The mass ratio (A) / (C) of the component (A) to the component (C) is preferably 1 to 40, more preferably 2 to 20, further preferably 3 to 8, and even more preferably 3 to 6. ..

The solid powder cosmetic of the present invention can contain powders other than the above. As the powder other than the above, if it is a powder usually used for cosmetics, it has a spherical shape, a plate shape, a needle shape, etc. It can be used without particular limitation depending on the particle structure and the like. Specifically, mica, iron hydroxide, iron titanate, yellow iron oxide, black iron oxide, carbon black, navy blue, ultramarine, manganese violet, cobalt violet, chromium oxide, chromium hydroxide, cobalt oxide, cobalt titanate, etc. Colored pigments; titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, cerium oxide, aluminum oxide, barium sulfate, calcium sulfate, magnesium sulfate, magnesium carbonate, calcium carbonate, talc, mica, kaolin, sericite, silicic acid, Silica anhydride, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, bentonite, montmorillonite, hectrite, smectite, zeolite, White or extender pigments such as ceramic powder, dicalcium phosphate, alumina, silica, aluminum hydroxide, boron nitride, synthetic sericite; fish scale foil, titanium oxide-coated mica (mica titanium), bismuth oxychloride, titanium oxide-coated oxychloride Bismus, titanium oxide-coated talc, titanium oxide-coated colored mica, titanium oxide-coated mica, fine-grained titanium oxide-coated mica, fine-grained zinc oxide-coated mica titanium, organic pigment-treated mica titanium, low-order titanium oxide-coated mica, mica, oxidation Titanium coated synthetic mica, titanium oxide coated plate silica, hollow plate titanium oxide, iron oxide coated mica, plate iron oxide (MIO), aluminum flakes, stainless flakes, titanium oxide coated plate alumina, pearl shell, gold foil, gold Pearl pigments (brilliant powder) such as vapor-deposited resin film and metal vapor-deposited resin film; organic powders such as organopolysiloxane elastomer, polymethylsilsesquioxane, nylon powder, silk powder, urethane powder, cellulose powder; Examples thereof include organic tar pigments such as Red 104, Red 102, Red 226, Red 201, Red 202, Yellow 4, and Black 401, organic pigments and rakes thereof, and one of these or rakes thereof. Two or more types can be used.

Any of the powders (including the component (C)) used in the present invention can be used as they are, and one or more of these powders can be hydrophobized. The hydrophobizing treatment is not limited as long as it is a treatment applied to ordinary cosmetic powders, such as fluorine compounds, silicone compounds, metal soaps, amino acid compounds, lecithin, alkylsilanes, oils, and organic titanates. Dry treatment, wet treatment, etc. may be performed using the surface treatment agent of.
Specific examples of the surface treatment agent include fluorine compounds such as perfluoropolyether, perfluoroalkyl phosphate, perfluoroalkyl alkoxysilane, and fluorine-modified silicone; dimethylpolysiloxane, methylhydrogenpolysiloxane, cyclic silicone, and pieces. Silicone compounds such as terminal or both terminal trialkoxy group-modified organopolysiloxane, crosslinked silicone, silicone resin, fluorine-modified silicone resin, acrylic-modified silicone; aluminum stearate, aluminum myristate, zinc stearate, magnesium stearate, etc. Metal soaps; amino acid compounds such as proline, hydroxyproline, alanine, glycine, sulfosin, glutamate, aspartic acid, lysine and derivatives thereof; lecithin, hydrogenated lecithin; methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane , Alkoxysilanes such as octyltrimethoxysilane and octylriethoxysilane; oils such as polyisobutylene, waxes and fats and oils; organic titanates such as isopropyltitanium triisostearate and the like.

Further, as the powder used in the present invention, one or more of these powders that have been hydrophilized can also be used. The hydrophilization treatment is not limited as long as it is a treatment applied to ordinary cosmetic powder.
For example, Arabic gum, tragacant, arabinogalactan, locust bean gum (carob gum), guar gum, karaya gum, carrageenan, pectin, agar, quince seed (malmero), starch (rice, corn, potato, wheat), algae colloid, tranth gum, Plant-based polymers such as locust bean gum; microbial polymers such as xanthan gum, dextran, succinoglucan, and purulan; animal-based polymers such as collagen, casein, albumin, deoxyribonucleic acid (DNA) and salts thereof; carboxymethyl starch , Methylhydroxypropyl starch and other starch-based polymers; methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, cellulosic powder of cellulose Polymers; Arginic acid-based polymers such as sodium alginate and propylene glycol alginate; Vinyl-based polymers such as polyvinyl methyl ether, polyvinylpyrrolidone and carboxyvinyl polymers; Polyoxyethylene-based polymers such as polyethylene glycol and polyethylene glycol silane; Poly Oxyethylene polyoxypropylene copolymerization system polymer; acrylic polymer such as sodium polyacrylate, polyethyl acrylate and polyacrylic acid amide, and inorganic silicic acid compound such as silica can be mentioned.

The solid powder cosmetic of the present invention can contain an oil component that is liquid at 25 ° C. It is an oil component that becomes fluid at 25 ° C., and as long as it has fluidity, a paste-like oil component is also included.
The oil component liquid at 25 ° C. may be any oil component used in ordinary cosmetics, for example, linear or branched hydrocarbons such as liquid paraffin, light isoparaffin, liquid isoparaffin, mineral oil, squalane, and squalane. Oils; avocado oil, macadamia nut oil, olive oil, rapeseed oil, sesame oil, wheat germ oil, flaxseed oil, cottonseed oil, soybean oil, palm oil. Vegetable oils such as palm oil, sunflower oil, jojoba oil, sunflower oil, camellia oil, corn oil; animal oils such as liquid lanolin; isopropyl myristate, octyldodecyl myristate, isopropyl isostearate, isononyl isononanoate, isotorideyl isononanoate, stearic acid Butyl, oleyl oleate, octyldodecyl ricinoleate, octyl hydroxystearate, 2-ethylhexyl paramethoxysilicate, neopentyl glycol dicaprate, diisostearyl malate, polyglyceryl diisostearate, polyglyceryl triisostearate, glyceryl diisostearate, Glyceryl triisostearate, Tri (capril capric acid) glyceryl, Glyceryl tri2-ethylhexanoate, Trimethylolpropane tri-2-ethylhexanoate, Trimethylolpropane triisostearate, dl-α-tocopherol, dl-nicotinate Fatty acid esters such as α-tocopherol; silicone oils such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher alcohol-modified organopolysiloxane; fluoropolyether, perfluoroalkyl ether silicone, etc. Fluorine oil; as creamy or paste-like oil components, trilanolin fatty acid glyceryl, soft lanolin fatty acid, vaseline, branched or hydroxylated fatty acid cholesteryl, dipentaerytrit fatty acid ester (dipentaerytrit hexaoxystearate, etc.), isostear Acid-cured castor oil, monohydroxystearic acid-cured castor oil, tri (capril, caprin, myristin, stearic acid) glyceride, myristyl lactate, dimer dilinoleic acid hydrogenated castor oil, dimer dilinoleic acid (phytorteryl / isostearyl / cetyl / Stearyl / behenyl), phytosteryl oleate, di-lauroyl-L-glutamate (phytosteryl behenyl 2-octyldodecyl) and the like. Among them, linear or branched hydrocarbon oil liquid at 25 ° C., fatty acid ester liquid at 25 ° C., silicone oil liquid at 25 ° C. are preferable, fatty acid ester liquid liquid at 25 ° C. is more preferable, and liquid fatty acid ester at 25 ° C. Fatty acid diester is even more preferred, and neopentyl glycol dicaprate is even more preferred.

The content of the oil component liquid at 25 ° C. is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, and 3 to 8% in the total composition from the viewpoint of improving the moldability of the solid powder cosmetic. Mass% is more preferred.

In addition to the above-mentioned components, the solid powder cosmetics of the present invention include components used in ordinary cosmetics, such as oily components other than the above, surfactants, preservatives, antioxidants, pigments, thickeners, and pH adjustments. It can contain agents, fragrances, UV absorbers, moisturizers, blood circulation promoters, cold sensation agents, antiseptic agents, bactericides, skin activators and the like.

The solid powder cosmetic of the present invention can be produced according to a usual method, for example, by mixing the ingredients, filling the container and pressing.
In the present invention, excellent moldability can be obtained even at a molding pressure lower than usual ( ^{about 2 to 6 kg / cm 2).}
The solid powder cosmetics of the present invention are suitable as, for example, makeup cosmetics such as foundations, pressed powders, cheeks, and eye shadows.

Production Example 1 (Production of poly (N-propionylethyleneimine) modified silicone 1)
12.9 g (0.13 mol) of 2-ethyl-2-oxazoline and 27.7 g of ethyl acetate are mixed, and the mixed solution is 2.0 g of molecular sieve (Zeolam A-4, manufactured by Tosoh Corporation) at 28 ° C. 15 Time dehydration was performed.
Further, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8015, manufactured by Shinetsu Silicone Co., Ltd., weight average molecular weight 100,000, amine equivalent 20000) and 203 g of ethyl acetate were mixed, and the mixed solution was prepared with 15.2 g of molecular sieve. Dehydration was performed at 28 ° C. for 15 hours.
0.77 g (0.005 mol) of diethyl sulfate was added to the above-mentioned ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, and the mixture was heated under reflux at 80 ° C. for 8 hours under a nitrogen atmosphere to undergo terminal-reactive poly (N-propionyl). Ethylimine) was synthesized. The number average molecular weight measured by GPC was 2700.
This terminal-reactive poly (N-propionylethyleneimine) solution was collectively added with the above-mentioned dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution, and the mixture was heated under reflux at 80 ° C. for 10 hours.
The reaction mixture was concentrated under reduced pressure to give an 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.

Production Example 2 (Production of poly (N-propionylethyleneimine) modified silicone 2)
2.36 g (0.0153 mol) of diethyl sulfate and 30.3 g (0.306 mol) of 2-ethyl-2-oxazoline were dissolved in 43 mL of chloroform, heated and refluxed for 5 hours under a nitrogen atmosphere, and poly (N-propionyl). A terminally reactive polymer (molecular weight 2000) of (ethyleneimine) was synthesized. A solution of 100 g of tertiary amino-modified silicone (0.0139 mol as an amino group) in chloroform (270 mL) was added thereto, and the mixture was heated under reflux for 16 hours.
The reaction mixture was concentrated under reduced pressure to give an N-propionylethyleneimine-dimethylsiloxane copolymer as a white rubbery solid (129 g). The mass ratio of the organopolysiloxane segment in the final product was 0.75, and the weight average molecular weight of the final product was 28,900.

(Preparation of aqueous dispersion of poly (N-propionylethyleneimine) modified silicone)
The final products obtained in Production Example 1 and Production Example 2 were dissolved in ethanol to prepare a 12% by mass aqueous dispersion by solvent substitution.

Examples 1-10 and Comparative Examples 1-5
When a solid powder foundation with the composition shown in Table 1 is manufactured and molded at a molding pressure of 2.3 kg / cm ² , moldability (no chipping, uniformity of pressed surface), no swelling, and when pressed with a finger The softness, powder removal, smoothness at the time of application, and smoothness at the time of application were evaluated. The results are also shown in Table 1.

(Production method)
Using a Henschel mixer, an oil agent was added to the components (A), (C) and other powders to prepare a bulk of the mixture. Next, the aqueous dispersion of the component (B) was added to the mixture of the powder and the oil agent and mixed. Approximately 20 g of this mixture is filled in an aluminum inner plate having a diameter of 75 mm and a depth of 7 mm at a molding pressure of 2.3 kg / cm ² , press-molded, and then dried at 50 ° C. and normal pressure for 3 hours to form a solid powder foundation. Obtained.

(Evaluation method)
(1) Moldability (no chipping):
5; There is no chipping in the press molded product.
4; There is almost no chipping in the press molded product.
3; The press-molded product is slightly chipped.
2; The press-molded product is chipped.
1; The press-molded product has a large chip.

(2) Moldability (uniformity of pressed surface):
5; The pressed surface is uniform and the texture is quite fine.
4; The pressed surface is uniform and the texture is fine.
3; The pressed surface is uniform and the texture is slightly fine.
2; The pressed surface is uneven and the texture is slightly rough. 1; The pressed surface is uneven and the texture is rough.

(3) No bulge:
5; There is no change in the thickness of the solid powder foundation after press molding.
4; The solid powder foundation after press molding is slightly swollen.
3; The solid powder foundation after press molding is slightly swollen.
2; The solid powder foundation after press molding is swollen.
1; The solid powder foundation after press molding is considerably swollen.

(4) Softness when pressed with a finger:
5; The solid powder foundation is fairly soft when pressed with a finger from above.
4; Soft when the solid powder foundation is pressed with a finger from above.
3; Slightly soft when the solid powder foundation is pressed with a finger from above.
2; The solid powder foundation is not very soft when pressed with a finger from above.
1; The solid powder foundation is not soft at all when pressed with a finger from above.

(5) Powder removal when the press surface is slid with a finger:
A; It can be taken just right.
B; Hard to remove.
C; Too much.

(6) Smoothness at the time of application:
5; The feel at the time of application is quite smooth.
4; Smooth feel when applied.
3; The feel when applied is slightly smooth.
2; The feel at the time of application is not very smooth.
1; The feel at the time of application is not smooth.

(7) Smooth feeling at the time of application:
5; There is a considerable feeling of smoothness when applied.
4; There is a smooth feel when applied.
3; There is a slight feeling of smoothness when applied.
2; There is not much smoothness when applied.
1; There is no smooth feeling when applied.

Claims (4)

The following components (A), (B) and (C):
(A) Spherical silicone resin elastic powder 11-70% by mass,
(B) The following general formula (1);

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3).
It is an organopolysiloxane formed by binding poly (N-acylalkyleneimine) segments consisting of repeating units represented by.
The poly (N-acylalkyleneimine) segment has a number average molecular weight of 500 to 4000 and
The mass average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments is 1000-40,000.
The mass average molecular weight of the organopolysiloxane segment constituting the main chain is 1500 to 20000.
Organopolysiloxane 1 to the mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkyleneimine) segment (b) is 65/35 to 95/5. 6% by mass
(C) Synthetic phlogopite and synthetic phlogopite selected from iron-containing synthetic phlogopite having an iron content of 0.5 to 10% by mass in terms of iron oxide 1 to 25% by mass.
A solid powder cosmetic containing, and the mass ratio (B) / (C) of the component (B) to the component (C) is 0.1 to 0.7. The solid powder cosmetic according to claim 1, wherein the component (A) is a silicone resin-coated silicone rubber elastic powder. The solid powder cosmetic according to claim 1 or 2, wherein the mass ratio (A) / (C) of the component (A) to the component (C) is 1 to 40. The solid powder cosmetic according to any one of claims 1 to 3, wherein the average particle size of the component (C) is 5 to 100 μm.