JP6903024B2 - Topical skin agent - Google Patents

Description

The present disclosure relates to external preparations for skin.

Since ultraviolet rays cause photoaging such as wrinkles, sagging, and dullness of the skin, various techniques containing an ultraviolet absorber have been proposed in order to improve the ultraviolet shielding effect of external preparations for skin such as cosmetics. ..
Of the ultraviolet rays from sunlight, 99% of the ultraviolet rays that reach the surface of the earth are ultraviolet rays in the UVA region (wavelength 320 nm to 400 nm). There is a requirement for formulation. 4-tert-Butyl-4'-methoxydibenzoylmethane (also referred to as "avobenzone") is known as an ultraviolet absorber capable of absorbing ultraviolet rays in a wide range of UVA regions.

As one aspect of the organic UV absorber compounded in the external preparation for skin, a composite powder in which an inorganic powder and an organic compound UV absorber are compounded is known, and titanium oxide and 4-tert- It has been proposed to use a composite powder with butyl-4'-methoxydibenzoylmethane. For example, Patent Document 1 discloses a water-in-oil skin external preparation containing a composite powder of titanium oxide and an ultraviolet absorber and a whitening compound, and uses it as a composite powder of titanium oxide and an ultraviolet absorber. 4-tert-Butyl-4'-methoxydibenzoylmethane is mentioned as an ultraviolet absorber contained in the composite powder. Patent Document 2 describes a cosmetic containing titanium oxide and 4-tert-butyl-4'-methoxydibenzoylmethane, a composite powder having an average particle size of less than 1 μm, and a sorbitan fatty acid ester having a specific structure. Is disclosed.
Further, Patent Document 3 discloses a sunscreen cosmetic containing a specific siliconeized polysaccharide compound and an organic ultraviolet absorber, and it is said that an ultraviolet ray preventing effect can be obtained without increasing the amount of the ultraviolet absorber.

JP-A-2017-031081 Japanese Unexamined Patent Publication No. 2013-09569 Japanese Unexamined Patent Publication No. 10-29921

Since it is desired that the external preparation for skin having an ultraviolet shielding effect lasts for a long time with a high ultraviolet shielding effect, it is important that the external preparation for skin after application is kept as uniform as possible on the skin. ..
A composite powder of titanium oxide and an ultraviolet absorber (hereinafter, also referred to as "composite powder") has a high ultraviolet absorption effect, and is therefore useful for external preparations for skin where a high ultraviolet shielding effect is desired. As disclosed in 1 and 2, various improvements have been made to the preparation containing such a composite powder.
However, when the skin external preparation containing the composite powder is aged after application, phenomena such as film cracking, streaks, and peeling occur on the coated surface, and the skin familiarity tends to be impaired, and further improvement is desired. ing. This tendency is more pronounced when the skin external preparation uses a silicone-based component in order to facilitate the formulation of the composite powder into the skin external preparation or to impart water resistance to the skin external preparation. It is easy to occur.
It is conceivable to add a thickening polymer to the external preparation for skin to reduce the change over time on the coated surface, but when the thickening polymer for general use is added to the external preparation for skin, the coated surface may become sticky. is there.

One embodiment of the present disclosure has been made in view of the above circumstances, and provides an external preparation for skin that contains a composite powder of titanium oxide and an ultraviolet absorber and has excellent skin compatibility. Is an issue.

Specific means for solving the above problems include the following embodiments.
<1> The siliconeized polysaccharide compound contains more than 0% by mass and 1% by mass or less based on the total mass of the external preparation for skin, and a composite powder of titanium oxide and an ultraviolet absorber, and contains titanium oxide and an ultraviolet absorber. A skin external preparation having a mass ratio of the siliconeized polysaccharide compound to the composite powder of 0.084 to 0.000125.
<2> The external preparation for skin according to <1> above, which further contains particles having a particle size of 5 μm to 50 μm.
<3> The external preparation for skin according to <2> above, wherein the particle size of the particles is 10 μm to 50 μm.
<4> The external preparation for skin according to <2> or <3> above, wherein the particles contain resin particles.
<5> The external preparation for skin according to <4> above, wherein the resin particles contain an acrylate-based crosspolymer.
<6> The skin external preparation according to <5> above, wherein the content of the resin particles containing the acrylate-based crosspolymer with respect to the total mass of the skin external preparation is 0.4% by mass to 1.2% by mass.
<7> The skin external preparation according to <1> to <6> above, wherein the content of the composite powder of titanium oxide and the ultraviolet absorber is 14% by mass or less with respect to the total mass of the skin external preparation.
<8> The external preparation for skin according to any one of <1> to <7> above, which further contains an ultraviolet absorber other than a composite powder of titanium oxide and an ultraviolet absorber.
<9> Further, 1,3-butylene glycol is contained, and the content of the siliconeized polysaccharide compound with respect to the total mass of 1,3-butylene glycol is 0.0012% by mass to 0.006% by mass. The external preparation for skin according to any one of 1> to <8>.
<10> Any one of <1> to <9> above, wherein the composite powder of titanium oxide and an ultraviolet absorber contains a composite powder of titanium oxide and 4-tert-butyl-4'-methoxydibenzoylmethane. One of the external preparations for skin.
<11> The above-mentioned <1> to <10>, further comprising dimethicone and cyclopentasiloxane, wherein the mass ratio of dimethicone to cyclopentasiloxane is 0.2 to 0.5. External preparation for skin.
<12> The external preparation for skin according to any one of <1> to <11> above, which is a sunscreen cosmetic.

According to one embodiment of the present disclosure, it is possible to provide a skin external preparation which contains a composite powder of titanium oxide and an ultraviolet absorber and has excellent skin compatibility.

Hereinafter, an example of the embodiment of the external preparation for skin of the present disclosure will be described in detail.

The numerical range indicated by using "~" in the present specification means a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
In the present specification, the amount of each component in the external preparation for skin is a plurality of types present in the external preparation for skin unless otherwise specified, when a plurality of substances corresponding to each component are present in the external preparation for skin. It means the total amount of substances.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
As used herein, the term "oil phase" means a continuous phase in a water-in-oil type formulation, a dispersed phase in an oil-in-water type formulation, and a liquid medium of the oil phase and its Contains components dispersed or dissolved in a liquid medium.
As used herein, the term "aqueous phase" means a dispersed phase in a water-in-oil type formulation and a continuous phase in an oil-in-water type formulation, and is a liquid medium of the dispersed phase and its liquid state. Includes components dispersed or dissolved in the medium.

In the present disclosure, "excellent in skin compatibility" means that the applied external preparation for skin adheres to the skin, follows the movement of the skin well, and cracks on the coated surface even after a lapse of time. , Streaks, peeling, etc. are suppressed.
Here, the "film crack" means a crack formed on the coating film that reaches the skin surface, and the "streak" means a streak-like thickness unevenness that does not reach the skin surface formed on the coating film. , "Peeling" means that at least a part of the coating film is peeled off from the skin surface.
In the present disclosure, "stickiness" refers to the feeling after applying the external preparation for skin to the skin, and refers to the feeling of sticking or sticking between the fingers or the like and the skin to which the external preparation for skin is applied.

<External skin preparation>
The external preparation for skin of the present disclosure contains a siliconeized polysaccharide compound in an amount of more than 0% by mass and 1% by mass or less based on the total mass of the external preparation for skin, and a composite powder (composite powder) of titanium oxide and an ultraviolet absorber. The mass ratio of the siliconeized polysaccharide compound to the composite powder of titanium oxide and the ultraviolet absorber is 0.084 to 0.000125.

The skin external preparation of the present disclosure preferably contains a siliconeized polysaccharide compound and a composite powder, and further contains particles having a particle size of 5 μm to 50 μm, which will be described later. In addition, the external preparation for skin of the present disclosure may contain other components such as an ultraviolet absorber, water, an emulsifier, etc. other than the composite powder, if necessary.

The external preparation for skin of the present disclosure is preferably an emulsion. The emulsion may be an oil-in-water emulsion (O / W-type emulsion) or a water-in-oil emulsion (W / O-type emulsion), and may be used as an external preparation for skin. It can be selected accordingly.
In particular, from the viewpoint of stable inclusion of an ultraviolet absorbing component such as a composite powder, the skin external preparation of the present disclosure is more preferably a water-in-oil type skin external preparation (W / O type skin external preparation).

When the external preparation for skin of the present disclosure is an oil-in-water emulsion (O / W-type emulsion) or a water-in-oil emulsion (W / O-type emulsion), from the viewpoint of suppressing changes over time on the coated surface, The ratio of the aqueous phase / oil phase is preferably 20/80 to 80/20, more preferably 30/70 to 70/30, and even more preferably 35/65 on a mass basis.

The external preparation for skin containing the composite powder may cause film cracking, streaks, peeling, etc. on the coated surface after a lapse of time after being applied to the skin. If such a state occurs on the coated surface, it may not be possible to sufficiently obtain the protective effect of ultraviolet rays.

On the other hand, the external preparation for skin of the present disclosure contains the siliconeized polysaccharide compound in an amount of more than 0% by mass and not more than 1% by mass with respect to the total mass of the external preparation for skin, and the siliconeized polysaccharide with respect to the composite powder. By setting the mass ratio of the compound to 0.084 to 0.000125, it is possible to prepare a skin external preparation that contains a composite powder of titanium oxide and an ultraviolet absorber and has excellent skin compatibility and durability. it can.

The present inventors speculate that the reason why the external preparation for skin of the present disclosure exerts the above-mentioned effects is as follows. However, the following speculation does not limit the interpretation of the external preparation for skin disclosed in the present disclosure, but is described as an example.

As will be described later, the siliconeized polysaccharide compound contained in the external preparation for skin of the present disclosure has a partial structure having a sugar residue containing a large number of hydroxy groups and having a siloxane bond.
In the external preparation for skin of the present disclosure, a siliconeized polysaccharide compound having such a structure is added in a small amount of more than 0% by mass and 1% by mass or less based on the total mass of the external preparation for skin, and the compound powder is added. By setting the mass ratio of the siliconeized polysaccharide compound to 0.084 to 0.000125, the siliconeized polysaccharide compound has good spreadability on the skin even though it is an external preparation for the skin containing a composite powder. It is considered that due to the action of a large number of hydroxy groups possessed by the skin, a thin and soft film having an affinity with the skin is formed and adheres to the skin surface, and the followability of the external preparation for skin to the skin lasts for a long time.
As described above, the external preparation for skin of the present disclosure adheres to the skin and maintains its followability to the skin. Therefore, by using the external preparation for skin of the present disclosure, an excellent ultraviolet shielding effect due to the inclusion of the composite powder can be obtained. Although it is obtained, it is estimated that good skin familiarity will last for a long time.

On the other hand, the above-mentioned Patent Document 1 (Japanese Patent Laid-Open No. 2017-031081), Patent Document 2 (Japanese Patent Laid-Open No. 2013-095699 ), and Patent Document 3 (Japanese Patent Laid-Open No. 10-29921) are familiar to the skin. There is no focus on improving and sustaining its effects.

Hereinafter, the components that can be contained in the external preparation for skin of the present disclosure will be described in detail.

[Siliconeized polysaccharide compound]
The external preparation for skin of the present disclosure contains a siliconeized polysaccharide compound. The external preparation for skin may contain one type of siliconeized polysaccharide compound alone, or may contain two or more types.

In the present disclosure, the silicone-modified polysaccharide compound refers to a sugar residue derived from the polysaccharide compound and a siloxy group (-OSiR ^a R ^b R ^c R ^d ; R ^a , R ^b , R ^c and R) in the structure of the compound. ^d is a compound having at least a monovalent organic group) and. Polysaccharide compounds include known polysaccharides and derivatives thereof. The siliconeized polysaccharide compound is obtained by reacting a reactive functional group (hydroxy group, carboxy group, etc.) of the polysaccharide compound with a silicone compound having a functional group capable of reacting with the reactive functional group of the polysaccharide compound. be able to. That is, the silicone-modified polysaccharide compound in the present disclosure is preferably a silicone-modified polysaccharide compound obtained by modifying the polysaccharide compound with a silicone compound.

The siliconeized polysaccharide compound is preferably a compound represented by the following formula (I).

In formula (I), Glu represents a sugar residue derived from a polysaccharide compound, and X represents a carbonyl group, an amino group, an ether group, a carbamoyl group, or -CH ₂ CH (OH)-. Y represents an alkylene group having a total carbon number of 2 to 8 which may have an oxygen atom, a nitrogen atom, a sulfur atom, a phenylene group, a carbonyloxy group or an oxycarbonyl group in the main chain. The alkylene group represented by Y may further have a substituent, and examples of the substituent include a substituent selected from a hydroxy group, an alkoxy group and an alkyl group.
R ¹ represents a monovalent organic group having a total carbon number of 1 to 8, and R ² , R ³ and R ⁴ are independently ^{monovalent organic groups having a total carbon number of 1 to 8 or -OSiR 5} R ⁶ R. Represents the siloxy group represented by ^7. R ⁵ , R ⁶ and R ⁷ each independently represent a monovalent organic group having 1 to 8 total carbon atoms. a represents an integer of 0, 1 or 2.

As the polysaccharide compound from which the sugar residue represented by Glu is derived, various known polysaccharide compounds can be used. Examples of such polysaccharide compounds include cellulose, hemicellulose, arabic gum, tragant gum, tamarind gum, pectin, starch, mannan, guar gum, locust bean gum, quince seed gum, alginic acid, carrageenan, agar, xanthan gum, dextran, pullulan, etc. Examples include chitin, chitosan, hyaluronic acid, and chondroitin sulfate. In the present disclosure, the polysaccharide compound includes a derivative of the polysaccharide compound. As the derivative of the polysaccharide compound, for example, carboxymethylation, sulfation, phosphorylation, methylation, ethylation, addition of alkylene oxides such as ethylene oxide and propylene oxide, acylation, cationization, and reduction in molecular weight were carried out. Derivatives of polysaccharide compounds can be mentioned.

As the polysaccharide compound from which the sugar residue represented by Glu is derived, ethyl cellulose or pullulan is preferable, and pullulan is more preferable. The average molecular weight of the polysaccharide compound varies depending on the type of the polysaccharide compound, but is preferably about 1,000 to 5,000,000.

X represents a carbonyl group, an amino group, an ether group, a carbamoyl group, or −CH ₂ CH (OH) −, and is preferably a carbamoyl group (= CONH).
The alkylene group having a total carbon number of 2 to 8 represented by Y is an alkylene group having an oxygen atom, a nitrogen atom, a sulfur atom or the like in the main chain, and an alkylene group having an arylene group such as a phenylene group in the main chain. The main chain contains an alkylene group having a carbonyloxy group or an oxycarbonyl group. These alkylene groups can have substituents such as a hydroxy group, an alkoxy group and an alkyl group, and the terminal atom of the alkylene group may be a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.

Specific examples of Y include-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₆ -,-(CH ₂ ) ₈ -,-[CH ₂ CH (CH ₃ )]-,-(CH ₂ ) ₂ O (CH ₂ ) _3- , -CH ₂ CH (OH) -CH _2-, etc. are mentioned, and-(CH ₂ ) ₃ -is preferable.

The ^{monovalent organic group having 1 to 8 carbon atoms represented by R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ or R ⁷ includes an alkyl group (methyl group, ethyl group, propyl group, etc.). Butyl group, etc.), cycloalkyl group (cyclopentyl group, cyclohexyl group, etc.), aryl group (phenyl group, etc.), aralkyl group (benzyl group, etc.), alkenyl group (vinyl group, allyl group, etc.) or alkylfluoride group (, 3,3-Tolufluoropropyl group).

In R ^{2, R 3} or ^{R 4,} as the siloxy group represented by -OSiR ⁵ R ⁶ R ^7, trimethylsiloxy group, ethyl dimethylsiloxy group, phenyl dimethylsiloxy group, vinyldimethylsiloxy group, 3,3,3 Examples thereof include a trifluoropropyldimethylsiloxy group.

A preferred embodiment of the compound represented by the formula (I) comprises a compound in which a = 0 and R ² , R ³ and R ⁴ are methyl groups.

Examples of commercially available silicone-modified polysaccharide compounds include TSP-30-D5 (Shin-Etsu Chemical Co., Ltd.).

The siliconeized polysaccharide compound can be obtained by reacting the reactive functional group (hydroxy group, carboxy group, etc.) of the polysaccharide compound as described above with the silicone compound represented by the following formula (II). A known method can be used for the reaction between such a silicone compound and a polysaccharide compound.

Wherein ^{(II), Y, R 1} , R 2, R 3, R 4 and a are the same as in formula (I) ^Y, and ^{R 1, R 2, R 3} , R 4 and a.
A represents a functional group capable of reacting with the reactive functional group of the polysaccharide compound, for example, isocyanate group, epoxy group, vinyl group, acryloyl group, methacryloyl group, amino group, imino group, hydroxy group, carboxy group, mercapto. The group etc. can be mentioned.

As the siliconeized polysaccharide compound, a compound represented by the following formula (III) (silicone-modified pullulan) is preferable. In formula (III), PL represents the glucose residue of pullulan.

In the siliconeized polysaccharide compound, the binding ratio of the silicone compound to the reactive functional group of the polysaccharide compound does not necessarily have to be 100%, but from the viewpoint of the effect, the binding ratio of the silicone compound to the polysaccharide compound is not too low. Is preferable. From the viewpoint of solubility in an oil agent contained in an external preparation for skin (for example, an oil agent such as dimethicone and cyclopentasiloxane), it is desirable that the silicone compound is bound to the polysaccharide compound to the extent that it dissolves in the oil agent. Specifically, although it varies depending on the type, it is usually preferable that the average number of bonds (degree of substitution) of the silicone compound per unit of the constituent sugar of the polysaccharide compound is 0.5 to 2.5. In the present disclosure, the degree of substitution is converted from the Si content (mass%) in the compound.

The content of the siliconeized polysaccharide compound in the external preparation for skin is more than 0% by mass and 1% by mass or less, preferably 0.8% by mass or less, and 0.0001% by mass, based on the total mass of the external preparation for skin. More than 0.5% by mass is more preferable, and 0.0003% by mass or more and 0.3% by mass or less is further preferable. When the content of the siliconeized polysaccharide compound is within the above range, the skin fits well when applied to the skin, and even after a lapse of time, film cracks, streaks, peeling, etc. occur on the applied surface. It is suppressed. As described above, in the external preparation for skin of the present disclosure, the inclusion of a trace amount of the siliconeized polysaccharide compound within the above range is one of the characteristic components in which the excellent effects of the present disclosure are exhibited.

When the external preparation for skin is in the form of an emulsion, the siliconeized polysaccharide compound is preferably contained in the oil phase.

[Composite powder of titanium oxide and UV absorber]
The external preparation for skin of the present disclosure contains a composite powder (composite powder) of titanium oxide and an ultraviolet absorber. The external preparation for skin may contain one type of composite powder alone, or may contain two or more types of composite powder.

By containing the composite powder, the external preparation for skin of the present disclosure can improve the shielding effect of ultraviolet rays (UVA region and / or UVB region) harmful to the skin.

The titanium oxide constituting the composite powder is not particularly limited, and may be any crystalline type titanium oxide such as anatase type, rutile type, and brookite type. The crystal type of titanium oxide is preferably a rutile type from the viewpoint of improving the ultraviolet shielding ability.

The titanium oxide may be surface-treated with an inorganic substance such as aluminum hydroxide, silicon oxide or zirconium oxide, or may be surface-treated with a fatty acid such as stearic acid, isostearic acid or lauric acid. , It may be surface-treated with both inorganic substances and fatty acids. Titanium oxide can be inactivated by surface-treating titanium oxide with an inorganic substance such as aluminum hydroxide. Further, by surface-treating titanium oxide with a fatty acid such as stearic acid, the surface of titanium oxide can be made hydrophobic.

The average primary particle size of titanium oxide is preferably, for example, 1 nm to 90 nm, and more preferably 5 nm to 50 nm, from the viewpoint of ultraviolet shielding ability and transparency of the external preparation for skin. The average primary particle size of titanium oxide is the value obtained by photographing 1000 or more particles with a transmission electron microscope, performing image processing on each of the photographed particles using an image analysis type particle size distribution measuring device, and measuring the equivalent circle diameter. To do. When a commercially available product is used as titanium oxide, the average primary particle size described in a catalog or the like can be applied as it is.

As the ultraviolet absorber, an organic ultraviolet absorber is preferable from the viewpoint of ease of compounding with titanium oxide. Among the organic ultraviolet absorbers, an organic ultraviolet absorber having an absorbing ability in at least one of the UVA region (wavelength 320 nm to 450 nm) and UVB (wavelength 280 nm to 320 nm) is preferable, and the organic ultraviolet absorber having an absorbing ability at least in the vicinity of the UVA region Absorbents are more preferred.

Specific examples of the ultraviolet absorber include 4-tert-butyl-4'-methoxydibenzoylmethane, hexyl diethylaminohydroxybenzoylbenzoate, and 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy. } -Phenyl] -6- (4-Methoxyphenyl) -1,3,5-triazine, 2,4,6-tris (4- (2-ethylhexyloxycarbonyl) anilino) -1,3,5-triazine, Examples thereof include ethylhexyl salicylate, tetrahydroxybenzophenone, dihydroxybenzophenone, sodium dihydroxydimethoxybenzophenone disulfonate, 2-hydroxy-4-methoxybenzophenone, homomentyl salicylate, and 2-ethylhexyl paramethoxycinnamate.
Among these UV absorbers, 4-tert-butyl-4'-methoxydibenzoylmethane, hexyl diethylaminohydroxybenzoyl benzoate, and 2,4-bis from the viewpoint of ease of compounding with titanium oxide and cost. -[{4- (2-Ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-At least one selected from the group consisting of triazine is preferable, and the UVA region is preferable. From the viewpoint of the effect of shielding ultraviolet rays in the vicinity, 4-tert-butyl-4'-methoxydibenzoylmethane (abobenzon) is more preferable. That is, a preferred embodiment of the composite powder is a composite powder of titanium oxide and 4-tert-butyl-4'-methoxydibenzoylmethane (hereinafter, also referred to as "avobenzone composite titanium oxide").

The composite powder preferably has a surface treatment layer containing an ultraviolet absorber on the surface of titanium oxide. The surface treatment layer is preferably present on the entire surface of titanium oxide, but there may be a portion where the surface treatment layer does not exist. The bonding mode between the surface of titanium oxide (inorganic substance or fatty acid arranged on the surface when titanium oxide is surface-treated at least one of the inorganic substance and the fatty acid) and the ultraviolet absorber is the titanium oxide and the ultraviolet absorber. As long as it behaves integrally with, there is no particular limitation, and it may be a chemical bond such as a covalent bond or a non-chemical bond such as adsorption.

The presence of the ultraviolet absorber on the surface of titanium oxide can be confirmed by measuring the reflection spectrum of the composite powder.

The ratio of titanium oxide and the ultraviolet absorber in the composite powder is not particularly limited. From the viewpoint of the ultraviolet shielding ability of the composite powder, for example, the amount of the ultraviolet absorber may be 0.03 part by mass to 1 part by mass with respect to 1 part by mass of titanium oxide.

The average particle diameter of the composite powder is preferably less than 1 μm. When the average particle diameter of the composite powder is less than 1 μm, the coloring of the external preparation for skin by the composite powder itself is suppressed, and so-called whitening is less likely to occur. The average particle diameter of the composite powder is more preferably 1 nm to 500 nm, and further preferably 3 nm to 100 nm, from the viewpoint of the ultraviolet shielding effect and the feeling of use.
The average particle size of the composite powder can be measured by the same method as the average primary particle size of titanium oxide.

As the composite powder, for example, the composite powder disclosed in International Publication No. 2010/098249 can be used. The composite powder is also available as a commercial product. Examples of commercially available composite powders include HXMT-100ZA manufactured by TAYCA CORPORATION. HXMT-100ZA has a surface-treated layer containing 4-tert-butyl-4'-methoxydibenzoylmethane formed on the surface of titanium oxide surface-treated with aluminum hydroxide and stearic acid.

The mass ratio of the siliconeized polysaccharide compound to the composite powder in the external preparation for skin is 0.084 to 0.000125, and by satisfying this range, the familiarity with the skin when the external preparation for skin is applied is improved.

The content of the composite powder in the external preparation for skin is preferably, for example, 15% by mass or less, more preferably 1% by mass to 15% by mass, based on the total mass of the external preparation for skin. It is more preferably mass% to 15% by mass. Further, from the viewpoint of making a skin external preparation having a light feeling of use, the content of the composite powder can be, for example, 14% by mass or less. The lower limit of the content of the composite powder is such that the UV shielding effect of the composite powder can be obtained and the mass ratio of the siliconeized polysaccharide compound to the composite powder satisfies 0.084 to 0.000125. For example, it can be 6% by mass.

The composite powder may be contained in either an oil phase or an aqueous phase when the external preparation for skin is an emulsion. The composite powder is preferably contained in the oil phase from the viewpoints of water resistance of the external preparation for skin, a feeling of use (smoothness, refreshing feeling), an effect of improving the ultraviolet shielding effect, and the like.

For example, when blending the composite powder into the oil phase, a slurry may be prepared using an oil agent such as silicone oil and blended with other components in the form of a slurry.
The content of the composite powder in the slurry is not particularly limited. In general, the content of the composite powder in the slurry is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 60% by mass, based on the total mass of the slurry. When the content of the composite powder in the slurry is within the above range, the composite powder tends to be stably contained in the external preparation for skin.

[UV absorbers other than composite powder]
The external preparation for skin of the present disclosure may contain an ultraviolet absorber other than the composite powder (hereinafter, also referred to as "another ultraviolet absorber") from the viewpoint of further improving the ultraviolet shielding effect.
Other UV absorbers may be contained alone or in combination of two or more in the external preparation for skin.

The other ultraviolet absorber is not particularly limited as long as it is an ultraviolet absorber usually used for external preparations for skin. As the other ultraviolet absorber, an organic ultraviolet absorber is preferable, and specific examples thereof include compounds similar to specific examples of the ultraviolet absorber contained in the composite powder.

The ultraviolet absorber contained in the composite powder and other ultraviolet absorbers may be the same or different, and can be appropriately selected depending on the desired ultraviolet shielding effect. For example, when the same UV absorber as the UV absorber contained in the composite powder is selected as another UV absorber, the mass ratio with the siliconeized polysaccharide is limited to a predetermined range. In the external preparation, the ultraviolet shielding effect expected from the inclusion of the composite powder can be further improved.
Examples of combinations of the composite powder and other UV absorbers include a combination of a composite powder of titanium oxide and avobenzone and avobenzone, a combination of a composite powder of titanium oxide and avobenzone and methylenebisbenzotriazolyltetramethylbutylphenol. Examples thereof include a combination of a composite powder of titanium oxide and avobenzone and hexyl diethylaminohydroxybenzoyl benzoate.

When the external preparation for skin of the present disclosure contains another ultraviolet absorber, the content of the other ultraviolet absorber is for external use on the skin from the viewpoint of the stability of the preparation such as the ultraviolet shielding effect and the suppression of precipitation of the ultraviolet absorber. It is preferably 0.2% by mass or less based on the total mass of the agent.

[Particles with a particle size of 5 μm to 50 μm]
The external preparation for skin of the present disclosure preferably contains particles having a particle size of 5 μm to 50 μm (hereinafter, also referred to as “specific particles”). By containing the particles having a particle size of 5 μm to 50 μm, the stickiness of the coated surface of the external preparation for skin can be effectively suppressed.

In the present disclosure, the particle size of a specific particle means an average primary particle size obtained by arithmetically averaging the circle-equivalent diameters evaluated for 100 particles using a scanning electron microscope (SEM). To do.
The specific method for measuring the particle size of the specific particles is as follows.
First, each external preparation for skin to be measured is diluted 100-fold with water to obtain a diluted solution. Next, the diluted solution is dropped onto the carbon foil, and the dried solution is used as a sample. An image of the prepared sample is obtained by appropriately using a magnification at which the entire appearance of the particles can be observed using SEM. Next, the number of pixels is calculated for the area of the particles in the obtained image by image processing, and the obtained number of pixels is converted into the area. The diameter when the obtained area is converted into a circle is calculated, and the diameter converted into a circle evaluated for 100 particles is arithmetically averaged to confirm.
When only an image in which particles overlap each other can be obtained, a clear image can be obtained by increasing the dilution ratio, stirring, or changing the dilution solvent to ethanol or the like as appropriate.
The morphology of the specific particles includes a spherical shape, a plate shape, a cubic shape, and the like even in a dry state, and particles maintaining such a clear three-dimensional structure can be preferably used as the specific particles.

The particle size of the specific particles is preferably 5 μm to 50 μm, more preferably 10 μm to 50 μm, and even more preferably 10 μm to 45 μm. When the particle size of the specific particles is 5 μm or more, the effect of suppressing stickiness is improved, and a good tactile sensation tends to be obtained. Further, when the particle size of the specific particles is 50 μm or less, the particles are suppressed from falling off from the coating film of the external preparation for skin, remarkable protrusion, and the like, and the tactile sensation tends to be further improved.

The specific particles may be inorganic particles or resin particles, and any of the particles can be used to obtain a good tactile sensation in which stickiness is suppressed on the surface to which the external preparation for skin is applied. On the other hand, from the viewpoint of obtaining a light feeling of use, the specific particles are preferably resin particles.

Examples of resin particles include nylon, polyethylene, polypropylene, melamine, polyphenylene sulfide, polyether sulfone, polyamideimide, polylactic acid, ethyl cellulose, dimethicone (siloxane), dimethiconol, vinyl dimethicone, silsesquioxane, polyethylene oxide, or these. Examples thereof include particles containing a resin or polymer such as a cross polymer, an acrylate-based cross polymer, and collagen, and particles containing an acrylate-based cross polymer are preferable from the viewpoint of suppressing stickiness.

In the present disclosure, the acrylate-based crosspolymer refers to a crosspolymer containing a structural unit derived from an acrylic acid ester and / or a methacrylic acid ester.

Examples of the acrylate-based crosspolymer include methyl methacrylate crosspolymer, (methyl methacrylate / glycol dimethacrylate) crosspolymer, (butyl acrylate / glycol dimethacrylate) crosspolymer, (acrylic acid / VP) crosspolymer, and (acrylic acid / VP) crosspolymer. Acid / phosphorylcholine glycolic acid) crosspolymer, (Na acrylate / acryloyldimethyltaurine / dimethylacrylamide) crosspolymer, (butyl acrylate / isopropylacrylamide / PEG-18 dimethacrylate) crosspolymer, (Acrylate / alkyl acrylate) C10-30)) Crosspolymer, (Acrylate / Alkyl Acrylate (C10-30)) Crosspolymer K, (Acrylate / Alkyl Acrylate (C10-30)) Crosspolymer Na, (Acrylate / Ethylhexyl Acrylate) Crosspolymer, (Acrylate / ethylhexyl acrylate / glycidyl methacrylate) crosspolymer, (Acrylate / vinyl isodecanoate) crosspolymer, (Acrylate / vinyl isodecanoate) crosspolymer Na, (Acrylate / PEG-4 dimethacrylate) crosspolymer, (Acrylates / PEG-4 dimethacrylate) / Vinyl neodecanoate) Crosspolymer, (Acrylate / Alkyl methacrylate (C12, 13) / methoxyethyl methacrylate) Crosspolymer, (Acrylate / Steareth methacrylate-20) Crosspolymer, (Acrylate / Ceteareth methacrylate-20) Cross Polymers, (Acrylate / trimethylsiloxypropyl methacrylate) crosspolymer, (Acrylate / Behenes methacrylate-25) crosspolymer Na, (Acrylate / methoxymethacrylate PEG-90) crosspolymer,

(Acryloyldimethyltaurin Na / VP) crosspolymer, (Acryloyldimethyltaurin Na / PEG-8 diacrylate) crosspolymer, (Acryloyldimethyltaurinammonium / carboxyethylammonium acrylate) crosspolymer, (Acryloyldimethyltaurinammonium / steareth methacrylate) -25) Crosspolymer, (Acryloyldimethyltaurinammonium / Behenes methacrylate-25) Crosspolymer, (Hexylene glycol dimethacrylate / Glycoldimethacrylate) Crosspolymer, (Styline / Acrylate / Dimethicone acrylate) Crosspolymer, ( Styrene / stearyl methacrylate) crosspolymer, (polyurethane-24 / methyl methacrylate) crosspolymer, (diethylaminoethyl methacrylate / HEMA / perfluorohexylethyl methacrylate) crosspolymer, (stearyl methacrylate / lauryl methacrylate) crosspolymer , (Methyl methacrylate / PEG methacrylate / PPG-4 / 3) crosspolymer, (lauryl methacrylate / glycol dimethacrylate) crosspolymer, (lauryl methacrylate / Na methacrylate) crosspolymer, Na acrylate crosspolymer, Lauryl Acrylate Cross Polymer, Acrylate Cross Polymer, Acrylate Cross Polymer-2-Na, Acrylate Cross Polymer-3, Acrylate Cross Polymer-4, Acrylate Polyacrylate Cross Polymer-9-AMP, Acrylate Cross Polymer K, Dimethacrylate glycol crosspolymer, polyacrylate-1 crosspolymer, polyacrylate-2 crosspolymer, polyacrylate crosspolymer-1-Na, polyacrylate crosspolymer-10, polyacrylate crosspolymer-11, polyacrylate crosspolymer-14 , Polyacrylate crosspolymer-3, Polyacrylate crosspolymer-5, Polyacrylate crosspolymer-6, allyl methacrylate crosspolymer, propyltrimethicone methacrylate crosspolymer, and the like.

Those containing the above acrylate-based crosspolymer and in the form of particles can be suitably used as the specific particles in the present disclosure.
In the above example of the acrylate-based cross polymer, "VP" represents "vinylpyrrolidone", "HEMA" represents "hydroxyethyl methacrylate", and "AMP" represents "aminomethylpropanol".
The resin particles may contain only one type of acrylate-based crosspolymer, or may contain two or more types.

When the external preparation for skin contains specific particles, the content of the specific particles is preferably, for example, 0.0001% by mass to 0.01% by mass, based on the total mass of the siliconeized polysaccharide compound. It is more preferably 005% by mass to 0.009% by mass, and further preferably 0.008% by mass to 0.008% by mass.

When acrylate-based cross-polymer particles are used as the specific particles, the content of the acrylate-based cross-polymer particles with respect to the total mass of the external preparation for skin is determined from the viewpoint of being familiar with the skin, suppressing stickiness, and parallelizing the ultraviolet shielding effect. It is preferably 0.4% by mass to 1.2% by mass, more preferably 0.4% by mass to 1% by mass.

Examples of the inorganic particles include silica particles, porous silica particles, zinc oxide, mica, kaolin, bentonite, calcium carbonate, and talc.
Examples of the silica particles include particles such as silica, silylated silica, dimethylsilylated silica, and silica dimethicone silicate.

Commercially available products of specific particles include Matsumoto Microsphere S-100 (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., acrylate-based crosspolymer particles, 20 μm), Matsumoto Microsphere S-102 (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., acrylate-based cloth). Polymer particles, 20 μm), Matsumoto Microsphere M (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., acrylate-based cross-polymer particles, 15 μm), Matsumoto Microsphere M-305 (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., acrylate-based cross-polymer particles, 15 μm) ), Techpolymer ACX-1502C (Sekisui Chemicals Co., Ltd., particle size 15 μm), Techpolymer ACX-2502 (Sekisui Chemicals Co., Ltd.), SILICA MICRO BEAD (Nikki Catalyst Kasei Co., Ltd., silica particles) , Particle size: 5 μm) and the like.

[Oil]
The external preparation for skin of the present disclosure preferably contains an oil preparation. The oil agent is a component that serves as a solvent or a dispersion medium in the composition forming the oil phase when the external preparation for skin is composed as an emulsion. The oil agent is not particularly limited as long as it is liquid at room temperature (25 ° C.).
Examples of the oil agent include silicone oil, ester oil, hydrocarbon oil and the like, and it is preferable to contain silicone oil.
The external preparation for skin may contain one oil agent alone or two or more oil agents.

Examples of the silicone oil include linear or branched polysiloxanes such as dimethicone (dimethylpolysiloxane), methylphenylpolysiloxane, methylhydrogenpolysiloxane, and diphenylsiloxyphenyltrimethicone, octamethylcyclotetrasiloxane, and cyclopentasiloxane (cyclopentasiloxane). Decamethylcyclopentasiloxane), dodecamethylcyclohexasiloxane, cyclic polysiloxane such as tetramethyltetrahydrogencyclotetrasiloxane, caprylyl methicone, and the like.
Commercially available silicone oil products include KF-96L-0.65cs, KF-96L-1cs, KF-96L-1.5cs, KF-96L-2cs, KF-96L-5cs, KF-96A-5cs, KF- 96A-6cs, KF-96-10cs, KF-96-20cs, KF-995, KF-56A (Shin-Etsu Chemical Co., Ltd.), SH200 C Fluid 1CS, SH200 Fluid 1.5CS, SH200 C 2CS, SH200 C Fluid 5CS, SH200 C Fluid 6CS, SH200 C Fluid 10CS, SH200 C Fluid 20CS, 2-1184 Fluid, SH245 Fluid, DC246 Fluid, DC345 Fluid, SS-3408 (above, Toray Dow Corning Co., Ltd.) Examples thereof include TSF405 and TSF4045 (above, Momentive Performance Materials Co., Ltd.).

Ester oils include pentaerythrityl tetraethylcaproate, cetyl ethylcaproate, jojoba oil, di (phytosteryl / octyldodecyl) lauroyl glutamate, triisostea, glyceryl diisostearate, triethylhexanoin, dimer dilinoleic acid (phytosteryl / behenyl). , Dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), isopropyl palmitate, macadamia nut fatty acid phytosteryl, tetra (bechenic acid / benzoic acid / ethylcaproic acid) pentaerythrityl, ethylhexyl palmitate, myristyl myristate, Examples thereof include tripropylene glycol dipivalate and isotridecyl isononanoate.

The hydrocarbon oil may be either linear or branched. Examples of the hydrocarbon oil include isoalkane (isoparaffin) having 8 to 16 carbon atoms such as isodecane, isododecane, and isohexadecane.

The content of the oil agent in the external preparation for skin is preferably, for example, 5% by mass to 80% by mass, more preferably 10% by mass to 80% by mass, based on the total mass of the external preparation for skin. It is more preferably 15% by mass to 80% by mass, particularly preferably 30% by mass to 80% by mass, and most preferably 40% by mass to 80% by mass.
When the skin external preparation of the present disclosure is a water-in-oil skin external preparation, it is preferable that the silicone oil is contained in an amount of 50% by mass or more based on the total mass of the oil phase excluding the composite powder. When the content of the silicone oil in the oil phase excluding the composite powder of the external preparation for skin is 50% by mass or more, the water resistance and the feeling of use (refreshing feeling) of the external preparation for skin tend to be improved.
The content of the oil agent includes the oil contained together with the silicone gel when a commercially available product of the silicone gel described later is used in producing the external preparation for skin of the present disclosure.

The external preparation for skin of the present disclosure preferably contains dimethicone (dimethylpolysiloxane) and cyclopentasiloxane (decamethylcyclopentasiloxane) from the viewpoint of suppressing the occurrence of film cracking and improving skin compatibility. In this case, the mass ratio of dimethicone to cyclopentasiloxane is preferably 0.2 to 0.5, more preferably 0.25 to 0.45.

The total content of dimethicone and cyclopentasiloxane in the external preparation for skin is preferably, for example, 10% by mass to 50% by mass, and 15% by mass to 45% by mass, based on the total mass of the external preparation for skin. More preferably, it is more preferably 20% by mass to 45% by mass.

[Polyether-modified silicone]
The external preparation for skin of the present disclosure may contain a polyether-modified silicone. When the external preparation for skin contains a polyether-modified silicone, the emulsification stability tends to be improved when the external preparation for skin is formed as an emulsion. The external preparation for skin may contain one type of polyether-modified silicone alone, or may contain two or more types.

The polyether-modified silicone is a polymer having a silicone chain as a main chain and a polyether chain introduced by modification. The silicone chain may be a linear silicone chain or a branched silicone chain. Examples of the polyether chain include a polyethylene glycol (PEG) chain and a polypropylene glycol (PPG) chain. The polyether-modified silicone may further have an alkyl chain having 8 to 22 carbon atoms introduced by the modification.

The HLB (Hydrophile-Lipophile Balance) value of the polyether-modified silicone is preferably 1 to 10 and more preferably 2 to 8 from the viewpoint of emulsification stability of the external preparation for skin. In the present specification, the HLB value of the polyether-modified silicone is a value obtained from the molecular weight and the number of ethylene oxide groups. When a commercially available product is used, the HLB value described in a catalog or the like can be applied as it is.

Examples of the polyether-modified silicone include PEG-11 methyl ether dimethicone, PEG / PPG-20 / 22 butyl ether dimethicone, PEG / PPG-19 / 19 dimethicone, PEG-9 dimethicone, PEG-9 methyl ether dimethicone, and PEG-10 dimethicone. Examples thereof include PEG-21 methyl ether dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, and lauryl PEG-9 polydimethylsiloxyethyl dimethicone.
The polyether-modified silicone is also available as a commercial product. Commercially available products include, for example, KF-6011, KF-6011P, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6017P, KF-6043, KF-6028, KF-6028P. , KF-6038 (above, Shin-Etsu Chemical Co., Ltd.) and the like.

As the polyether-modified silicone, a polyether-modified silicone having a branched silicone chain is preferable from the viewpoint of emulsion stability of the external preparation for skin. Among them, the polyether-modified silicone is more preferably at least one selected from PEG-9 polydimethylsiloxyethyl dimethicone and lauryl PEG-9 polydimethylsiloxyethyl dimethicone.

When the external preparation for skin contains a polyether-modified silicone, the content of the external preparation for skin is preferably 0.01% by mass to 10% by mass, for example, 0% by mass, based on the total mass of the external preparation for skin. .1% by mass to 8% by mass is more preferable, and 0.5% by mass to 6% by mass is further preferable. When the content of the polyether-modified silicone is 0.01% by mass or more, the emulsification stability of the external preparation for skin tends to be improved, and when the content of the polyether-modified silicone is 10% by mass or less, the external preparation for skin is used. The stickiness after application of the agent tends to decrease.

[Silicone gel]
The external preparation for skin of the present disclosure may contain a silicone gel from the viewpoint of emulsion stability and the like.
In the present disclosure, the silicone gel refers to a crosslinked product in which the silicone chains forming the main chain skeleton are crosslinked with a polyether chain, a polyglycerin chain, a silicone chain, or the like.
Depending on the structure of the chain used for cross-linking, there are types such as polyether-modified silicone gel, polyglycerin-modified silicone gel, polyether-alkyl co-modified silicone gel, and polyglycerin-alkyl co-modified silicone gel. The external preparations for skin of the present disclosure can be used without limitation.

Specific examples of the silicone gel include (dimethicone / (PEG-10 / 15) crosspolymer, (PEG-15 / lauryldimethicone) crosspolymer, (PEG-10 / lauryldimethicone) crosspolymer, (PEG-15 / lauryl). Polydimethylsiloxyethyl dimethicone) crosspolymer, (dimethicone / polyglycerin-3) crosspolymer, (lauryldimethicone / polyglycerin-3) crosspolymer, (polyglyceryl-3 / laurylpolydimethylsiloxyethyl dimethicone) crosspolymer, (dimethicone / Examples include (vinyl dimethicone) crosspolymer, (dimethicone / phenylvinyldimethicone) crosspolymer, (vinyldimethicone / lauryldimethicone) crosspolymer, (laurylpolydimethylsiloxyethyldimethicone / bisvinyldimethicone) crosspolymer, etc.

Commercially available silicone gel products include KSG-210, KSG-240, KSG-310, KSG-320, KSG-330, KSG-340, KSG-320Z, KSG-350Z, KSG-360Z, KSG-380Z, KSG- 710, KSG-810, KSG-820, KSG-830, KSG-840, KSG-820Z, KSG-850Z, KSG-15, KSG-1510, KSG-16, KSG-1610, KSG-18A, KSG-19, Examples thereof include KSG-016F, KSG-41A, KSG-42A, KSG-43A, KSG-44A, KSG-042Z, KSG-045Z, KSG-048Z (above, Shin-Etsu Chemical Co., Ltd.).

Among silicone gels, from the viewpoints of availability, swellability to oils such as silicone oil, and emulsion stability, (dimethicone / (PEG-10 / 15) crosspolymer and (dimethicone / vinyldimethicone) crosspolymer At least one selected from the above group is preferable, and it is more preferable to use (dimethicone / (PEG-10 / 15) crosspolymer and (dimethicone / vinyldimethicone) crosspolymer in combination.

The content of the silicone gel in the external preparation for skin is preferably, for example, 0.1% by mass to 8% by mass, and 0.25% by mass to 4.5% by mass, based on the total mass of the external preparation for skin. Is more preferable, and 0.5% by mass to 3% by mass is further preferable.
In the external preparation for skin, the silicone gel may be contained alone or in combination of two or more. When two or more types of silicone gels are contained, the above content is the total content of two or more types of silicone gels.

[Surfactant]
The external preparation for skin of the present disclosure may contain a surfactant. When the external preparation for skin contains a surfactant, the viscosity stability and emulsification stability of the external preparation for skin tend to be improved. The external preparation for skin may contain one type of surfactant alone, or may contain two or more types of surfactants.

The surfactant may be either a nonionic surfactant or an ionic surfactant. Examples of the ionic surfactant include alkyl sulfonates, alkyl sulfates, monoalkyl phosphates, lecithin and the like. Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, organic acid monoglyceride, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyglycerin condensed ricinoleic acid ester, sucrose fatty acid ester, polyethylene glycol fatty acid ester, and polyoxy. Ethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid Examples include esters, polyoxyethylene glycol oil, polyoxyethylene hydrogenated castor oil and the like.

When the external preparation for skin contains a surfactant, the content of the surfactant is preferably, for example, 0.01% by mass to 30% by mass, preferably 0.05% by mass, based on the total mass of the external preparation for skin. It is more preferably from% to 20% by mass, and even more preferably 0.1% by mass to 10% by mass. When the content of the surfactant is 0.01% by mass or more, the viscosity stability of the external preparation for skin tends to be improved, and when the content of the surfactant is 30% by mass or less, the usability is improved. Tend to do.

[water]
The external preparation for skin of the present disclosure preferably contains water. Water is a component that serves as a solvent or a dispersion medium in the composition constituting the aqueous phase when the external preparation for skin is composed as an emulsion. The water is not particularly limited as long as it is water that can be applied to an external preparation for skin.

[Multivalent alcohol]
The external preparation for skin of the present disclosure may contain a polyhydric alcohol. When the external preparation for skin contains polyhydric alcohol, the feeling of use (moisturizing property) of the external preparation for skin tends to be improved. The external preparation for skin may contain one type of polyhydric alcohol alone, or may contain two or more types of polyhydric alcohol.

Polyhydric alcohols include glycerin, polyglycerin, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,2-pentanediol, 1,2-hexanediol, polyethylene glycol, glucose, galactose, and sucrose. , Sorbitol, Martinol, Erythritol, Xylitol, Trehalose and the like.

The external preparation for skin of the present disclosure preferably contains 1,3-butylene glycol from the viewpoint of improving the affinity with the skin. The content of the siliconeized polysaccharide compound is preferably 0.0012% by mass to 0.006% by mass, preferably 0.0018% by mass to 0.004% by mass, based on the total mass of 1,3-butylene glycol. Is more preferable.

1,3-butylene glycol is a hydrophilic compound and has a high affinity for siliconeized polysaccharide compounds. Therefore, the external preparation for skin of the present disclosure contains 1,3-butylene glycol, and the ratio with the siliconeized polysaccharide compound is set to a specific value to adjust the skin compatibility, water resistance, etc. of the external preparation for skin. be able to. That is, by containing 0.0012% by mass or more of the siliconeized polysaccharide compound with respect to the total mass of 1,3-butylene glycol, the skin external preparation is due to the hydrophilicity of 1,3-butylene glycol. The affinity between the skin and the skin is further improved, and the skin compatibility of the external preparation for skin is further improved. When the external preparation for skin has water resistance, the amount of the siliconeized polysaccharide compound is preferably 0.006% by mass or less based on the total mass of 1,3-butylene glycol.

[Other ingredients]
The external preparation for skin of the present disclosure may contain other components as long as the effects of the present invention are not impaired.
Other ingredients include fatty acids, lipophilic thickeners, water-soluble organic solvents (ethanol, etc.), preservatives (phenoxyethanol, methylparaben, etc.), pH regulators, emollients, moisturizers, antioxidants, colorants, fragrances. , Other functional ingredients and the like.

<Use of external preparations for skin>
The external preparation for skin of the present disclosure can be applied to applications such as cosmetics and transdermal quasi-drugs, but is not limited thereto.
The dosage form of the cosmetic to which the external preparation for skin of the present disclosure is applied may be an oil-in-water type or a water-in-oil type. It is more preferably a cosmetic.
Examples of cosmetics include skin care cosmetics, sunscreen cosmetics, make-up cosmetics such as makeup bases, and the like, which can be suitably applied to sunscreen cosmetics.

<Manufacturing method of external preparation for skin>
The method for producing the external preparation for skin of the present disclosure is not particularly limited, and the external preparation for skin can be produced according to a known method for producing an external preparation for skin.
Hereinafter, an example of a manufacturing method in the case where the skin external preparation of the present disclosure is used as a water-in-oil type skin external preparation is shown.

For example, when the composite powder is blended in the oil phase, an oil phase composition containing a siliconeized polysaccharide compound, the composite powder, and other oil phase components (for example, specific particles and other optional components) is prepared. Then, the obtained oil phase composition and the aqueous phase composition can be mixed to produce a water-in-oil type skin external preparation.
When the composite powder is blended in the aqueous phase, an aqueous phase composition containing the composite powder and other aqueous phase components is prepared, and the obtained aqueous phase composition and a siliconeized polysaccharide compound are contained. A water-in-oil skin external preparation can be produced by mixing with an oil phase composition.
The emulsification method for obtaining a water-in-oil type skin external preparation as a water-in-oil emulsion by mixing the oil phase composition and the aqueous phase composition is not particularly limited and can be carried out according to a conventional method. ..

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
In addition, all of the external preparations for skin of each example can be suitably applied as sunscreen cosmetics.

[Example 1]
Cyclopentasiloxane (trade name: KF-995, Shin-Etsu Chemical Co., Ltd.), avobenzone composite titanium oxide (trade name: HXMT-100ZA, composite powder, TAYCA Corporation), and PEG-9 polydimethylsiloxyethyl dimethicone. (Product name: KF-6028, Shin-Etsu Chemical Co., Ltd.) was thoroughly stirred and mixed with a disper at room temperature (25 ° C., the same applies hereinafter).
After that, Dimethicon 5CS (trade name: KF-96A-5cs, Shin-Etsu Chemical Co., Ltd.), (Dimethicon / Vinyl Dimethicon) cross polymer (trade name: KSG-15, Shin-Etsu Chemical Co., Ltd.), and (Dimethicon / (PEG-10 / 15) cross polymer (trade name: KSG-210, Shin-Etsu Chemical Co., Ltd.), (butyl acrylate / glycol dimethacrylate) cross polymer (trade name: Matsumoto Microsphere S-100, specified) Particles, particle size: 15 μm, Matsumoto Yushi Pharmaceutical Co., Ltd., sorbitan sesquioleate (trade name: NIKKOL SO-15V, Nikko Chemicals Co., Ltd.), diphenylsiloxyphenyl trimeticon (trade name: KF-56A, Shin-Etsu Chemical Co., Ltd.) Co., Ltd.), Tri (trimethylsiloxy) Cyrilpropylcarbamic acid purulan (trade name: TSP-30-D5, silicone-modified purulan, Shin-Etsu Chemical Co., Ltd.) Further added, stirred and mixed to homogenize, and oil phase composition. I got something.
Then, water, phenoxyxyethanol, BG (1,3-butylene glycol), and ethanol were stirred and mixed at room temperature to homogenize to obtain an aqueous phase composition.
Next, the oil phase composition and the aqueous phase composition are mixed according to a conventional method, and the mixture is stirred with a homogenizer (trade name: HM-310, AS ONE Corporation) for 10 minutes at 1000 rpm. A water-in-oil type skin external preparation was obtained.

The composition of the external preparation for skin prepared in Example 1 is shown in Table 1. “%” In the component column in Table 1 indicates “mass%”.

[Evaluation]
The following evaluations were performed on the external preparation for skin of Example 1. The results are shown in Table 2.

(Film cracking)
Ten expert evaluators were ^{asked to apply an external preparation for skin to the face with their fingers at a ratio of 2} mg / cm 2, and evaluated according to the following four evaluation criteria. Then, A: 4 points, B: 3 points, C: 2 points, C: 1 point, the evaluation points of 10 people are averaged, and the evaluation rank corresponding to the value rounded to the first decimal place is the film cracking. It was used as the evaluation result. The results are shown in Table 2. If the evaluation ranks are "A" and "B", it is practically acceptable, and "A" is more preferable.
− Criteria −
A: No film cracking has occurred.
B: Streaks have occurred, but film cracking has not occurred.
C: Film cracks occur on a part of the coated surface D: Film cracks occur on the entire surface of the coated surface.

(Transmittance at a wavelength of 400 nm)
The external preparation for skin was applied on a ^{polymethylmethacrylate substrate (0.5 mm thick, 5 cm square) at a ratio of 2} mg / cm 2 using an applicator, and dried at room temperature in the air for 15 minutes. An evaluation substrate was prepared.
The coating speed at the time of coating was 10 mm / sec, and the gap of the applicator was 10 μm. The transmittance (%) of the obtained evaluation substrate at a wavelength of 400 nm was measured at 10 points on the evaluation substrate with a spectrophotometer V-7200 (JASCO Corporation). The average value of the measured values was calculated and evaluated according to the following four-stage evaluation criteria. The results are shown in Table 2. The evaluation results of "A" and "B" are practically acceptable levels, and "A" is preferable.
− Criteria −
A: Less than 10% B: 10% or more and less than 12% C: 12% or more and less than 20% D: 20% or more

(Stick)
Ten expert evaluators were asked to apply an external preparation for skin to the face with their fingers, and the stickiness after application was evaluated according to the following four evaluation criteria. Then, A: 4 points, B: 3 points, C: 2 points, C: 1 point, the evaluation points of 10 people are averaged, and the evaluation rank corresponding to the value rounded to the first decimal place is evaluated as sticky. As a result. The results are shown in Table 2. If the evaluation ranks are "A", "B" and "C", it is practically acceptable, "A" and "B" are preferable, and "A" is more preferable.
− Criteria −
A: I don't feel sticky B: I don't feel sticky C: I feel a little sticky D: I feel sticky strongly

(Erythema suppression)
We asked 10 expert evaluators to apply an external preparation for skin to the outer arm with a finger at ^{a ratio of 2} mg / cm 2, and after drying for 15 minutes, use a solar simulator (HAL-100, Asahi Spectral Co., Ltd.). The skin was irradiated with pseudo-solar at an intensity of 75 mW / cm ² for 3 hours, and the erythema of the skin after the irradiation was visually observed and evaluated according to the following four evaluation criteria. And, compared with the unirradiated part, no erythema is observed: 4 points, it is difficult to clearly distinguish between erythema and skin color: 3 points, slight redness is observed: 2 points, clear redness is observed: 1 point. The evaluation points of 10 people were averaged, and the evaluation rank corresponding to the value rounded off to the first decimal place was used as the evaluation result of erythema suppression. The criteria are as follows.
If the evaluation ranks are "A" and "B", it is practically acceptable, and "A" is more preferable. The results are shown in Table 2.
− Criteria −
A: 4 points or more B: 3 points or more and less than 4 points C: 2 points or more and less than 3 points D: 2 points or less

[Examples 2 to 6, Comparative Examples 1 to 2]
Examples 2 to 6 and Comparative Examples were the same as in Example 1 except that the amount of silicone-modified pullulan added was changed to the amount (% by mass) shown in Table 2 in the preparation of the external preparation for skin of Example 1. 1-2 oil-in-oil type skin external preparations were obtained.
Each of the obtained external preparations for skin was evaluated in the same manner as in Example 1. The results are shown in Table 2.

In Examples 2 to 6 and Comparative Examples 1 and 2, an oil phase composition was prepared by increasing or decreasing the amount of water to be blended in the aqueous phase by an amount corresponding to an increase or decrease in silicone-modified pullulan. did.
In Table 2, only the essential or arbitrary components characteristic of the external preparation for skin of the present disclosure are shown, but the compositions other than the components changed in each Example and Comparative Example are shown in the Examples shown in Table 1. It is the same as the composition of 1. (The same applies to Tables 3 to 6 described later.)

As can be seen from Table 2, the external preparation for skin of the examples is excellent in the evaluation of film cracking, and it can be seen that the external preparation for skin is familiar to the skin. Further, it can be seen that the skin external preparations of the examples all show practically acceptable performance in terms of 400 nm transmittance, stickiness and erythema suppression.
On the other hand, in Comparative Example 1 in which the ratio of silicone-modified pullulan to the composite powder was out of the range of 0.084 to 0.00125, the evaluation of film cracking was significantly inferior, and the content of silicone-modified pullulan was high. Comparative Example 2 outside the range of more than 0% by mass and 1% by mass or less (3% by mass) was inferior in the evaluation of film cracking, and marked stickiness also occurred.

[Examples 7 to 13, Comparative Example 3]
In Examples 7 to 10 and 13, the same as in Example 4 except that the amount of avobenzone composite titanium oxide added was changed to the amount (mass%) shown in Table 3 in Example 4. Water-in-oil type skin external preparations of 7 to 11 and Comparative Example 3 were obtained.
In Examples 11 to 12, avobenzone (trade name: Eusolex (registered trademark) 9020, Merck Performance Materials Co., Ltd.) was further added in Example 4, and the amount of avobenzone composite titanium oxide and avobenzone added was adjusted. A water-in-oil type skin external preparation of Examples 11 to 12 was obtained in the same manner as in Example 4 except that the amount (% by mass) shown in Table 3 was changed.
Each of the obtained external preparations for skin was evaluated in the same manner as in Example 1. The results are shown in Table 3. In addition, for convenience of comparison, Example 4 is described side by side.

In Examples 7 to 13 and Comparative Example 3, the amount of water blended in the aqueous phase was increased or decreased by an amount corresponding to the amount of increase or decrease of avobenzone composite titanium oxide and / or avobenzone. , An oil phase composition was prepared. The composition of the other components not shown in Table 3 is the same as the composition of Example 4.

As shown in Table 3, the skin external preparations of each example in which the content ratio of the composite powder was 14% by mass or less with respect to the total mass of the skin external preparation had film cracking, 400 nm transmittance, stickiness and erythema suppression. It turns out that all of them are excellent. Further, from the comparison between Examples 10 and 12, it can be seen that the addition of an ultraviolet absorber other than the composite powder further improves the ultraviolet shielding effect (400 nm transmittance and suppression of erythema).

[Examples 14 to 17]
In Example 4, the same as in Example 4 except that the amount of the butyl acrylate / glycol dimethacrylate crosspolymer added was changed to the amount (% by mass) shown in Table 4, of Examples 14 to 17. A water-in-oil type skin external preparation was obtained.
Each of the obtained external preparations for skin was evaluated in the same manner as in Example 1. The results are shown in Table 4. For convenience of comparison, Example 4 will be described side by side.

In Examples 14 to 17, the amount of water blended in the aqueous phase was increased or decreased by an amount corresponding to the amount of increase or decrease of the (butyl acrylate / glycol dimethacrylate) crosspolymer. , An oil phase composition was prepared. The composition of the other components not shown in Table 4 is the same as the composition of Example 4.

As shown in Table 4, all of the skin external preparations of each example containing specific particles (acrylate-based crosspolymer) in an amount of 0.4% by mass to 1.2% by mass with respect to the total mass of the skin external preparation. It is excellent in the evaluation of film cracking, and it can be seen that when the range is in the range of 0.4% by mass to 1% by mass, excellent effects can be obtained in all of film cracking, 400 nm permeability, stickiness and erythema suppression.

[Examples 18 to 21]
In Example 4, the same as in Example 4 except that the amount of 1,3-butylene glycol (referred to as “BG” in Table 5) was changed to the amount (mass%) shown in Table 5. Then, the water-in-oil type skin external preparations of Examples 18 to 21 were obtained.
Each of the obtained external preparations for skin was evaluated in the same manner as in Example 1. The results are shown in Table 5. For convenience of comparison, Example 4 will be described side by side.

In Examples 18 to 21, an aqueous phase composition was prepared by increasing or decreasing the amount of water in an amount corresponding to an increase or decrease in 1,3-butylene glycol. The composition of the other components not shown in Table 5 is the same as the composition of Example 4.

As shown in Table 5, the skin external preparations of each example containing the content of the siliconeized polysaccharide compound in the range of 0.0012% by mass to 0.006% by mass with respect to the total mass of 1,3-butylene glycol , All were excellent in the evaluation of film cracking. Further, it can be seen that an excellent effect can be obtained in any of film cracking, 400 nm transmittance, stickiness and erythema suppression when the range is in the range of 0.0018% by mass to 0.004% by mass.

[Examples 22 to 25]
Examples 4, 17 to 20 except that the amounts of cyclopentasiloxane and dimethicone CS5 were changed so that the mass ratio of dimethicone to cyclopentasiloxane was the ratio shown in Table 6. In the same manner as in the above, a water-in-oil type skin external preparation of Examples 22 to 25 was obtained.
Each of the obtained external preparations for skin was evaluated in the same manner as in Example 1. The results are shown in Table 6.

As shown in Table 6, the external preparations for skin of each example in which the mass ratio of dimethicone to cyclopentasiloxane is in the range of 0.2 to 0.5 are excellent in the evaluation of film cracking. I understand.

[Example 26]
In Example 4, the fermented Alteromonas extract (trade name: Abyssin PF, manufactured by Arista) was further added in an amount of 0.003% by mass, and the amount of water was reduced by that amount, but the same procedure as in Example 4 was carried out. The skin external preparation of Example 26 was prepared. When the obtained external preparation for skin was evaluated in the same manner as in Example 1, the same performance as in Example 4 was shown except that the stickiness was "C".

[Example 27]
In Example 4, techpolymer ACX-2502 (Sekisui Plastics Co., Ltd.) was used instead of the (butyl acrylate / glycol dimethacrylate) crosspolymer (trade name: Matsumoto Microsphere S-100). Prepared an external preparation for skin of Example 27 in the same manner as in Example 4. When the obtained external preparation for skin was evaluated in the same manner as in Example 1, the same performance as in Example 4 was shown except that the stickiness was "C".

[Example 28]
In Example 4, except that SILICA MICRO BEAD (diameter 5 μm, manufactured by JGC Catalysts and Chemicals) was used instead of the (butyl acrylate / glycol dimethacrylate) crosspolymer (trade name: Matsumoto Microsphere S-100). The skin external preparation of Example 28 was prepared in the same manner as in Example 4. When the obtained external preparation for skin was evaluated in the same manner as in Example 1, the same performance as in Example 4 was shown except that the stickiness was "C".

[Comparative Example 3]
In Example 4, Cover Leaf AR-80TM (powder in which titanium oxide, aluminum oxide, and silica are coated in order on talc, Catalytic Chemical Industry Co., Ltd.), and Cover Leaf AR-20121M (oxidized to sericite). A skin external preparation of Comparative Example 3 was prepared in the same manner as in Example 4 except that a powder coated with titanium, aluminum oxide, and silica in that order and Catalyst Kasei Kogyo Co., Ltd. were used instead of the avobenzone composite titanium oxide. .. When the obtained external preparation for skin was evaluated in the same manner as in Example 1, the evaluation results were "D" for film cracking, "D" for 400 nm transmittance, and "C" for erythema suppression.

Claims (12)

The siliconeized polysaccharide compound contains more than 0% by mass and 1% by mass or less based on the total mass of the external preparation for skin, and a composite powder of titanium oxide and an ultraviolet absorber, and is a composite powder of titanium oxide and an ultraviolet absorber. A skin external preparation having a mass ratio of the siliconeized polysaccharide compound to the body of 0.084 to 0.000125. The external preparation for skin according to claim 1, further comprising particles having a particle size of 5 μm to 50 μm. The external preparation for skin according to claim 2, wherein the particle size of the particles is 10 μm to 50 μm. The skin external preparation according to claim 2 or 3, wherein the particles contain resin particles. The external preparation for skin according to claim 4, wherein the resin particles contain an acrylate-based crosspolymer. The skin external preparation according to claim 5, wherein the content of the resin particles containing the acrylate-based crosspolymer with respect to the total mass of the skin external preparation is 0.4% by mass to 1.2% by mass. The skin external preparation according to claim 1 to 6, wherein the content of the composite powder of titanium oxide and the ultraviolet absorber is 14% by mass or less with respect to the total mass of the skin external preparation. The external preparation for skin according to any one of claims 1 to 7, further comprising an ultraviolet absorber other than a composite powder of titanium oxide and an ultraviolet absorber. Further, claims 1 to claim that the content of 1,3-butylene glycol is contained, and the content of the siliconeized polysaccharide compound with respect to the total mass of 1,3-butylene glycol is 0.0012% by mass to 0.006% by mass. Item 8. The external preparation for skin according to any one of Item 8. The one according to any one of claims 1 to 9, wherein the composite powder of titanium oxide and an ultraviolet absorber contains a composite powder of titanium oxide and 4-tert-butyl-4'-methoxydibenzoylmethane. External skin preparation. The external preparation for skin according to any one of claims 1 to 10, further comprising dimethicone and cyclopentasiloxane, and the mass ratio of dimethicone to cyclopentasiloxane is 0.2 to 0.5. The external preparation for skin according to any one of claims 1 to 11, which is a sunscreen cosmetic.