JP2016069282A - Water-in-oil type emulsion cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic which is excellent in balance of effects such as no stickiness, dry feeling, good makeup performance, no oiliness, no powdery feel, and long lasting makeup, as well as is excellent in ultraviolet light-shielding effect.SOLUTION: The invention provides a water-in-oil type emulsion cosmetic containing the following components (A)-(G): (A) 9-20 mass% of organic ultraviolet light-shielding agent; (B) 9.5-20 mass% of zinc oxide; (C) 0.1-1.5 mass% of a polymer containing, as a constitutional unit, a hydrophilic segment with N-acyl alkylene imine as a repeating unit, and an organopolysiloxane segment; (D) 3-25 mass% of a spherical cross linkage (meth) acrylic ester resin powder which fulfills specific conditions about compressive strength; (E) 0.1-2 mass% of silicone resin particles; (F) 10- 50 mass% of silicone oil; and (G) water.SELECTED DRAWING: None

Description

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

Patent Documents 1 and 2 disclose techniques for preventing ultraviolet rays using cosmetics.
Patent Document 1 (Japanese Patent Application Laid-Open No. 9-227331) discloses an ultraviolet ray having a high ultraviolet protection effect and its sustaining effect, excellent water and oil repellency, good usability, and excellent safety and stability. As a technique relating to protective cosmetics, an ultraviolet protective cosmetic containing an ultraviolet protective agent and a poly (N-acylalkylenimine) -modified silicone is described.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2000-281554) discloses cyclic silicone 4 as a technology relating to a powder-containing water-in-oil emulsified cosmetic that has a smooth feel, enables a natural finish, and has excellent storage stability. -Powder-containing water-in-oil emulsification containing a specific ratio of hexamer, sorbitan monoisostearate and / or diglyceryl monoisostearate, methylsiloxane network polymer and / or cross-linked silicone powder, titanium oxide and water Cosmetics are listed.

  Further, although technical fields are different, Patent Document 3 (Japanese Patent Laid-Open No. 2010-90153) describes a gel cosmetic containing a crosslinked (meth) acrylate resin powder having specific physical properties. Yes. In addition, it is described that such a gel-like cosmetic can give a smooth feel without being sticky while keeping the skin non-sticky, and is excellent in the sustainability of the smoothness and non-stickiness of the skin. ing.

JP-A-9-227331 JP 2000-281554 A JP 2010-90153 A

As a result of examination of the techniques described in Patent Documents 1 and 2 described above, the present inventor has found that when the UVA protection index (Protection Grade of UVA: PA) is increased, the oil content may increase and become sticky. It became clear that there was room for improvement.
Therefore, the present invention has an excellent UV protection effect, and also has a good balance of non-stickiness, smooth feeling, good makeup, no oiliness, no powderiness and makeup sustainability. Provide cosmetics.

According to the present invention,
The following components (A) to (G):
(A) 9-20% by mass of an organic ultraviolet protective agent,
(B) zinc oxide 9.5 to 20% by mass,
(C) 0.1 to 1.5% by mass of a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as structural units,
(D) Spherical cross-linked (meth) acrylic ester resin powder having a compressive strength of 0.7 to 10 kgf / mm ² determined from the following test method and formula, 3 to 25% by mass,
Compressive strength (kgf / mm ² ) = 2.8 × load (kgf) / {π × particle diameter (mm) × particle diameter (mm)}
(In the above formula, the compressive strength is determined when the resin powder particles are subjected to a compression test at 25 ° C. using a microcompression tester MCT-M200 manufactured by Shimadzu Corporation. (It is a value calculated by the above formula from the load and the particle diameter.)
(E) Silicone resin particles 0.1-2% by mass,
There is provided a water-in-oil emulsified cosmetic containing (F) 10 to 50% by mass of silicone oil and (G) water.

  According to the present invention, it has an excellent UV protection effect, and also has a good balance of non-stickiness, smoothness, good makeup, no oiliness, no powderiness and makeup sustainability. Can get cosmetics.

In this embodiment, a water-in-oil (W / O) emulsified cosmetic is a composition containing the following components (A) to (G).
(A) 9-20% by mass of an organic ultraviolet protective agent,
(B) zinc oxide 9.5 to 20% by mass,
(C) 0.1 to 1.5% by mass of a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as structural units,
(D) Spherical cross-linked (meth) acrylic ester resin powder having a compressive strength of 0.7 to 10 kgf / mm ² determined from the following test method and formula, 3 to 25% by mass,
Compressive strength (kgf / mm ² ) = 2.8 × load (kgf) / {π × particle diameter (mm) × particle diameter (mm)}
(In the above formula, the compressive strength is determined when the resin powder particles are subjected to a compression test at 25 ° C. using a microcompression tester MCT-M200 manufactured by Shimadzu Corporation. (It is a value calculated by the above formula from the load and the particle diameter.)
(E) Silicone resin particles 0.1-2% by mass,
(F) 10 to 50% by mass of silicone oil, and (G) water.

Hereinafter, each component will be described with specific examples. Each component can be used alone or in combination of two or more.
Further, in the present embodiment, the feeling of use means that when cosmetics are used, there is no stickiness, and the feeling of smoothness, goodness of makeup, lack of oiliness, lack of powderiness, and makeup persistence. It means to feel.

(Ingredient (A))
Component (A) is an organic ultraviolet absorber.
The component (A) is preferably oil-soluble, and includes a benzoic acid UV absorber, an anthranilic acid UV absorber, a salicylic acid UV absorber, a cinnamic acid UV absorber, a benzophenone UV absorber, and a triazine UV. An absorbent etc. are mentioned.
As benzoic acid-based UV absorbers, para-aminobenzoic acid (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, and a cinnamic acid type ultraviolet absorber It is more preferable to contain.

The organic ultraviolet absorber of component (A) can be used singly or in combination of two or more, and the combination and blending amount depends on, for example, the ultraviolet protective effect of the water-in-oil emulsion cosmetic. It is determined.
From the viewpoint of making the UV protection effect of the water-in-oil emulsified cosmetic more manifest, the content of the component (A) is 9% by mass or more, preferably 9. The content is 5% by mass or more, and more preferably 9.8% by mass or more. Further, from the viewpoint of further improving the feeling of use of the water-in-oil emulsified cosmetic, that is, from the viewpoint of suppressing stickiness and imparting a smooth feeling, the amount of the component (A) is determined as follows. It is 20 mass% or less with respect to the whole of this, Preferably it is 18 mass% or less, More preferably, it is 15 mass% or less.

(Ingredient (B))
Component (B) is zinc oxide. The zinc oxide of the component (B) may be zinc oxide usually used for cosmetics. Preferably, those having superior dispersibility, for example, those whose surfaces have been subjected to a hydrophobic treatment by a known method can be used as necessary.

  Surface treatment methods include silicone treatment such as methylhydrogenpolysiloxane and methylpolysiloxane; fluorine treatment with perfluoroalkyl phosphate ester, perfluoroalcohol, etc .; amino acid treatment with N-acyl glutamic acid, etc .; other, lecithin treatment; metal Examples include soap treatment; fatty acid treatment; alkyl phosphate treatment. Of these, zinc oxide whose surface is treated with silicone is preferably used.

  The silicone used for the surface treatment is not limited. For example, methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octadeca Methyltrisiloxane, tetradecamethylhexasiloxane, dimethylsiloxane methyl (polyoxyethylene) siloxane methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane methyl (Polyoxypropylene) siloxane copolymer, dimethylsiloxane / methylcetyloxysiloxane copolymer, dimethylsiloxane / medium It can include various silicone oils such as pulse stearoyl carboxymethyl copolymer. Methyl hydrogen polysiloxane and methyl polysiloxane are preferable.

  Commercially available products may be used as the component (B) zinc oxide, and as a specific example, FINEX-50-LPTM (dimethicone treatment, manufactured by Sakai Chemical Co., Ltd.), MZ-300 (no surface treatment agent, Teika) MZ-504R3M (hydrogen dimethicone treatment, manufactured by Teica), MZY-303S (hydrogen dimethicone treatment, manufactured by Teica), MZ-306X (triethoxysilylethylpolydimethylsiloxyethylhexyl dimethicone treatment, manufactured by Teica), MZ -200 (no surface treatment agent, manufactured by Teica), MZY-203S (hydrogen dimethicone treatment, manufactured by Teica), MZ-150 (no surface treatment agent, manufactured by Teica), MZY-153S (hydrogen dimethicone treatment, Teica) Manufactured), FINEX-25 (no surface treatment agent, manufactured by Sakai Chemical Co., Ltd.), FINEX-2 LP (dimethicone treatment, Sakai made Gakusha), and the like. However, it is not limited to these examples.

  In the present embodiment, the content of the component (B) in the water-in-oil emulsified cosmetic is 9.5% by mass or more based on the total amount of the water-in-oil emulsified cosmetic from the viewpoint of achieving a higher SPF. Yes, preferably 9.7% by mass or more, and more preferably 9.9% by mass or more. In addition, the content of the component (B) in the water-in-oil emulsified cosmetic is prevented from being excessively whitened when applied to the skin, and from the viewpoint of reducing oiliness. It is 20 mass% or less with respect to the whole material, Preferably it is 16 mass% or less, More preferably, it is 14 mass% or less.

  When the component (B) is in the form of particles, the number average particle size is, for example, 1 nm or more, preferably 5 nm or more, more preferably 8 nm or more, and further preferably 10 nm or more. For example, it is 500 nm or less, preferably 300 nm or less, more preferably 100 nm or less, and further preferably 60 nm or less.

  Here, the number average particle diameter of the component (B) is measured, for example, with a transmission electron microscope (TEM) under the condition of 50000 magnification, the particle diameter of 300 particles in the image, It is obtained by calculating the average value. For example, for the FINEX-50-LPTM, the number average particle size measured by such a method is about 20 nm.

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

In the component (C), 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 durability of the UV protection effect of cosmetics and the suppression of stickiness, and from the viewpoint of improving cosmetic paste and reducing powderiness, for example, a / b = 45/55 or more Yes, preferably 65/35 or more, more preferably 85/15 or more, for example 94/6 or less, preferably 92/8 or less, more preferably 90/10 or less.
In the present specification, the mass ratio is defined as the alkyl group in the organopolysiloxane segment by dissolving 5% by mass of the organopolysiloxane of the present embodiment in deuterated chloroform and analyzing by nuclear magnetic resonance ( ¹ H-NMR). 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 (C), the weight average molecular weight of the organopolysiloxane segment is determined from the viewpoint 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 (C), the number average molecular weight of the poly (N-acylalkyleneimine) segment has 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 component (C) polymer 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 component (C), 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 (C) in the water-in-oil emulsified cosmetic is the viewpoint of improving the sustainability of the smooth feeling, the viewpoint of improving the sustainability of the UV protection effect of the cosmetic, and the makeup. From the viewpoint of improving the paste and reducing the powderiness, the total amount of the water-in-oil emulsified cosmetic is, for example, 0.1% by mass or more, preferably 0.2% by mass or more, more preferably It is 0.3 mass% or more, more preferably 0.5 mass% or more. In addition, from the viewpoint of obtaining a smooth feeling by suppressing the stickiness of the cosmetic, and from the viewpoint of ensuring the storage stability of the cosmetic while ensuring that the feel during application of the cosmetic is not too heavy, The content of the component (C) in the type emulsified cosmetic is, for example, 1.5% by mass or less, preferably 1.3% by mass or less, more preferably, based on the whole water-in-oil emulsified cosmetic. 1.0 mass% or less, More preferably, it is 0.9 mass% or less.

  In this embodiment, the mass ratio between the component (A) and the component (C) in the water-in-oil emulsified cosmetic is, for example, (component (A)) from the viewpoint of suppressing powderiness and oiliness. / Component (C)) is 60/1 to 5/1, preferably 40/1 to 8/1, more preferably 22/1 to 10/1, still more preferably 18/1 to 12/1. .

(Component (D))
Component (D) is a spherical cross-linked (meth) acrylate resin powder that satisfies a specific condition for compressive strength.
More specifically, the component (D) has a compressive strength of 0.7 to 10 kgf / mm ² obtained from the following test method and formula.
Compressive strength (kgf / mm ² ) = 2.8 × load (kgf) / {π × particle diameter (mm) × particle diameter (mm)}
(In the above formula, the compressive strength is determined when the resin powder particles are subjected to a compression test at 25 ° C. using a microcompression tester MCT-M200 manufactured by Shimadzu Corporation. (It is a value calculated by the above formula from the load and the particle diameter.)

In this embodiment, the crosslinked (meth) acrylic acid ester resin powder of component (D) has a compressive strength of 0.7 to 10 kgf / mm ² from the viewpoint of obtaining a non-sticky and smooth skin. Preferably it is 2-8 kgf / mm < ² >.

  Here, the compression strength is obtained by the following formula from the load and the particle diameter at the time of 10% deformation of the particle diameter when the resin particle is subjected to a compression test with a micro compression tester MCT-M200 manufactured by Shimadzu Corporation. This is a calculated value. The compressive strength is measured at 25 ° C.

Compressive strength (kgf / mm ² ) = 2.8 × load (kgf) / {π × particle diameter (mm) × particle diameter (mm)}
The compressive strength of the resin particles can be adjusted as appropriate by controlling the types and blending amounts of the monomer and the crosslinking agent constituting the resin particles.

As the crosslinked (meth) acrylic acid ester resin powder of component (D), at least one monomer selected from acrylic acid ester and methacrylic acid ester (hereinafter referred to as (meth) acrylic acid ester monomer) and Cross-linked (meth) acrylic ester resin powder obtained by copolymerizing a monomer component containing a monomer having a carboxyl group is preferable.
In the present specification, “(meth) acryl” is a concept including both acrylic and methacrylic.

  Moreover, a part of carboxyl group contained in the crosslinked (meth) acrylic acid ester resin powder of the component (D) may be neutralized. The base for neutralization is preferably an inorganic base such as sodium hydroxide, potassium hydroxide or ammonia, but organic bases such as amines, alkanolamines and basic amino acids can also be used. From the viewpoint of further improving the smoothness and smoothness of the powder, the degree of neutralization is preferably 1 to 30%, and more preferably 1 to 20%. Here, the degree of neutralization represents the ratio of the number of moles of the added base to the number of moles of the carboxyl group of the monomer having a carboxyl group, expressed as a percentage.

  In this embodiment, as a component used for manufacture of a component (D), and the manufacturing method of a component (D), the component and method as described in Unexamined-Japanese-Patent No. 2010-90153 can be used, for example. More specifically, the component (D) can be obtained by the aqueous suspension polymerization method described in the document.

  Further, as the surfactant used in the aqueous suspension polymerization method, those having a sulfonic acid (salt) group are preferable. Thereby, it is possible to obtain a more smooth and smooth resin powder. As the surfactant having a sulfonic acid (salt) group, for example, those described in JP-A-2010-90153 are used.

  In the present embodiment, the shape of the resin powder of component (D) is preferably a spherical body because the feel on the skin is good. Further, the average particle diameter of the component (D) is preferably 1 μm or more, more preferably 1.5 μm or more, and particularly preferably 2 μm or more from the viewpoint of reducing squeaky feeling. On the other hand, from the viewpoint of suppressing roughness and further improving skin fixation, 10 μm or less is preferable, 8 μm or less is more preferable, and 6 μm or less is particularly preferable.

  The average particle size was measured using a laser diffraction type particle size distribution measuring device (for example, LA-920 manufactured by Horiba, Ltd.), and the powdered water suspension was a weight average particle having a relative refractive index of 1.1 at 20 ° C. It can be determined by measuring the diameter.

  Further, the powder of component (D) refers to a powder having a substantially spherical shape, and may be a spheroid, a spherical powder having irregularities on the surface, etc., and does not need to be a perfect sphere. .

The content of the component (D) in the water-in-oil emulsified cosmetic is 3% by mass or more, preferably 8% by mass or more, based on the whole water-in-oil emulsified cosmetic from the viewpoint of suppressing stickiness. More preferably, it is 10% by mass or more.
Further, from the viewpoint of improving the smooth feeling and the sustainability thereof, the content of the component (D) in the water-in-oil emulsified cosmetic is 25% by mass or less based on the entire water-in-oil emulsified cosmetic. , Preferably 22% by mass or less, more preferably 20% by mass or less.

(Ingredient (E))
Component (E) is silicone resin particles.
Specific examples of the component (E) include silicone resin particles such as a methylsiloxane network polymer, a crosslinked silicone / network type silicone block copolymer, or a cured product of polyorganosilsesquiosan (polymethylsilsesquiosan). .
The number average particle size of the component (E) is 1 μm from the viewpoint of excellent feel when the cosmetic is applied, that is, from the viewpoint of improving the dry feeling and suppressing stickiness and oiliness. It is above, Preferably it is 3 micrometers or more, More preferably, it is 4 micrometers or more. Further, from the above viewpoint, the number average particle diameter is 10 μm or less, preferably 8 μm or less, and more preferably 6 μm or less.
Here, the average particle diameter of the component (E) 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.

As the component (E), more specifically, as a cross-linked silicone / reticulated silicone block copolymer, KMP-599 (3 μm), KSP-100 (5 μm), KSP-105 (2 μm), KSP-300 (5 μm) ), X-52-1621 (5 μm) (above, manufactured by Shin-Etsu Chemical Co., Ltd.);
As the methylsiloxane network polymer, 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)
Commercial products such as these can be used.
Among them, X-52-1621 (5 μm) (manufactured by Shin-Etsu Chemical Co., Ltd.) and Tospearl 145A (4.5 μm) (manufactured by Momentive Performance Materials Japan) provide a smooth feel when applied. That is, it is preferable in that a more excellent feeling of smoothness can be obtained and a finish that does not whiten is achieved.

The content of the component (E) in the water-in-oil emulsified cosmetic is smooth, from the viewpoint of realizing a natural finish, from the viewpoint of improving storage stability, and from the viewpoint of suppressing oiliness, The content is 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 0.9% by mass or more with respect to the entire water-in-water emulsified cosmetic.
Further, from the viewpoint of improving the feeling of use and improving the cosmetic paste, the content of the component (E) in the water-in-oil emulsified cosmetic is 2 with respect to the whole water-in-oil emulsified cosmetic. It is not more than mass%, preferably not more than 1.8 mass%, more preferably not more than 1.5 mass%.

  In the present embodiment, the mass ratio of the component (D) and the component (E) in the water-in-oil emulsified cosmetic is, for example, (component) from the viewpoint of reducing stickiness and oiliness and improving a smooth feeling. (D) / component (E)) is 25/1 to 2/1, preferably 22/1 to 5/1, more preferably 18/1 to 10/1.

  Moreover, the sum of the content of the component (D) and the component (E) in the water-in-oil emulsified cosmetic is, for example, (component) from the viewpoint of reducing stickiness and oiliness and improving the smooth feeling. (D) + component (E)) is 3.1 to 27% by mass, preferably 9 to 20% by mass, and more preferably 15 to 18% by mass.

(Ingredient (F))
Ingredient (F) is silicone oil.
Examples of the component (F) include linear polyorganosiloxane and cyclic polysiloxane.
Among these, as the linear polyorganosiloxane, a linear alkyl polysiloxane having an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Examples thereof include linear alkylaryl polysiloxanes, and specific examples thereof include linear dimethylpolysiloxane and linear methylphenyl polysiloxane. Among these linear organopolysiloxanes, those having a viscosity at 20 ° C. of 1 to 1000 mPa · s, and more preferably 5 to 10 mPa · s are preferable.
Examples of the cyclic polysiloxane include 4- to 6-membered cyclic siloxane having an alkyl group having 1 to 5 carbon atoms as a substituent, and specific examples include octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. Can be mentioned.

  From the viewpoint of reducing oiliness, the content of the component (F) in the water-in-oil emulsified cosmetic is 10% by mass or more, preferably 15%, based on the total amount of the water-in-oil emulsified cosmetic. From the same viewpoint, it is 50% by mass or less, and preferably 40% by mass or less.

(Ingredient (G))
Ingredient (G) is water.
The water content can be the remainder excluding components other than water in the water-in-oil emulsified cosmetic, for example.

In this embodiment, the water-in-oil emulsified cosmetic may further contain the following component (H).
(H) Titanium oxide The titanium oxide of the component (H) may be titanium oxide usually used in cosmetics. In addition, as the component (H), those appropriately treated with alumina, silica, zinc white, and those treated with a hydrophobic material such as silicon are used.

  The content of the component (H) in the water-in-oil emulsified cosmetic in the present embodiment is, for example, 0.5% by mass or more with respect to the entire water-in-oil emulsified cosmetic from the viewpoint of further enhancing the shielding effect. , Preferably it is 1 mass% or more. Further, from the viewpoint of preventing the touch from becoming too heavy, the content of the component (H) in the water-in-oil emulsified cosmetic is, for example, 5% by mass or less with respect to the entire water-in-oil emulsified cosmetic. Preferably, it is 3 mass% or less.

  In addition, the water-in-oil emulsified cosmetic of the present embodiment includes components other than those described above, such as surfactants, oily components, fragrances, moisturizers, cosmetic ingredients, medicinal ingredients, thickeners, bactericides, A pH adjuster, an antioxidant, a preservative, alcohols, and other components used in ordinary cosmetics can also be contained.

The water-in-oil emulsified cosmetic in the present embodiment can be produced according to a usual method.
In addition, the water-in-oil emulsified cosmetic obtained by the present embodiment includes makeup cosmetics such as makeup foundations, emulsion foundations, and eye shadows; sunscreen cosmetics such as sunscreen creams, and the like. Moreover, as a dosage form, it can be set as emulsions, creams, etc., for example.

In this embodiment, by using the specific components (A) to (G) in combination at a specific ratio, it is excellent in sunscreen effect, is non-sticky, and has a smooth use feeling. Can do.
For this reason, according to the present embodiment, even when the PA is increased as in the case of PA ++++, for example, stickiness can be suppressed and a preferable feeling of use can be given.

The water-in-oil emulsified cosmetic of the present embodiment can be used by applying it to the skin, particularly the skin excluding the hair, preferably the face, body, limbs and the like. For example, by applying the water-in-oil emulsified cosmetic of the present embodiment to the skin, ultraviolet rays can be protected, stickiness can be suppressed, and a smoother feeling can be obtained. Moreover, the water-in-oil emulsified cosmetic of this embodiment can also be used for scalp and hair.
Moreover, the water-in-oil emulsified cosmetic of the present embodiment can be suitably used as an ultraviolet protective cosmetic, a sunscreen cosmetic or the like. For example, according to this embodiment, it is also possible to obtain sunscreen cosmetics having an SPF value of 50 or more and a PA value of +++ or more.

  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.

  In the following example, each raw material is blended so that the content of each component in the resulting composition is as described in Tables 1 to 3 according to the amount of the component contained in the raw material, and the composition Got.

(Production Examples 1 and 2)
Production Example 1 (Production 1 of N-propionylpolyethyleneimine / methylpolysiloxane copolymer)
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 2 of N-propionylpolyethyleneimine / methylpolysiloxane copolymer)
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 1-13 and Comparative Examples 1-6)
A water-in-oil emulsified cosmetic composition having the composition shown in Table 1 and Table 2 was produced, and was not sticky, smooth feeling, good makeup, no oily, no powdery by the method described below. , Makeup persistence (no shine after 5 hours), SPF value and UVA value (PA value) were evaluated. The results are also shown in Table 1 and Table 2.

(Evaluation method)
(UV protection)
The SFP value was measured according to the ISO 24444 SF measurement method.
The PA value was measured according to the measurement method for the UVA prevention effect of ISO24442.

(sensory evaluation)
Ten professional panelists gave no stickiness, smoothness, good makeup, no oiliness, no powderiness, and makeup sustainability (5 Sensory evaluation of the lack of light after time. Evaluation criteria are shown below.
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.
A: Ten people evaluated that there was no stickiness, a smooth feeling, good makeup, no oiliness, no powderiness, or no “light” after 5 hours. .
B: 7-9 people have no stickiness, smoothness, good makeup, no oiliness, no powderiness, or no “light” after 5 hours. evaluated.
C: 4-6 people don't feel sticky, have a smooth feeling, good makeup, no oiliness, no powderiness, or no shine after 5 hours evaluated.
D: 1-3 people are not sticky, have a smooth feeling, good makeup, no oiliness, no powderiness, or no shine after 5 hours evaluated.
E: None evaluated that there was no stickiness, a smooth feel, good makeup, no oiliness, no powderiness, or no “shine” after 5 hours .

  From Table 1 and Table 2, since the cosmetics described in each example contain components (A) to (G) at a specific ratio, they have high UV protection ability of PA ++++ and SPF50 or higher, and Compared to products, the evaluation is C or better for the effects of non-stickiness, smooth feeling, good makeup, no oiliness, no powderiness, and long-lasting makeup. It was.

(Prescription Examples 1 and 2)
Water-in-oil emulsified cosmetics having the formulations shown in Table 3 were prepared. Regarding the resulting cosmetics, the balance of UV protection and non-stickiness, smooth feeling, good makeup, no oiliness, no powderiness, and the effect of long-lasting makeup are described above. Good evaluation results comparable to those of the respective examples were obtained.

Claims (5)

The following components (A) to (G):
(A) 9-20% by mass of an organic ultraviolet protective agent,
(B) zinc oxide 9.5 to 20% by mass,
(C) 0.1 to 1.5% by mass of a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as structural units,
(D) Spherical cross-linked (meth) acrylic ester resin powder having a compressive strength of 0.7 to 10 kgf / mm ² determined from the following test method and formula, 3 to 25% by mass,
Compressive strength (kgf / mm ² ) = 2.8 × load (kgf) / {π × particle diameter (mm) × particle diameter (mm)}
(In the above formula, the compressive strength is determined when the resin powder particles are subjected to a compression test at 25 ° C. using a microcompression tester MCT-M200 manufactured by Shimadzu Corporation. (It is a value calculated by the above formula from the load and the particle diameter.)
(E) Silicone resin particles 0.1-2% by mass,
(F) Water-in-oil type emulsified cosmetics containing 10-50 mass% of silicone oils, and (G) water.   The mass ratio of the component (D) and the component (E) in the water-in-oil emulsified cosmetic is (component (D) / component (E)) = 25/1 to 2/1. Item 2. A water-in-oil emulsified cosmetic according to Item 1. Next component (H):
The water-in-oil emulsified cosmetic according to claim 1 or 2, further comprising (H) titanium oxide.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the component (B) is in the form of particles having a number average particle diameter of 5 to 500 nm.   The mass ratio between the component (A) and the component (C) in the water-in-oil emulsified cosmetic is (component (A) / component (C)) = 60/1 to 5/1. Item 2. A water-in-oil emulsified cosmetic according to Item 1.