JP5872720B2 - Skin cosmetics - Google Patents

Description

  The present invention relates to a skin cosmetic.

As techniques for preventing ultraviolet rays using cosmetics, there are those described in Patent Documents 1 to 3.
Patent Document 1 (Japanese Patent Application Laid-Open No. 11-343224) describes a cosmetic obtained by filling a pressure-resistant container with an aerosol composition containing ethanol and a specific compound.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2012-140342) discloses an oil-in-water emulsion sunscreen cosmetic containing an acrylic acid / alkyl methacrylate copolymer, a specific block-type alkylene oxide derivative, an ultraviolet absorber, an oil and water. The technology about is described. Further, it is described that when a block-type alkylene oxide derivative having a specific structure is blended, an oil-in-water emulsion sunscreen cosmetic having excellent stability and excellent usability can be obtained.

  Patent Document 3 (Japanese Patent Laid-Open No. 9-227331) describes an ultraviolet protective cosmetic containing an ultraviolet protective agent and poly (N-acylalkylenimine) -modified silicone.

JP-A-11-343224 JP 2012-140342 A JP-A-9-227331

  As a result of the study by the present inventors, by including a large amount of ethanol in the cosmetic as in the technique described in Patent Document 1, a favorable feeling of use can be obtained in that a familiarity and a high cooling feeling can be obtained, It has been found that there is room for improvement in that the durability of the UV protection effect is poor.

  Therefore, the present invention provides a skin cosmetic that is compatible with both the durability of the UV protection effect and the contradictory effect of improving the feeling of use because it is less sticky and has a smooth feeling. provide.

According to the invention, the following components (A), (B), (C), (D1), (D2) and (E):
(A) UV protection agent,
(B) a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as structural units,
(C) an alcohol having 1 to 4 carbon atoms,
(D1) a powder having a number average particle size of 1 μm or more and 10 μm or less,
(D2) a skin cosmetic comprising a powder having a number average particle size of more than 10 μm and 25 μm or less, and (E) a propellant,
In all components except the component (E) of the skin cosmetic, the content of the component (C) is 40% by mass or more and 95% by mass or less,
Provided is a skin cosmetic in which the mass ratio of the component (D1) and the component (D2) in the skin cosmetic is (component (D1) / component (D2)) = 1/2 to 20/1 Is done.

  According to the present invention, there is provided a skin cosmetic that is compatible with the durability of the UV protection effect and the contradictory effect of improving the feeling of use that the stickiness is suppressed and has a smooth feeling, and that is excellent in powder redispersibility. Can be obtained.

In the present embodiment, the skin cosmetic is a composition containing the following components (A), (B), (C), (D1), (D2) and (E).
(A) UV protection agent,
(B) a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as structural units,
(C) an alcohol having 1 to 4 carbon atoms,
(D1) a powder having a number average particle size of 1 μm or more and 10 μm or less,
(D2) Powder whose number average particle diameter is larger than 10 μm and 25 μm or less, and (E) propellant Further, the content of component (C) is 40 mass in all components except component (E) of skin cosmetics. % To 95% by mass, and the mass ratio of the component (D1) to the component (D2) in the skin cosmetic is (component (D1) / component (D2)) = 1/2 to 20/1 .

Hereinafter, each component will be described with specific examples. Each component can be used alone or in combination of two or more.
In the present embodiment, the feeling of use means that when cosmetics are used, there is no stickiness and a smooth feeling is felt.

(Ingredient (A))
Ingredient (A) is a UV protection agent. As the component (A), any of commonly used ultraviolet scattering agents and organic ultraviolet absorbers can be suitably used. Among these, as a specific example of the ultraviolet scattering agent, the number average particle diameter is, for example, 1 nm or more, preferably 10 nm or more, more preferably 30 nm or more, and for example, 500 nm or less, preferably 300 nm or less, more Titanium oxide, fine particle titanium oxide (such as those described in JP-A-57-67681), zinc oxide, fine zinc white (such as those described in JP-A-62-228006), preferably 200 nm or less Flaky zinc oxide (such as those described in JP-A-1-175921), iron oxide, fine-particle iron oxide, cerium oxide, zirconium oxide, and the like. These include silicone, metal soap, N-acyl glutamic acid, It may be surface-treated with a fluoroalkyl phosphate ester or the like. These shapes and forms are not limited and may be used in the form of sol.

The organic ultraviolet absorber is preferably an oil-soluble one. A benzoic acid ultraviolet absorber, an anthranilic acid ultraviolet absorber, a salicylic acid ultraviolet absorber, a cinnamic acid ultraviolet absorber, a benzophenone ultraviolet absorber, a triazine. System ultraviolet absorbers and the like.
As benzoic acid ultraviolet absorbers, paraaminobenzoic acid (hereinafter abbreviated as PABA), glyceryl PABA, ethyldihydroxypropyl PABA, N-ethoxylate PABA ethyl ester, N-dimethyl PABA ethyl ester, N-dimethyl PABA butyl ester, N -Dimethyl PABA amyl ester, octyl dimethyl PABA, diethylaminohydroxybenzoyl hexyl benzoate and the like. Paraaminobenzoic acid and diethylaminohydroxybenzoyl hexyl hexyl are preferable, and diethylaminohydroxybenzoyl hexyl hexyl is more preferable from the viewpoint of suppressing stickiness while enhancing the ultraviolet absorption effect.
An anthranilic acid type ultraviolet absorber includes homomenthyl-N-acetylanthranilate.
Examples of salicylic acid ultraviolet absorbers include amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, and the like.
Cinnamic acid UV absorbers include octyl cinnamate, ethyl-4-isopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxycinnamate, isopropyl- p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β -Phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl diparamethoxycinnamate and the like. Of these, octylcinnamate and 2-ethylhexyl-p-methoxycinnamate are preferable, and 2-ethylhexyl-p-methoxycinnamate is more preferable from the viewpoint of suppressing stickiness while enhancing the ultraviolet absorption effect. preferable.
As benzophenone-based ultraviolet absorbers, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n -Octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc. are mentioned.
Examples of triazine ultraviolet absorbers include 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, 2,4-bis-[{4- (2 -Ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine and the like.
Others include 3- (4′-methylbenzylidene) -dl-camphor, 3-benzylidene-dl-camphor, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2′-hydroxy- 5-methylphenylbenzotriazole, 2- (2′-hydroxy-5-t-octylphenyl) benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4′-t-butyldibenzoylmethane, 5- (3 3-dimethyl-2-norbornidene) -3-pentan-2-one, benzene bis-1,3-diketone derivatives described in JP-A-2-212579, benzoylpinacolone derivatives described in JP-A-3-220153, etc. Is mentioned.

  Component (A) is at least selected from benzoic acid-based UV absorbers, benzophenone-based UV absorbers, cinnamic acid-based UV absorbers, and triazine-based UV absorbers from the viewpoint of suppressing stickiness while enhancing the UV protection effect. 1 type is preferable, it is more preferable to contain at least 1 sort (s) chosen from a benzoic acid type ultraviolet absorber, a cinnamic acid type ultraviolet absorber, and a triazine type ultraviolet absorber, A benzoic acid type ultraviolet absorber More preferably, it contains at least two selected from cinnamic acid-based UV absorbers and triazine-based UV absorbers.

  The ultraviolet protective agent of component (A) can be used singly or in combination of two or more, and the combination and blending amount are determined, for example, according to the ultraviolet protective effect of the skin cosmetic. From the viewpoint of further developing the UV protection effect of the skin cosmetic, the content of the component (A) is, for example, 0.1% by mass or more, preferably 1% or more in all components except the component (E) of the skin cosmetic. % By mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more. From the viewpoint of further improving the feeling of use of the skin cosmetic, that is, from the viewpoint of suppressing stickiness and imparting a smooth feeling, the blending amount of the component (A) is the entire amount excluding the component (E) of the skin cosmetic. In a component, it is 30 mass% or less, for example, Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 18 mass% or less.

  In addition, as component (A), when 2-ethylhexyl-p-methoxycinnamate and diethylaminohydroxybenzoyl hexyl benzoate are used in combination, 2-ethylhexyl-p-methoxycinnamate with respect to hexyl diethylaminohydroxybenzoyl benzoate The ratio is, for example, 10/1 or less in terms of mass ratio (2-ethylhexyl-p-methoxycinnamate / diethylaminohydroxybenzoyl hexyl benzoate) from the viewpoint of suppressing stickiness and further developing the UV protection effect. , Preferably 8/1 or less, more preferably 7/1 or less, for example 2/1 or more, preferably 3/1 or more, more preferably 4/1 or more.

(Ingredient (B))
The component (B) is a polymer having a hydrophilic segment having N-acylalkylenimine as a repeating unit and an organopolysiloxane segment as constituent units.

In the component (B), the mass ratio of the organopolysiloxane segment to the hydrophilic segment having N-acylalkyleneimine as a repeating unit (organopolysiloxane segment a / hydrophilic segment b having N-acylalkyleneimine as a repeating unit) is From the viewpoint of improving the balance between the persistence of the UV protection effect of cosmetics and the suppression of stickiness, for example, a / b = 45/55 or more, preferably 65/35 or more, more preferably 85/15 or more. Yes, for example, 94/6 or less, preferably 92/8 or less, more preferably 90/10 or less.
In the present specification, the weight ratio of the organopolysiloxane of the present invention is dissolved in deuterated chloroform at 5 wt%, by nuclear magnetic resonance ⁽¹ H-NMR) analysis, alkyl groups in the organopolysiloxane segment Or the value calculated | required from the integral ratio of the methylene group in a phenyl group and a poly (N-acyl alkyleneimine) segment.

In the component (B), the weight average molecular weight of the organopolysiloxane segment is selected from the viewpoints of improving the durability of the UV protection effect of the cosmetic, the viewpoint of suppressing stickiness, the viewpoint of improving the ease of extending the cosmetic, and the organic UV absorption From the viewpoint of improving the compatibility with the agent, it is, for example, 1 × 10 ⁴ or more, preferably 2 × 10 ⁴ or more, more preferably 3.5 × 10 ⁴ or more, and for example, 3 × 10 ⁵ or less. Yes, preferably 2 × 10 ⁵ or less, more preferably 1.5 × 10 ⁵ or less.
Since the organopolysiloxane constituting the main chain has a skeleton common to the modified organopolysiloxane that is the raw material compound, the weight average molecular weight of the organopolysiloxane constituting the main chain is approximately equal to the average molecular weight of the modified organopolysiloxane. Are the same.
Here, the weight average molecular weight of the modified organopolysiloxane is a polystyrene equivalent weight average molecular weight measured under the following conditions by gel permeation chromatography (GPC).
Column: Super HZ4000 + Super HZ2000 (manufactured by Tosoh Corporation)
Eluent: 1 mM triethylamine / THF
Flow rate: 0.35 mL / min
Column temperature: 40 ° C
Detector: UV detector Sample: 50 μL

In addition, in the component (B), the number average molecular weight of the poly (N-acylalkyleneimine) segment is determined from the viewpoint of improving the durability of the UV protection effect of the cosmetic, the viewpoint of suppressing stickiness, and the ease of extending the cosmetic. From the viewpoint of improving the compatibility with the organic ultraviolet absorber, and from the viewpoint of increasing the flexibility of the cosmetic film and the solubility in the solvent, it is, for example, 5 × 10 ² or more, preferably 7 × 10 ^2. As described above, it is more preferably 8 × 10 ² or more, for example, 4 × 10 ³ or less, preferably 3.5 × 10 ³ or less, more preferably 3 × 10 ³ or less.
The number average molecular weight of the poly (N-acylalkylenimine) segment can be measured by the method of calculating from the molecular weight of the N-acylalkyleneimine unit and the degree of polymerization or the GPC measurement method described above. In the form, it means the number average molecular weight measured by the GPC measurement method.

  Specific examples of the polymer of component (B) include those represented by the following general formula (3).

(In the general formula (3), n represents a number of 1 to 5, R ⁹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, m is a degree of polymerization of the monomers, 1 to 1000 of R is 10 to 2000 on average, p is 0 to 20 on average, q is 1 to 20 on average, X ⁻ is a counter ion of quaternary ammonium ion, ethyl sulfate ion, methyl Sulfuric acid ion, chlorine ion, iodine ion, sulfuric acid ion, p-toluenesulfonic acid ion or perchloric acid ion, and a polymerization initiator residue is bonded to the N-terminal of the repeating unit of N-acylalkylenimine. .)
As the polymerization initiator, diethyl sulfate, dimethyl sulfate, hydrochloric acid, hydrogen iodide, sulfuric acid, p-toluenesulfonic acid, perchloric acid and the like are used, and these residues are bonded to the N-terminal after polymerization.

  As the polymer of the component (B), N-propionyl polyethyleneimine / methyl polysiloxane copolymer (POLYSILICONE-9) is preferable. As POLYSILICONE-9, for example, those described in JP2009-256367A can be used.

  In the present embodiment, the content of the component (B) in the skin cosmetic is determined from the viewpoint of improving the sustainability of the smooth feeling and improving the sustainability of the UV protection effect of the cosmetic ( In all components except E), it is 0.1 mass% or more, for example, Preferably it is 0.3 mass% or more, More preferably, it is 0.5 mass% or more, More preferably, it is 0.8 mass% or more. From the viewpoint of suppressing the stickiness of the cosmetic to obtain a smooth feeling, and from the viewpoint of ensuring that the feel during application of the cosmetic is not too heavy and stably obtaining the storage stability of the cosmetic, The content of the component (B) in the content is, for example, 3% by mass or less, preferably 2.5% by mass or less, more preferably 1.5% by mass in all the components excluding the component (E) of the skin cosmetic. It is as follows.

(Ingredient (C))
Component (C) is an alcohol having 1 to 4 carbon atoms.
More specifically, the component (C) is one or more selected from the group consisting of methanol, ethanol, propanol, and butanol, and the viewpoint of improving the solubility and dispersibility of the component (B) and Ethanol is preferable from the viewpoint of improving the handleability when blended into a cosmetic.

Content of the component (C) in skin cosmetics is 40 mass% or more in all the components except a component (E) from a viewpoint of suppressing stickiness, Preferably it is 60 mass% or more.
Further, from the viewpoint of improving the smooth feeling and the sustainability thereof, the content of the component (C) of the skin cosmetic is 95% by mass or less, preferably 90% by mass or less, in all the components except the component (E). It is.
Moreover, in the stock solution comprised by all the components except the component (E) in cosmetics composition, content of a component (C) can be made into the remainder except components other than the component (C) in stock solution. .

(powder)
The skin cosmetic in this embodiment contains components (D1) and (D2) as powder components.
Among these, the component (D1) is a powder having a number average particle size of 1 μm to 10 μm. The component (D2) is a powder having a number average particle size of more than 10 μm and 25 μm or less.

  Here, in this specification, the average particle diameter is a number average particle diameter measured by a light scattering method. The number average particle diameter means a value obtained by arithmetically averaging the particle diameter of each particle.

The powders of components (D1) and (D2) refer to powders having a substantially spherical shape, and may be spheroids, spherical powders with irregularities on the surface, etc., and must be perfectly spherical. And not.
The shapes of components (D1) and (D2) may be the same or different.

The materials of the components (D1) and (D2) are not limited as long as they are used in ordinary cosmetics. Specific examples of the components (D1) and (D2) include polyamide powder, nylon powder, polyester powder, polyethylene. Powder, Polypropylene powder, Polystyrene powder, Benzoguanamine powder, Polymethylbenzoguanamine powder, Polymethylmethacrylate powder, Polyurethane powder, Vinyl resin, Fluorine resin, Acrylic resin, Melamine resin Silicone powder such as sun powder; butyl acrylate / vinyl acetate copolymer, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, 1 type selected from poly (meth) acrylic acid, poly (meth) acrylic acid sodium, poly (meth) acrylic acid ester, poly (meth) acrylic acid alkylene glycol, such as ethylene glycol / ethylene methacrylate copolymer) Alternatively, a crosslinked or non-crosslinked organic spherical powder such as a powder of two or more kinds of polymers or copolymers may be mentioned.
The materials of components (D1) and (D2) may be the same or different.
Hereinafter, the structures of the components (D1) and (D2) will be described more specifically.

  The number average particle size of the component (D1) is 1 μm or more, preferably 2 μm or more, more preferably 3 μm from the viewpoint of improving the feeling of freezing when the cosmetic is applied, that is, from the viewpoint of improving the dry feeling. That's it. From the above viewpoint, the number average particle diameter of the component (D1) is 10 μm or less, preferably 9 μm or less, and more preferably 8 μm or less.

  As the component (D1), nylon powder, ethylene powder, silicone powder, polymethyl methacrylate are used from the viewpoint of suppressing stickiness, improving the smoothness and sustainability, and improving the redispersibility of the powder. One or two or more polymer or copolymer powders selected from powder, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, alkylene glycol acrylate and alkylene glycol methacrylate are preferred, nylon powder, silicone One or two or more polymer or copolymer powders selected from powder, polymethyl methacrylate powder, alkyl acrylate, and alkyl methacrylate are more preferable, and silicone powder is more preferable.

As a component (D1), more specifically, as a silicone powder, KMP-599 (3 μm), KSP-100 (5 μm), KSP-105 (2 μm), KSP-300 (5 μm), X-52-1621 ( 5 μm) (Shin-Etsu Chemical Co., Ltd.);
Tospearl 120A (2 μm), Tospearl 145A (4.5 μm) (above, manufactured by Momentive Performance Materials Japan);
Trefill E506S (4 μm), Trefill E508 (4 μm), BY29-129 (4 μm) (above, manufactured by Toray Dow Corning);
Gantzpearl GMP-0820 (8 μm) (above, as Gantzpearl GMP-0800 (8 μm), polyacrylic acid as Gantzpearl SI-045C (4.5 μm), Gantzpearl SIG-070 (7 μm), alkyl methacrylate Made by Aika Industries);
As a copolymer of alkyl methacrylate and alkylene glycol methacrylate, Matsumoto Microsphere M-201 (4 μm), Matsumoto Microsphere M-305 (8 μm), Matsumoto Microsphere M312 (5.5 μm) (and above, Matsumoto) Manufactured by Yushi Seiyaku)
As the nylon powder, commercially available products such as nylon SP-500 (5 μm) and nylon SP-10 (10 μm) (manufactured by Toray Industries, Inc.) can be used.

  Among them, as the component (D1), silicone powder X-52-1621 (5 μm) (manufactured by Shin-Etsu Chemical Co., Ltd.), Tospearl 145A (4.5 μm) (manufactured by Momentive Performance Materials Japan), Gantz Pearl SI-045C (4.5 μm) (manufactured by Aika Kogyo Co., Ltd.) can provide a smooth feel when applied, that is, it can obtain a better smooth feel and a finish that does not cause white floating. Is preferable.

Next, the component (D2) will be described.
The number average particle diameter of the component (D2) is larger than 10 μm, preferably 11 μm or more, more preferably 13 μm or more, from the viewpoint of improving the familiarity with the skin and improving the redispersibility of the powder. Preferably it is 15 micrometers or more. From the above viewpoint, the number average particle diameter of the component (D2) is 25 μm or less, preferably 24 μm or less, more preferably 23 μm or less.

  The particle size ratio of the component (D1) to the component (D2) ((D1) / (D2)) is excellent in the feeling of freezing when the cosmetic is applied to the skin, that is, the viewpoint of improving the feeling of freezing. From the viewpoint of improving the familiarity with the skin and improving the redispersibility of the powder, it is, for example, 1/2 or less, preferably 1 / 2.5 or less, more preferably 1 / 2.8 or less. More preferably 1/3 or less, for example 1/10 or more, preferably 1/8 or more, more preferably 1/7 or more, and more preferably 1/6 or more.

  As the component (D2), one type selected from nylon powder, ethylene powder, silicone powder, polymethyl methacrylate powder, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, alkylene glycol acrylate, and alkylene glycol methacrylate Two or more kinds of polymer or copolymer powders are preferred, and a copolymer of at least one selected from alkyl acrylate and alkyl methacrylate and at least one selected from alkylene glycol acrylate and alkylene glycol methacrylate More preferred is a powder of a copolymer of alkyl methacrylate and alkylene glycol methacrylate.

As component (D2), more specifically, as a silicone powder, KMP-601 (12 μm), KMP-598 (13 μm), KSP-101 (12 μm) (above, Shin-Etsu Chemical Co., Ltd.);
As alkyl methacrylate, Gantzpearl GM-2000 (20 μm), Gantzpearl GMX-2001 (20 μm), and divinylbenzene-styrene copolymer as Gantzpearl GS-1105 (11 μm) (manufactured by Aika Kogyo Co., Ltd.);
As a copolymer of alkyl methacrylate and alkylene glycol methacrylate, Matsumoto Microsphere M-503 (20 μm) (above, Matsumoto Yushi Seiyaku Co., Ltd.);
As ethylene powder, flow beads CL-2080 (11 μm), flow beads CL-3080 (13 μm) (above, manufactured by Sumitomo Seika Co., Ltd.);
As nylon powder, commercially available products such as nylon TR-1 (13 μm) and nylon TR-2 (20 μm) (above, manufactured by Toray Industries, Inc.) can be used.

  Among them, as the component (D2), Matsumoto Microsphere M-503 (20 μm) (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), which is a copolymer of alkyl methacrylate and alkylene glycol methacrylate, and Gantzpearl GMX-2001 (20 μm). Gantzpearl GM-2000 (20 μm) (manufactured by Aika Kogyo Co., Ltd.) is preferable from the viewpoint of improving the redispersibility of the powder and having good spread at the time of applying the cosmetic.

  In addition, from the viewpoint of improving the smooth feeling and its sustainability, and improving the redispersibility of the powder, the component (D1) or the component (D2) is nylon powder, ethylene powder, silicone powder, polymethyl methacrylate. It may be a powder of one or two or more polymers or copolymers selected from powder, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, alkylene glycol acrylate and alkylene glycol methacrylate.

  Further, as specific examples of the combination of components (D1) and (D2), component (D1) is silicone powder, nylon powder, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, alkylene glycol acrylate and alkylene methacrylate. 1 type or 2 types or more selected from the group consisting of 1 type or 2 types or more of polymer or copolymer powder selected from glycol, and component (D2) is acrylic acid, methacrylic acid, alkyl acrylate, One or more selected from the group consisting of powders of one or more polymers or copolymers selected from alkyl methacrylate, alkylene glycol acrylate and alkylene glycol methacrylate, ethylene powder and nylon powder. is there Seen together is preferable.

  The mass ratio of the component (D1) to the component (D2), that is, the mass ratio of the component (D1) to the component (D2) ((D1) / (D2)) improves the redispersibility of the powder in cosmetics. For example, 20/1 or less, preferably 15/1 or less, and more preferably 10/1 or less, from the viewpoint of making it adhere well to the skin and improving the dry feel (smooth feeling) during application. Yes, more preferably 8/1 or less, for example, 1/2 or more, preferably 1/1 or more, and more preferably 2/1 or more.

In addition, the content of the components (D1) and (D2) in the skin cosmetic according to the present embodiment suppresses the stickiness of the cosmetic during application, and imparts a smooth feel (smooth feeling) to the skin. When all components excluding component (E), that is, the stock solution is 100%, the sum of components (D1) and (D2) is preferably 0.5% by mass or more, for example, and preferably 1% by mass or more. More preferably, it is more preferable to set it as 1.5 mass% or more.
Further, from the viewpoint of maintaining good redispersibility of the powder and suppressing the clogging of the skin cosmetic when the cosmetic is sprayed, the contents of the components (D1) and (D2) in the skin cosmetic are the components ( The total of components (D1) and (D2) when the total component excluding E), that is, the stock solution is 100%, is, for example, 10% by mass or less, preferably 6% by mass or less, more preferably 5% by mass or less, More preferably, it is 4 mass% or less.
In this embodiment, clogging of skin cosmetic when spraying cosmetic refers to any part of the container from the container to the discharge outlet when the cosmetic stored in the container is applied to the skin. In this case, the discharge of cosmetics is suppressed.

  In addition, the ratio of the component (B) to the sum of the components (D1) and (D2) ((B) / ((D1) + (D2))) is preferably in close contact with the skin and maintains the UV protection effect. From the viewpoint of further improving the sustainability of the smooth feeling, the mass ratio is, for example, 0.05 or more, preferably 0.1 or more, more preferably 0.2 or more, more preferably 0.25 or more, 1 or less, preferably 0.8 or less, more preferably 0.75 or less.

(Ingredient (E))
Ingredient (E) is a propellant.
Specific examples of the propellant of component (E) include one or more selected from liquefied natural gas (LPG), dimethyl ether (DME), carbon dioxide gas, nitrogen gas, a mixture thereof, and the like. Further, alternative chlorofluorocarbons such as HFC-152a can be used.
The boiling point of the propellant of component (E) is, for example, −50 ° C. or higher, preferably −40 ° C. or higher, for example, 0 ° C. or lower, preferably −20 ° C. or lower, from the viewpoint of obtaining a good cooling feeling. It is. A further preferred example of component (E) is LPG.

  The content of the propellant of the component (E) in the skin cosmetic is from the viewpoint of obtaining a good cool feeling and from the viewpoint of suitably attaching the cosmetic to the skin and improving the UV protection effect and the feeling of use. Ingredients excluding ingredient (E) in cosmetics, that is, mass ratio of stock solution and propellant composed of components (A) to (C), (D1), (D2) and optional components. Is, for example, 10/90 or more, preferably 20/80 or more, more preferably 30/70 or more, and for example 70/30 or less, preferably 60/40 or less, more preferably 50/50 or less. It is.

  The amount of component (E) is such that the pressure in the pressure-resistant container filled with the skin cosmetic is, for example, 0.15 MPa to 0.40 MPa, preferably 0.18 MPa to 0.35 MPa at a temperature of 25 ° C. Alternatively, it is preferable to adjust the ratio.

Moreover, in this embodiment, skin cosmetics may further contain the following components (F).
(F) Alkylene oxide derivative Gly- [O (PO) m (EO) n- (BO) pH] _{3 represented by the following} general formula (I) (I)
(In the above general formula (I), Gly is a residue obtained by removing a hydroxyl group from glycerin, PO is an oxypropylene group, and EO is an oxyethylene group. M and n are average added moles of PO and EO, respectively. 1 to 50, and the mass ratio of PO to EO (PO / EO) is 1/5 to 5/1, BO is an oxyalkylene group having 4 carbon atoms, p is the average addition of BO (The number of moles and a value of 0.5 to 5.)

  As the component (F), specifically, materials described in JP-A-2006-225324 can be used. That is, the component (F) is obtained by adding propylene oxide (PO) and ethylene oxide (EO) to glycerin at a ratio of 3 to 150 molar equivalents with respect to glycerin, and then converting alkylene oxide of 4 carbon atoms to glycerin. It is obtained by adding at a ratio of 1.5 to 15 molar equivalents. That is, the component (F) is obtained by once synthesizing an adduct of PO and EO and then adding alkylene oxide having 4 carbon atoms in a block form.

  The average added moles of propylene oxide (PO) and ethylene oxide (EO) are each preferably 1 or more from the viewpoint of suppressing the stickiness of the cosmetic and improving the ease of extending the cosmetic. From the same viewpoint, the average added moles of PO and EO are each preferably 50 or less.

  The average added mole number of alkylene oxide (BO) having 4 carbon atoms is preferably 0.5 or more from the viewpoint of suppressing stickiness. Further, from the viewpoint of improving the easiness of extension of the cosmetic and the viewpoint of improving the adhesion of the cosmetic, the average added mole number of BO is preferably 5 or less.

  Examples of the alkylene oxide having 4 carbon atoms include 1,2-butylene oxide, 2,3-butylene oxide, and tetramethylene oxide (tetrahydrofuran). Among these, 1,2-butylene oxide is preferable from the viewpoint of easy availability and reaction control.

When these alkylene oxides are added to glycerin, an addition reaction is performed using an alkali catalyst, a phase transfer catalyst, a Lewis acid catalyst, or the like. In general, it is preferable to use an alkali catalyst such as potassium hydroxide.
From the viewpoint of suppressing the stickiness of cosmetics and improving the ease of extension of cosmetics, the alkylene oxide derivative of component (F) is polyoxybutylene polyoxyethylene polyoxypropylene glycerin (INCI name: PEG / PPG / polybutylene glycol). -8/5/3 glycerin), which is commercially available as Wilbride S-753 from Nippon Oil & Fats.

From the viewpoint of suppressing stickiness, the content of the component (F) in the skin cosmetic is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, in all components except the component (E), More preferably, it is 1 mass% or more, More preferably, it is 1.2 mass% or more.
Further, from the viewpoint of suppressing stickiness and obtaining a smooth feeling of use (smooth feeling), the content of the component (F) in the skin cosmetic is, for example, 3% by mass or less in all components except the component (E). Preferably, it is 2.5 mass% or less.

  Moreover, the mass ratio ((A) / (F)) of the component (A) to the component (F) in the skin cosmetic of the present embodiment obtains a viewpoint of suppressing stickiness and a smooth feeling of use (smooth feeling). From the viewpoint, it is preferably 25/1 or less, more preferably 15/1 or less, further preferably 10/1 or less, preferably 3/1 or more, more preferably 4/1 or more, and further Preferably it is 5/1 or more.

  In addition, the skin cosmetic of the present embodiment includes components other than the components described above, for example, surfactants, oily components, fragrances, moisturizers, beauty ingredients, medicinal ingredients, thickeners, bactericides, pH adjusters, Antioxidants, preservatives, and other components used in ordinary cosmetics can also be included.

Furthermore, in the skin cosmetic of the present embodiment, the content of water is preferably 1% by mass or less in the total composition excluding the component (E) from the viewpoint of obtaining a uniform and good appearance composition. % By mass or less is more preferable, 0.1% by mass or less is more preferable, 0.05% by mass or less is further more preferable, 0.01% by mass or less is further preferable, and substantially 0 is further more preferable.
Further, in the skin cosmetic of the present embodiment, the water content is 1% by mass or more in the total composition excluding the component (E) from the viewpoint of further improving the ultraviolet absorption ability and imparting freshness during use. Is preferable, and 3 mass% or more is more preferable. In addition, from the viewpoint of suppressing stickiness and imparting a refreshing feeling, the content of water in the skin cosmetic is preferably 8% by mass or less, and preferably 7% by mass or less in the total composition excluding the component (E). More preferred.

  In the skin cosmetic of the present embodiment, the content of the thickener is preferably 3% by mass or less, more preferably 2% by mass or less in the total composition excluding the component (E) from the viewpoint of realizing a good spray state. It is preferably 1% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less, and still more preferably 0. By ensuring a good spraying state, unevenness during application to the skin and unevenness of cosmetics can be improved. For this reason, the use feeling of the cosmetics about suppression of stickiness and provision of a smooth feeling, and the sustainability of an ultraviolet-ray protective effect can be improved.

  In the skin cosmetic of the present embodiment, it is also effective to contain a surfactant from the viewpoint of enhancing the dispersibility of the UV protection agent and the powder and further improving the redispersibility of the powder. . From the above viewpoint, the content of the surfactant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably 0.007% by mass or more in the total composition excluding the component (E). Moreover, 0.5 mass% or less is preferable, 0.3 mass% or less is more preferable, and 0.1 mass% or less is further more preferable.

Next, the manufacturing method of the skin cosmetics in this embodiment is demonstrated.
The skin cosmetic in the present embodiment is, for example,
Mixing a component other than the propellant of component (E) and dissolving or dispersing to prepare a stock solution;
Filling the pressure-resistant container with the stock solution obtained in the above step together with the propellant of component (E);
It is manufactured by the method containing.
As the pressure-resistant container, those used for ordinary aerosol preparations can be used.

  In the present embodiment, the components (A) to (C), (D1), (D2) and (E) are used in combination, and the content of the component (C) and the components (D1) and (D2) Since the mass ratio is in a specific range, it is possible to obtain a cosmetic that is excellent in the balance between the preferable feeling of use and the sustainability of the UV protection effect and that is excellent in the redispersibility of the powder in the cosmetic. More specifically, stickiness can be suppressed and a skin cosmetic with a smooth feeling can be obtained.

More specifically, by using the components (B) and (C) in combination, it is possible to improve the balance between the durability of the UV protection effect of the cosmetic and the effect of suppressing stickiness.
Further, as the components (D1) and (D2), by using a plurality of powders having different sizes in a specific combination, unevenness during application to the skin and unevenness of the cosmetic can be improved. For this reason, the use feeling of the cosmetics about suppression of stickiness and provision of a smooth feeling, and the sustainability of an ultraviolet-ray protective effect can be improved. Moreover, the redispersibility of the powder in cosmetics can also be improved.
Moreover, the skin cosmetic of this embodiment can be used suitably, for example as an ultraviolet protection cosmetic.
The skin cosmetic of the present embodiment can be used by applying it to the skin, preferably the face, body, limbs, or the like. Moreover, the skin cosmetics of this embodiment can also be used for scalp and hair.
Moreover, the skin cosmetic of this embodiment can protect ultraviolet rays by applying to skin, can suppress stickiness, and can obtain a further smooth feeling.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

  With respect to the embodiments described above, preferred aspects of the present invention will be further disclosed below.

<1> The following components (A), (B), (C), (D1), (D2) and (E):
(A) UV protection agent,
(B) a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as structural units,
(C) an alcohol having 1 to 4 carbon atoms,
(D1) a powder having a number average particle size of 1 μm or more and 10 μm or less,
(D2) a skin cosmetic comprising a powder having a number average particle size of more than 10 μm and 25 μm or less, and (E) a propellant,
In all components except the component (E) of the skin cosmetic, the content of the component (C) is 40% by mass or more and 95% by mass or less,
The skin cosmetic in which the mass ratio of the component (D1) and the component (D2) in the skin cosmetic is (component (D1) / component (D2)) = 1/2 to 20/1.

<2> In all components except the component (E) in the skin cosmetic, the total content of the component (D1) and the component (D2) is 0.5% by mass or more and 10% by mass or less. The skin cosmetic according to <1>.
<3> (F) The skin cosmetic according to <1> or <2>, further comprising 0.1% by mass or more and 3% by mass or less of an alkylene oxide derivative represented by the following general formula (I):
Gly- [O (PO) m (EO) n- (BO) pH] ₃ (I)
(In the above general formula (I), Gly is a residue obtained by removing a hydroxyl group from glycerin, PO is an oxypropylene group, and EO is an oxyethylene group. M and n are average added moles of PO and EO, respectively. 1 to 50, and the mass ratio of PO to EO (PO / EO) is 1/5 to 5/1, BO is an oxyalkylene group having 4 carbon atoms, p is the average addition of BO (The number of moles and a value of 0.5 to 5.)
<4> Component (A) is one or more selected from the group consisting of an ultraviolet scattering agent and an organic ultraviolet absorber, and has a number average particle diameter of 1 nm or more, preferably 10 nm or more. Preferably, it is 30 nm or more, and is 500 nm or less, preferably 300 nm or less, more preferably 200 nm or less, and preferably one or more selected from the group consisting of UV scattering agents and organic UV absorbers It is more preferable to contain at least one selected from a benzoic acid-based UV absorber, a benzophenone-based UV absorber, a cinnamic acid-based UV absorber, and a triazine-based UV absorber, and a benzoic acid-based UV absorber, cinnamic acid-based More preferably, it contains at least one selected from ultraviolet absorbers and triazine-based ultraviolet absorbers, More preferably, it contains at least two selected from benzoic acid-based UV absorbers, cinnamic acid-based UV absorbers, and triazine-based UV absorbers. 2-ethylhexyl-p-methoxycinnamate and diethylamino The skin cosmetic according to any one of <1> to <3>, wherein it is more preferable to use in combination with hexyl hydroxybenzoylbenzoate.
<5> The ratio of 2-ethylhexyl-p-methoxycinnamate to hexyl diethylaminohydroxybenzoylbenzoate is, for example, 10 / 1 or less, preferably 8/1 or less, more preferably 7/1 or less, for example 2/1 or more, preferably 3/1 or more, more preferably 4/1 or more. The skin cosmetic according to <4>, wherein
<6> The content of the component (A) in the skin cosmetic is 0.1% by mass or more, preferably 1% by mass or more, more preferably, in all components except the component (E) of the skin cosmetic. 5% by mass or more, more preferably 10% by mass or more, and 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, more preferably 18% by mass or less, The skin cosmetic according to any one of <1> to <5>.
<7> Mass ratio of organopolysiloxane segment to hydrophilic segment having N-acylalkyleneimine as a repeating unit in component (B) (hydrophilic segment having organopolysiloxane segment a / N-acylalkyleneimine as a repeating unit) b) a / b is 45/55 or more, preferably 65/35 or more, more preferably 85/15 or more, and 94/6 or less, preferably 92/8 or less, The skin cosmetic according to any one of <1> to <6>, preferably 90/10 or less.
In <8> component (B), the weight average molecular weight of the organopolysiloxane segment is 1 × 10 ⁴ or more, preferably 2 × 10 ⁴ or more, more preferably 3.5 × 10 ⁴ or more, The skin cosmetic according to any one of <1> to <7>, which is 3 × 10 ⁵ or less, preferably 2 × 10 ⁵ or less, more preferably 1.5 × 10 ⁵ or less.
In <9> component (B), the number average molecular weight of the poly (N-acylalkylenimine) segment is 5 × 10 ² or more, preferably 7 × 10 ² or more, more preferably 8 × 10 ² or more. The skin cosmetic according to any one of <1> to <8>, which is 4 × 10 ³ or less, preferably 3.5 × 10 ³ or less, and more preferably 3 × 10 ³ or less. .
<10> The skin cosmetic according to any one of <1> to <9>, comprising an N-propionylpolyethyleneimine / methylpolysiloxane copolymer (POLYSILICONE-9) as a polymer of the component (B).
<11> The content of the component (B) in the skin cosmetic is 0.1% by mass or more, preferably 0.3% by mass or more, in all components except the component (E) of the skin cosmetic. Preferably it is 0.5 mass% or more, more preferably 0.8 mass% or more, and 3 mass% or less, preferably 2.5 mass% or less, more preferably 1.5 mass% or less. The skin cosmetic according to any one of <1> to <10>.
<12> The component (C) is one or more selected from the group consisting of methanol, ethanol, propanol, and butanol, and ethanol is preferable. Any one of the above items <1> to <11> Skin cosmetics.
<13> The content of the component (C) in the skin cosmetic is 40% by mass or more, preferably 60% by mass or more, and 95% by mass or less in all components except the component (E). Yes, preferably 90% by mass or less, and may be the remainder excluding components other than the component (C) in the stock solution composed of all components except the component (E) in the cosmetic composition, The skin cosmetic according to any one of 1> to <12>.
<14> Components (D1) and (D2) are made of polyamide powder, nylon powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, benzoguanamine powder, polymethylbenzoguanamine powder, polymethylmethacrylate powder, polyurethane powder, vinyl Resin, fluororesin, acrylic resin, melamine resin; silicone powder such as silicone elastomer powder and polymethylsilsesquioxane powder crosslinked with dimethyl silicone; butyl acrylate / vinyl acetate copolymer, styrene / acrylic acid copolymer, Poly (meth) acrylic such as divinylbenzene / styrene copolymer, (lauryl methacrylate / ethylene glycol dimethacrylate) copolymer, etc. Crosslinkable or non-crosslinked, such as powders of one or two or more polymers or copolymers selected from sodium poly (meth) acrylate, poly (meth) acrylate, polyalkylene glycol (poly (meth) acrylate) The skin cosmetic according to any one of <1> to <13>, which is an organic spherical powder of a mold.
The number average particle diameter of <15> component (D1) is 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and 10 μm or less, preferably 9 μm or less, more preferably 8 μm or less. The skin cosmetic according to any one of the above <1> to <14>.
The particle size ratio ((D1) / (D2)) of the component (D1) to the <16> component (D2) is ½ or less, preferably 1 / 2.5 or less, more preferably ½. 8 or less, more preferably 1/3 or less, for example 1/10 or more, preferably 1/8 or more, more preferably 1/7 or more, more preferably 1/6 or more. The skin cosmetic according to any one of <1> to <15>.
<17> The component (D1) is one or two selected from nylon powder, silicone powder, polymethyl methacrylate powder, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, alkylene glycol acrylate, and alkylene glycol methacrylate One or more kinds of polymer or copolymer powder, and one or more kinds of polymer or copolymer powder selected from nylon powder, silicone powder, polymethylmethacrylate powder, alkyl acrylate, and alkyl methacrylate The skin cosmetic according to any one of <1> to <16>, wherein is more preferable, and silicone powder is more preferable.
The number average particle diameter of <18> component (D2) is larger than 10 μm, preferably 11 μm or more, more preferably 13 μm or more, more preferably 15 μm or more, and 25 μm or less, preferably 24 μm or less, The skin cosmetic according to any one of <1> to <17>, preferably 23 μm or less.
<19> Component (D2) is selected from nylon powder, ethylene powder, silicone powder, polymethyl methacrylate powder, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, alkylene glycol acrylate and alkylene glycol methacrylate A powder of a seed or two or more kinds of polymers or copolymers, and a powder of at least one selected from alkyl acrylate and alkyl methacrylate and at least one selected from alkylene glycol acrylate and alkylene glycol methacrylate. The powder according to any one of <1> to <18>, wherein a polymer powder is more preferable, and a powder of a copolymer of alkyl methacrylate and alkylene glycol methacrylate is further preferable. Cosmetics.
<20> The ratio of the component (D1) to the component (D2) ((D1) / (D2)) is 20/1 or less, preferably 15/1 or less, more preferably 10/1 or less in terms of mass ratio. Any one of the above <1> to <19>, more preferably 8/1 or less, and 1/2 or more, preferably 1/1 or more, and more preferably 2/1 or more. Skin cosmetics according to 1.
<21> The content of the components (D1) and (D2) in the skin cosmetic is 0.5% by mass or more and 1% by mass or more in total of the components (D1) and (D2). Preferably, 1.5% by mass or more, more preferably 10% by mass or less, preferably 6% by mass or less, more preferably 5% by mass or less, and still more preferably 4% by mass or less. The skin cosmetic according to any one of <1> to <20>.
<22> The ratio of component (B) to the sum of components (D1) and (D2) ((B) / ((D1) + (D2))) is 0.05 or more in terms of mass ratio, preferably 0. 1 or more, more preferably 0.2 or more, more preferably 0.25 or more, and 1 or less, preferably 0.8 or less, more preferably 0.75 or less, <1> The skin cosmetic according to any one of ~ <21>.
<23> Component (E) is one or more selected from liquefied natural gas (LPG), dimethyl ether (DME), carbon dioxide, nitrogen gas, alternative chlorofluorocarbons, and mixtures thereof, preferably LPG The skin cosmetic according to any one of <1> to <22>.
<24> The boiling point of the component (E) is −50 ° C. or higher, preferably −40 ° C. or higher, 0 ° C. or lower, preferably −20 ° C. or lower, <1> to <23>. The skin cosmetic according to any one of 23>.
<25> Content of component (E) in skin cosmetic is a component excluding component (E) in skin cosmetic, that is, components (A) to (C), (D1), (D2) and optional components The stock solution / propellant is 10/90 or more, preferably 20/80 or more, more preferably 30/70 or more, and 70/30 or less. The skin cosmetic according to any one of <1> to <24>, which is preferably 60/40 or less, more preferably 50/50 or less.
<26> (F) Further comprising an alkylene oxide derivative represented by the above general formula (I), wherein the alkylene oxide derivative of component (F) is polyoxybutylene polyoxyethylene polyoxypropylene glycerin (INCI name: PEG / PPG / poly) The skin cosmetic according to any one of <1> to <25>, which is butylene glycol-8 / 5/3 glycerin).
<27> The content of water in the skin cosmetic is 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, in all components except the component (E). The skin according to any one of <1> to <26>, further more preferably 0.05% by mass or less, further preferably 0.01% by mass or less, and still more preferably substantially 0% by mass or less. Cosmetics.
<28> (F) Further containing an alkylene oxide derivative represented by the above general formula (I), the content of the component (F) in the skin cosmetic is 0.1% by mass in all components except the component (E) % Or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.2% by mass or more, and 3% by mass or less, preferably 2.5% by mass. % Of skin cosmetics according to any one of <1> to <27>.
<29> The content of the thickener in the skin cosmetic is 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less, in all components except the component (E). The skin cosmetic according to any one of the above items <1> to <28>, more preferably 05% by mass or less, further preferably 0.01% by mass or less, and still more preferably 0.
<30> The content of the surfactant in the skin cosmetic is 0.001% by mass or more, preferably 0.005% by mass or more, and preferably 0.007% by mass or more in all components except the component (E). Is more preferably 0.5% by mass or less, preferably 0.3% by mass or less, and more preferably 0.1% by mass or less, and skin makeup according to any one of the above items <1> to <29> Fee.
<31> Mixing components other than component (E) and dissolving or dispersing them to prepare a stock solution;
Filling the pressure-resistant container with the stock solution obtained in the above step together with the propellant of component (E);
The manufacturing method of the skin cosmetics any one of said <1>-<30> containing this.
<32> including a step of applying the skin cosmetic according to any one of <1> to <30> to the skin, preferably including a step of applying to the skin, face, body, limbs, or the like. , How to use skin cosmetics.
<33> An ultraviolet protection method comprising a step of applying the skin cosmetic according to any one of <1> to <30> to the skin.
<34> A method for suppressing stickiness, comprising a step of applying the skin cosmetic according to any one of <1> to <30> to the skin.
<35> A method for creating a dry feeling or a method for improving the sustainability of the dry feeling, comprising the step of applying the skin cosmetic according to any one of <1> to <30> to the skin.
<36> Use of the skin cosmetic according to any one of <1> to <30> for UV protection, suppression of stickiness, and imparting a smooth feeling.
<37> Use of the skin cosmetic according to any one of <1> to <30> for the production of a UV-protective cosmetic, a stickiness-suppressing cosmetic, or a smooth-feeling cosmetic.

Production Example 1 (Production of N-propionylpolyethyleneimine / methylpolysiloxane copolymer 1)
Poly (N-propionylethyleneimine) having a number average molecular weight of 2700 was obtained from 0.8 g (0.005 mol) of diethyl sulfate, 12.8 g (0.14 mol) of 2-ethyl-2-oxazoline and 29 g of dehydrated ethyl acetate. Obtained. Further, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100000, amine equivalent 20000) was used to convert N-propionylethyleneimine-dimethylsiloxane copolymer into a pale yellow rubber-like solid (111 g, yield 98). %). The content of the organopolysiloxane segment in the final product was 88% by mass (a / b = 88/12), and the weight average molecular weight of the organopolysiloxane (Mwt) was 114,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Production Example 2 (Production of N-propionyl polyethyleneimine / methyl polysiloxane copolymer 2)
By a method according to Production Example 1, 6.17 g (0.04 mol) of diethyl sulfate and 34.7 g (0.35 mol) of 2-ethyl-2-oxazoline were dissolved in 83 g of dehydrated ethyl acetate, The mixture was heated to reflux for 8 hours to synthesize terminal reactive poly (N-propionylethyleneimine). The number average molecular weight was 1000 as measured by GPC. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, 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 rubber-like semisolid (141 g, yield 97%). The content of the organopolysiloxane segment in the final product was 71% by mass (a / b = 71/29), and the weight average molecular weight of the organopolysiloxane (Mwt) was 42,000. 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.

Production Example 3 (Production of N-propionylpolyethyleneimine / methylpolysiloxane copolymer 3)
By a method according to Production Example 1, 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) was obtained. Further, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 50000, amine equivalent 3800) was used to convert an 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 (a / b = 51/49), and the weight average molecular weight of the organopolysiloxane (Mwt) was 98,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that about 24% by mass of amino groups remained.

(Examples 1-36 and Comparative Examples 1-11)
Skin cosmetics having the compositions shown in Tables 1 to 4 were produced, and the UV protection ability was maintained, the feeling of use (no stickiness, the degree of smoothness, the smoothness of dryness), and the powder redispersion by the methods described below. The property (index of redispersion) was evaluated. The results are also shown in Tables 1 to 4.

(Production method)
All components except the propellant were mixed and dispersed with a disper to prepare a stock solution.
The obtained stock solution was filled in a pressure-resistant container together with a propellant (LPG) to obtain an aerosol preparation for skin cosmetics.

(Evaluation method)
(Persistence of UV protection)
Place 28.5 ± 0.5 mg of each sample (stock solution) on a polymethylmethacrylate (PMMA) plate (50 mm × 50 mm) with a syringe and place the sample on the plate using an index finger previously saturated with the sample. Spread evenly. Thereafter, the plate was stored for 15 minutes at room temperature in a light-shielded box, and in vitro SPF was measured with a UV-2000 SSPF analyzer (manufactured by Labsphere).
The water resistance test was performed using a 3 liter beaker filled with 2.5 liters of room temperature distilled water. After fixing the PMMA plate to the beaker wall with a spacer, water was constantly stirred (270 rpm / min) using a magnetic stirrer to ensure optimal laminar flow around the plate. After soaking for 60 minutes, the sample was taken out and dried at room temperature for 60 minutes, and then in vitro SPF was measured again to calculate SPF persistence (%) based on the following formula. Moreover, based on the obtained numerical value, water resistance was evaluated according to the following criteria. The higher the value, the higher the water resistance and the better the durability of UV protection.
SPF persistence (%) = (SPF value after water treatment / SPF value before water treatment) × 100

(Usage feeling: no stickiness)
When three specialized panelists sprayed each aerosol product on the arm for 1 second, the non-stickiness was evaluated according to the following criteria, and the average value was obtained.
5: No stickiness 4: Little stickiness 3: No stickiness 2: Feeling sticky and uncomfortable 1: Very sticky, very uncomfortable

(Usage feeling: degree of smooth feeling)
When three specialized panelists sprayed each aerosol product on the arm for 1 second, the degree of smoothness was evaluated according to the following criteria, and the average value was obtained.
5: Very free 4: 4: Free 3: Somewhat free 2: Almost free 1: No free

(Usage feeling: the degree of sustainability of the smooth feeling)
Three professional panelists sprayed each aerosol product on the arm for 1 second, and after extending it 5 times to the arm, the degree of smooth feeling was evaluated according to the following criteria, and the average value was obtained.
5: Very free 4: 4: Free 3: Somewhat free 2: Almost free 1: No free

(Redispersibility of powder)
The aerosol product is allowed to stand in a constant temperature room at 20 ° C. for one day, and the powder is settled on the bottom of the container. The number of times was measured. The redispersibility index was calculated based on the following formula. A higher numerical value indicates that the powder is redispersed in a shorter time, and the redispersibility of the powder is better.
Redispersibility index = (1 ÷ number of times) × 100

The components used in Examples or Comparative Examples are shown below.
* 1 2-ethylhexyl-p-methoxycinnamate: ubinal MC80, manufactured by BASF * 2 Mixture of 2-ethylhexyl-p-methoxycinnamate / diethylaminohydroxybenzoyl hexyl benzoate (64/36): ubinal A PLUS B * 3 N-propionylpolyethyleneimine / methylpolysiloxane copolymer produced by BASF: obtained in Production Example 1, a / b = 88/12
* 4 N-propionylpolyethyleneimine / methylpolysiloxane copolymer: obtained in Production Example 2, a / b = 71/29
* 5 N-propionylpolyethyleneimine / methylpolysiloxane copolymer: obtained in Production Example 3, a / b = 51/49
* 6 (Eicosene / vinyl pyrrolidone) copolymer: Antalon V-220, manufactured by ISP Japan * 7 (Acrylates / C12-22 alkyl methacrylate) Copolymer: SOLTEX OPT, manufactured by Sadau Chemical Company * 8 Polyacrylate-15 / 17: SYNTRAN PC5527, manufactured by Interpolymer * 9 Dextrin isostearate: Unifilm HVY, manufactured by Chiba Flour Mills * 10 Methylsiloxane network polymer: Tospearl 145A, manufactured by Momentive Performance Materials Japan LLC * 11 Nylon powder: Nylon SP- 500, manufactured by Toray Industries, Inc. * 12 Cross-linked polyacrylate: Matsumoto Microsphere M201, Matsumoto Yushi Seiyaku Co., Ltd. * 13 Cross-linked polyacrylate: Matsumoto Micros Air M305, Matsumoto Yushi Seiyaku Co., Ltd. * 14 Cross-linked polyacrylate: Matsumoto Microsphere M503B, Matsumoto Yushi Seiyaku Co., Ltd. * 15 Ethylene powder: Flow beads CL3080, Sumitomo Seika Oil Co., Ltd. * 16 Nylon powder: Nylon TR- 2. Toray Co., Ltd. * 17 Styrene / acrylic acid copolymer: Rohmsphere Powder, manufactured by Rohm and Haas Japan Co., Ltd. * 18 Polyoxybutylene polyethylene polyoxypropylene glyceryl ether (8EO) (5PO) (3BO): Willbride S-753, manufactured by NOF Corporation

  From Tables 1 to 4, the cosmetics described in each example include components (A) to (C), (D1), (D2), and (E), and the content and components of component (C). Since the mass ratio of (D1) to component (D2) is in a specific range, it is excellent in the durability of the UV protection ability as compared to those described in each comparative example, and has no stickiness, smoothness and its durability. In this respect, a cosmetic with an excellent balance in use feeling was obtained. In addition, the cosmetics described in each example were superior to those described in each comparative example in terms of redispersibility of the powder component in the cosmetic.

(Prescription Examples 1 and 2)
Table 5 shows examples of skin cosmetic formulations.

Claims (5)

The following components (A), (B), (C), (D1), (D2) and (E):
(A) a UV protection agent comprising 2-ethylhexyl-p-methoxycinnamate and hexyl diethylaminohydroxybenzoylbenzoate ;
(B) N-propionyl polyethyleneimine / methyl polysiloxane copolymer ,
(C) ethanol ,
(D1) a powder having a number average particle size of 1 μm or more and 10 μm or less,
(D2) a skin cosmetic comprising a powder having a number average particle size of more than 10 μm and 25 μm or less, and (E) a propellant,
In all components except the component (E) of the skin cosmetic, the content of the component (A) is 5% by mass or more and 20% by mass or less,
In all components except the component (E) of the skin cosmetic, the content of the component (B) is 0.1% by mass or more and 3% by mass or less,
The in all components the exception of component (E) of skin cosmetics, or less 9 0 wt% content of 6 0% by mass or more of said components (C),
The skin cosmetic in which the mass ratio of the component (D1) and the component (D2) in the skin cosmetic is (component (D1) / component (D2)) = 1/2 to 20/1.   The sum total of content of the said component (D1) and the said component (D2) is 0.5 mass% or more and 10 mass% or less in all the components except the said component (E) in the said skin cosmetics. Skin cosmetics according to 1. Wherein the component (D1) or the component (D2), nylon powder, ethylene powder, silicone powder, polymethyl methacrylate powder, powder of an acrylic acid polymer, powder methacrylic acid polymers, acrylic acid alkyl polymer powder, methacrylate 1 type or 2 types selected from powder of acid alkyl polymer, powder of alkylene glycol acrylate polymer, powder of alkylene glycol methacrylate, and powder of copolymer of alkyl methacrylate and alkylene glycol methacrylate it is on than, the skin cosmetic according to claim 1 or 2.   The mass ratio ((B) / ((D1) + (D2))) of the component (B) to the sum of the components (D1) and (D2) is 0.05 or more and 1 or less. 3. The skin cosmetic according to any one of 3 above. (F) The alkylene oxide derivative represented by the following general formula (I): further comprising 0.1% by mass or more and 3% by mass or less of all components except the component (E). Skin cosmetics.
Gly- [O (PO) m (EO) n- (BO) pH] ₃ (I)
(In the above general formula (I), Gly is a residue obtained by removing a hydroxyl group from glycerin, PO is an oxypropylene group, and EO is an oxyethylene group. M and n are average added moles of PO and EO, respectively. 1 to 50, and the mass ratio of PO to EO (PO / EO) is 1/5 to 5/1, BO is an oxyalkylene group having 4 carbon atoms, p is the average addition of BO (The number of moles and a value of 0.5 to 5.)