JP5833476B2 - Cosmetics - Google Patents

Description

  The present invention relates to a cosmetic.

  Conventionally, various cosmetics that do not easily lose makeup and have excellent makeup have been studied. For example, cosmetics containing at least one of zinc oxide and zinc carbonate having a specific surface area (Patent Document 1), and fluorine-modified silicones. And a cosmetic (patent document 2) in which zinc white having a specific surface area is blended.

Japanese Patent Laid-Open No. Sho 61-236708 JP-A-7-277914

The present inventor makes zinc oxide gel on the skin, so when applying cosmetics containing zinc oxide, the skin feels dry and tight as time passes, I found the problem that there was a sense of incongruity.
An object of the present invention is to provide a cosmetic that suppresses the feeling of dryness and tension of the skin even after a long time has elapsed after application, and adheres uniformly to the skin.

  The present inventor has found that a cosmetic that solves the above problems can be obtained by using a combination of fine particle zinc oxide, trimethylsiloxysilicic acid and hyaluronic acid and / or a salt thereof.

The present invention includes the following components (A), (B) and (C):
(A) Trimethylsiloxysilicic acid 0.2-15% by mass,
(B) fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g,
(C) Hyaluronic acid and / or salt thereof 0.005 to 0.12% by mass
The mass proportions of components (A) and (B) are (A) / (B) = 0.02-3, and the mass proportions of components (B) and (C) are (B) / (C) = 80-4000 cosmetics are provided.

  The cosmetic of the present invention can be applied smoothly and evenly on the skin with a feeling of dryness and tension of the skin being suppressed even after a lapse of time after application.

The trimethylsiloxysilicic acid of the component (A) used in the present invention is not limited as long as it is usually used in cosmetics, and any compound can be used, and it is a compound having a crosslinked structure with a siloxane structure as the main skeleton. , [(CH ₃ ) ₃ SiO _1/2 ] _X [SiO ₂ ] _Y (X is 1 to 3, Y is 0.5 to 8).
In addition, trimethylsiloxysilicic acid is preferably one having a molecular weight of 1000 to 10,000, more preferably 2000 to 9000, and still more preferably 3000 to 6000, from the viewpoint of feeling of use and longevity.
As a commercial item of component (A), KF-7312T, KF-7312J, and KF-7312K (manufactured by Shin-Etsu Chemical Co., Ltd.) previously dissolved in a solvent can be suitably used.

  Component (A) can be used singly or in combination of two or more, and the lower limit is 0.2% by mass or more and 0.5% by mass or more with respect to the entire cosmetic from the viewpoint of feeling of use and longevity. Is preferable, and 2 mass% or more is more preferable. Moreover, an upper limit is 15 mass% or less, 10 mass% or less is preferable and 8 mass% or less is more preferable. If these viewpoints are put together, it is 0.2-15 mass%, it is preferable to contain 0.5-10 mass%, and it is more preferable to contain 2-8 mass%.

Particulate zinc oxide component (B) used in the present invention has a specific surface area be of 10 to 100 m ² / g, preferably from 15~95m ² / g. By using the fine particle zinc oxide having such a specific surface area, the cosmetic durability is excellent and a good feeling of use can be obtained.

  The finely divided zinc oxide of component (B) can be used as it is, but if necessary, it is subjected to water and / or oil repellent treatment with silicone, metal soap, lecithin, N-acylamino acid, fluorine compound, etc. Can also be used. From the standpoint of preventing makeup collapse and improving the dispersibility of the fine zinc oxide in the cosmetic, a silicone-treated one is preferred, and a silicone treatment using methylhydrogenpolysiloxane is more preferred. These processes can be performed by a normal method.

  Component (B) can be used singly or in combination of two or more, and the lower limit is preferably 0.1% by mass or more, and more preferably 1% by mass or more, based on the feeling of use and makeup. Preferably, 5 mass% or more is more preferable. Further, the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 12% by mass or less. When these viewpoints are put together, 0.1 to 20% by mass is preferable, 1 to 15% by mass is more preferable, and 5 to 12% by mass is more preferable.

  In the present invention, the mass ratio (A) / (B) of the components (A) and (B) suppresses the dryness and crispness of the skin even when time passes and is applied smoothly and uniformly to the skin. Therefore, the lower limit is 0.02 or more, preferably 0.05 or more. Moreover, an upper limit is 3 or less, and 1 or less is preferable. When these viewpoints are put together, (A) / (B) = 0.03 to 3, and preferably 0.05 to 1.

The component (C) hyaluronic acid used in the present invention is a kind of acidic mucosaccharide, which is a linked polysaccharide in which β-DN-acetylglucosamine and β-D-glucuronic acid are alternately bonded, When dissolved in, a highly transparent solution can be obtained. Examples of the salt include sodium and potassium, and sodium is preferable.
As hyaluronic acid and its salt, commercially available products can be used, and those extracted from animal tissues and those produced by fermentation by culturing microorganisms can also be used. Examples of the fermentation method include a method using Streptococcus zooepidemic-us, a kind of streptococci.

The molecular weight of hyaluronic acid and its salt is preferably 30,000 to 3,000,000, more preferably 50,000 to 2,500,000 from the viewpoint of suppressing the feeling of tightness of the skin and improving the adhesion between the powder and the skin. 750,000 to 2 million are more preferable. Hydrolyzed hyaluronic acid and hyaluronic acid salts can also be used.
Although the measuring method of molecular weight is not limited, For example, the intrinsic viscosity is calculated | required from dynamic viscosity, The method of converting this intrinsic viscosity into molecular weight, the simple measuring method by a liquid chromatography, etc. are mentioned.
Of hyaluronic acid and hyaluronate, sodium hyaluronate is preferable from the viewpoints of solubility in water, feeling of use on the skin, and the like.

  Ingredient (C) can be used alone or in combination of two or more thereof, suppresses the feeling of tightness of the skin, improves the adhesion between the powder and the skin, and improves the makeup paste, so that the entire cosmetic is improved. The lower limit is 0.005% by mass or more, preferably 0.007% by mass or more, and more preferably 0.01% by mass or more. Moreover, an upper limit is 0.12 mass% or less, 0.1 mass% or less is preferable and 0.07 mass% or less is more preferable. If these viewpoints are put together, it is 0.005-0.12 mass%, it is preferable that it is 0.007-0.1 mass%, and 0.01-0.07 mass% is more preferable.

  In the present invention, the mass ratio of the components (B) and (C) is such that (B) / (C) is applied smoothly and uniformly to the skin, suppressing the dryness and crispness of the skin over time. Therefore, the lower limit is 80 or more, preferably 300 or more. Moreover, an upper limit is 4000 or less, and 2000 or less is preferable. When these viewpoints are put together, (B) / (C) = 80 to 4000, and 300 to 2000 is more preferable.

  In the present invention, the mass ratios of the components (A) and (C) are such that (A) / (C) suppresses the dryness and crispness of the skin even when time passes, and is smooth and uniform on the skin. From the standpoint of coating, the lower limit is preferably 4 or more, and more preferably 40 or more. Further, the upper limit is preferably 4000 or less, and more preferably 1000 or less. When these viewpoints are put together, (A) / (C) = 4 to 4000, and further preferably 40 to 1000.

The cosmetic of the present invention may further contain (D) a hydrophobized powder excluding component (B).
In addition, the component (D) used by this invention excludes a component (B), and does not contain a component (B).
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, fluorine compound treatment and silicone treatment are preferred, and fluorine compound treatment and silicone treatment may be used in combination. In that case, the lower limit of the powder treated with the fluorine compound is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, with respect to the whole component (C). Even more preferably,

  Examples of the fluorine compound used to treat the powder include perfluoroalkyl group-containing phosphate esters (US Pat. No. 3,632,744), monoesters and diesters of fluoroalkyl phosphate diethanolamine salts (JP-A-62). No.-250074), a resin having a perfluoroalkyl group (Japanese Patent Laid-Open No. 55-167209), a tetrafluoroethylene resin, a perfluoroalcohol, a perfluoroepoxy compound, a sulfoamide fluorophosphate, a perfluorosulfate, Examples thereof include perfluorocarboxylates, perfluoroalkylsilanes (JP-A-2-218603), compounds having a perfluoropolyether group (JP-A-8-33928), and perfluoroalkylsilanes are preferred.

As the fluorine compound, tridecafluorooctyltriethoxysilane represented by the following formula is preferable.
F ₃ C— (CF ₂ ) ₅ — (CH ₂ ) ₂ —Si— (OCH ₂ CH ₃ ) ₃
Among the fluorine compounds for surface-treating the powder, by using the powder surface-treated with tridecafluorooctyltriethoxysilane, the stability is excellent, the skin is familiar, and a moist feeling can be obtained. As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.

The powder to be treated is not particularly limited as long as it is an extender pigment or a color pigment used in ordinary cosmetics, for example, silicic acid, silicic anhydride, magnesium silicate, talc, sericite, mica, kaolin, Bengala, clay, bentonite, mica, titanium-coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, titanium oxide, zinc oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine , Inorganic powders such as chromium oxide, chromium hydroxide, calamine, carbon black, and composites thereof; polyamide, nylon, polyester, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, Acrylic resin, melami Organic powders such as resins, epoxy resins, polycarbonate resins, divinylbenzene / styrene copolymers, silk powder, cellulose, long-chain alkyl phosphate metal salts, N-mono long-chain alkyl acyl basic amino acids, and complexes thereof; Furthermore, the composite powder of the said inorganic powder and organic powder etc. are mentioned.
The shape of the powder to be treated may be any shape, such as a spherical shape, a plate shape, an indeterminate shape, and among them, the spherical powder is preferable because it spreads uniformly on the skin and does not feel dry for a long time.

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

  Although the treatment amount of the fluorine compound varies depending on the powder, the lower limit is preferably 0.05% by mass or more and more preferably 0.1% by mass or more with respect to 100% by mass of the fluorine-treated powder of the component (D). Moreover, 50 mass% or less is preferable and, as for an upper limit, 20 mass% or less is more preferable. If these viewpoints are put together, it is preferable that it is 0.05-50 mass%, and it is more preferable to process 0.1-20 mass%. If it is this processing amount, since water repellency and oil repellency will fully express and a touch is also favorable, it is preferable.

The powder of component (D) has an average particle size of preferably 0.1 to 20 μm, more preferably 0.1 to 15 μm, and more preferably 1 to 10 μm from the viewpoint of powderiness and finish at the time of application. Is more preferable.
In the present invention, the particle diameter of the component (D) is measured with an electron microscope observation and a particle size distribution measuring device by a laser diffraction / scattering method. Specifically, in the case of the laser diffraction / scattering method, measurement is performed with a laser diffraction / scattering particle size distribution analyzer (for example, LA-920, manufactured by Horiba, Ltd.) using ethanol as a dispersion medium.

The powder of component (D) preferably has a spherical shape. The spherical shape refers to a powder having a substantially spherical shape, and may be a spheroid, a spherical powder having irregularities on the surface, or the like, and does not need to be a perfect sphere.
The spherical powder of component (D) is not particularly limited as long as it is used in ordinary cosmetics. For example, polyamide powder, nylon powder, polyester powder, polyethylene powder, polytetrafluoroethylene powder, polypropylene powder , Polystyrene powder, benzoguanamine powder, polymethylbenzoguanamine powder, polymethyl methacrylate powder, polyurethane powder, vinyl resin, fluorine resin, acrylic resin, melamine resin; Silicone powder;
Poly (meth) acrylic acid, such as butyl acrylate / vinyl acetate copolymer, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, (lauryl methacrylate / ethylene glycol dimethacrylate) copolymer, Cross-linked or non-crosslinked type such as powder of one or more kinds of polymers or copolymers selected from sodium poly (meth) acrylate, poly (meth) acrylic ester, poly (meth) acrylate alkylene glycol The organic spherical powder is mentioned.
Among these, silicone powder such as nylon powder, polyurethane powder, silicone elastomer powder crosslinked with dimethyl silicone and polymethylsilsesquioxane powder is preferable.

  Component (D) can be used singly or in combination of two or more, and the lower limit is preferably 0.1% by mass or more with respect to the entire cosmetic from the viewpoint of feeling of use, makeup paste and makeup retention. More preferably, 5 mass% or more is more preferable, 1 mass% or more is further more preferable, and 2 mass% or more is further more preferable. Moreover, 30 mass% or less is preferable, as for an upper limit, 25 mass% or less is more preferable, 20 mass% or less is more preferable, and 15 mass% or less is more preferable. If these viewpoints are put together, it is preferable to contain 0.1-30 mass%, 0.5-25 mass% is more preferable, 1-20 mass% is further more preferable, and 2-15 mass% is contained. Is even more preferable.

  The cosmetic of the present invention further includes (E) at least two silicon atoms of the organopolysiloxane segment constituting the main chain via an alkylene group containing a hetero atom, the following general formula (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 mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is 80/20 to 95/5,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 10,000 to 40,000,
An organopolysiloxane having a weight average molecular weight of 50,000 to 150,000 in the organopolysiloxane segment constituting the main chain can be contained, and more excellent stability can be obtained.

  The poly (N-acylalkyleneimine) segment is bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a hetero atom. Further, it is preferably bonded to one or more silicon atoms excluding both ends of the organopolysiloxane segment via the alkylene group, and bonded to two or more silicon atoms excluding both ends via the alkylene group. More preferably. That is, the organopolysiloxane of component (E) is a graft polymer having a poly (N-acylalkyleneimine) segment composed of at least two 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 include a chain alkyl group or a branched or alkyl group having 3 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  In the general formula (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 80/20 to 95/5, and is preferably 83/17 to 93/7 from the viewpoint of excellent stability, adhesion to the skin and adhesion to the skin. Preferably, it is 85/15 to 90/10.
In this specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of component (E) 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 (E), the weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments (hereinafter also simply referred to as “MWg”) is in the range of 10,000 to 40,000. From the viewpoint of the flexibility of the film and the orientation to the oil-water interface, it is more preferably 15000 to 35000, and further preferably 18000 to 32000.

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

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

  The weight average molecular weight (hereinafter also simply referred to as “MWsi”) of the organopolysiloxane segment constituting the main chain is 50,000 to 150,000, preferably from 70000 to 130,000, more preferably from the viewpoint of flexibility and adhesion to the skin. 90000-110000. The organopolysiloxane of component (E) 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 the component (E) is preferably 60,000 to 160000, more preferably 80000 to the viewpoint of achieving both adhesion to the skin and emulsion stability. It is 140,000, More preferably, it is 100,000-120,000. 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 large deformable amount, the organopolysiloxane of component (E) remarkably improves plasticity when heated to a temperature range of 50 to 220 ° C., and in the process of returning to room temperature after heating is stopped. It has a characteristic thermoplasticity that immediately restores elasticity.

  The organopolysiloxane of component (E) 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 sulfate is preferably used.

  Examples of the polymerization solvent include acetates such as ethyl acetate and propyl acetate, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogen solvents such as chloroform and methylene chloride, acetonitrile. , Nitrile solvents such as benzonitrile, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, etc., among which acetates are preferred Is done. The usage-amount of a solvent is 20-2000 mass parts normally with respect to 100 mass parts of cyclic imino ether (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 making it react, the organopolysiloxane of a component (E) 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 50,000 to 150,000 from the viewpoint of solubility of the resulting organopolysiloxane in a polar solvent such as water and ease of handling after dissolution, More preferably, it is 70000-130,000, More preferably, it is 90000-110,000.

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 (E). From this viewpoint and the viewpoint of imparting appropriate hydrophobicity to the main chain, the functional group equivalent is preferably 10,000 to 40,000, more preferably 15,000 to 35,000, and still more preferably 18,000 to 32,000. Here, the functional group equivalent of the modified organopolysiloxane represented by the general formula (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 set to a value in the range of 80/20 to 95/5 from the viewpoint of the elastic modulus and the deformable amount of the resulting organopolysiloxane. From the same viewpoint, 83/17 to 93/7 are more preferable. Preferably, 85/15 to 90/10 are more preferable.

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

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

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

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

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

  Ingredient (E) can be used in one or more types, and from the viewpoint of excellent stability, adhesion to the skin and adhesion to the skin, the lower limit of the total cosmetic is preferably 0.01% by mass or more, 0.1 mass% or more is more preferable. Further, the upper limit is preferably 10% by mass or less, and more preferably 5% by mass or less. When these viewpoints are combined, 0.01 to 10% by mass is preferable, and 0.1 to 5% by mass is more preferable.

  The content of water used in the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and the upper limit is 70% with respect to the entire cosmetic from the viewpoint of usability and storage stability. The mass% or less is preferable, and 60 mass% or less is more preferable. When these viewpoints are put together, 10-70 mass% is preferable, and it is more preferable to contain 20-60 mass%.

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

  Examples of the surfactant used in the present invention include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Among these, nonionic surfactants are preferable, and polyether-modified silicones are more preferable. From the viewpoint of stably emulsifying the aqueous phase in the oil phase containing the component (A) and other oil agent, the HLB value is preferably 1 or more and 7 or less, and the HLB value is preferably 2 or more and 6 or less.

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

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

  The lower limit of the surfactant content is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, with respect to the entire cosmetic. The upper limit is preferably 6% by mass or less, and more preferably 3% by mass or less. If these viewpoints are put together, 0.1-6 mass% or less is preferable, and it is more preferable to contain 0.2-3 mass%.

  The cosmetics of the present invention include, in addition to the above components, components used in ordinary cosmetics, such as water-soluble and oil-soluble polymers; powders other than the above components; ethanol, polyhydric alcohols, preservatives, antioxidants, It can contain a pigment, a thickener, a pH adjuster, a fragrance, an ultraviolet absorber, a moisturizer, a blood circulation promoter, a cooling agent, an antiperspirant, a disinfectant, a skin activator, and the like.

  The cosmetic of the present invention can be produced according to a usual method, and may be any emulsion type such as a water-in-oil type, an oil-in-water type, or a two-layer separation type. Of these, water-in-oil emulsified cosmetics are preferable from the viewpoint of usability. Furthermore, examples of the dosage form include liquid, emulsion, cream, and gel, and emulsion is preferred.

  The cosmetics of the present invention can be produced according to a conventional method, and make-up cosmetics such as makeup foundations, liquid foundations, oily foundations, powder foundations, lipsticks, blushers, eye shadows; sunscreen emulsions and sunscreen creams UV protective cosmetics such as Of these, a makeup base and a liquid foundation are preferable.

Examples 1-5, Comparative Examples 1-4
Producing liquid foundations having the composition shown in Table 1 and immediately after applying each liquid foundation, "feels smooth on skin", "feels even on skin" and "the skin after application does not feel dry" Further, “no skin dryness” and “no tension” after 8 hours from application were evaluated. The results are also shown in Table 1.

(Production method)
About Examples 1-5 and Comparative Examples 1-4, the whole quantity is measured with a scale of 100 g. The oil phase (containing the active agent) containing the component (A) is preliminarily dispersed using a disper (500 r / min, 5 minutes). Next, the powder phase containing the components (B) and (D) is dispersed in the oil phase (1500 r / min, 10 minutes) to confirm that the powder phase is uniformly dispersed. Using an oil phase in which the powder phase is uniform, gradually add an aqueous phase while stirring with a disper (450 r / min), then add an ethanol phase to emulsify and hold the emulsification, and then a homomixer The viscosity was adjusted (3000 r / min) and defoamed to obtain a liquid foundation.

(Evaluation method)
Five expert panelists evaluated “feels smooth on skin”, “feels even on skin” and “no dryness on the skin after application” immediately after applying each liquid foundation to the skin with a sponge. Furthermore, after 8 hours from the application, “the skin does not feel dry” and “the skin does not feel tight” were evaluated according to the following criteria. A result is shown by the integrated value of 5 persons.
4: I think so.
3: I think so.
2: I think so.
1: I don't think so.

Test example (evaluation when using powder foundation)
Five specialist panelists applied the liquid foundations of Examples 1 and 2 to the skin with a sponge, and then applied the powder foundation (Sophina Fine Fit Powder Foundation UV, manufactured by Kao Corporation) immediately after applying “smooth skin” Evaluates “feeling of sticking”, “feeling of evenly touching the skin” and “no skin dryness after application”, and “no skin dryness” and “tasticity” 8 hours after application “No” was evaluated according to the same criteria as in Examples 1 to 5. The results are shown in Table 2 as the integrated values of five people.

Claims (6)

The following components (A), (B) and (C):
(A) Trimethylsiloxysilicic acid 0.2-15% by mass,
(B) fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g,
(C) Hyaluronic acid and / or salt thereof 0.005 to 0.12% by mass
The mass proportions of components (A) and (B) are (A) / (B) = 0.02-3, and the mass proportions of components (B) and (C) are (B) / (C) = Cosmetics with 80-4000.   The cosmetic according to claim 1, comprising 0.1 to 20% by mass of component (B).   The cosmetic according to claim 1 or 2, wherein the mass ratio of the components (A) and (C) is (A) / (C) = 4 to 4000.   The cosmetic according to any one of claims 1 to 3, wherein the component (C) has an average molecular weight of 30,000 to 3,000,000.   Furthermore, cosmetics of any one of Claims 1-4 containing the hydrophobization treatment powder except (D) component (B). Furthermore, (E) at least two silicon atoms of the organopolysiloxane segment constituting the main chain, via an alkylene group containing a hetero atom, the following general formula (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 mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is 80/20 to 95/5,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 10,000 to 40,000,
The cosmetic according to any one of claims 1 to 5, comprising an organopolysiloxane having a weight average molecular weight of 50,000 to 150,000 of the organopolysiloxane segment constituting the main chain.