WO2024122465A1

WO2024122465A1 - Emulsified topical composition and method for producing same

Info

Publication number: WO2024122465A1
Application number: PCT/JP2023/043131
Authority: WO
Inventors: 真佐人岡; 裕美子稲岡
Original assignee: ロート製薬株式会社
Priority date: 2022-12-05
Filing date: 2023-12-01
Publication date: 2024-06-13
Also published as: TW202430120A

Abstract

Provided is a novel composition having excellent ultraviolet ray absorption capability In the present invention, the following is prepared: an emulsified topical composition containing (C) diethylamino hydroxybenzoyl hexyl benzoate, and (A) porous silica including an ultraviolet absorber, where the average particle diameter of the porous silica is 1.4 to 40 μm, and the ultraviolet absorber included in the (A) component is solid at 25°C; or an emulsified topical composition containing (A2) porous silica including an ultraviolet absorber and (B) a non-ionic surfactant, where the average particle diameter of the porous silica is 1.4 to 40 μm, and the porous silica includes an ultraviolet absorber that is solid at 25°C.

Description

Emulsion composition for external use and method for producing same

The present invention relates to an emulsified composition for topical use. More specifically, the present invention relates to an emulsified composition for topical use that contains porous silica encapsulating an ultraviolet absorber.

Ultraviolet rays include ultraviolet A rays (UV-A), ultraviolet B rays (UV-B), and others. Of these, UV-A rays are less likely to cause sunburn, but recent research has shown that they play a major role in the development of age spots and wrinkles. UV-A rays have a long wavelength and penetrate deep into the skin, causing effects such as denaturing collagen.

UV-B has a short wavelength and is blocked by the ozone layer and clouds compared to UV-A, so only a small amount, about 10% of the total amount of UV light, reaches the ground. However, UV-B has high energy and can damage cells on the surface of the skin and cause inflammation, which can lead to skin cancer and blemishes.

As the effects of UV rays on the skin become clearer, there is an increasing demand for topical compositions with high UV blocking effects, and various topical compositions have been proposed (Patent Document 1).

JP 2015-17080 A

The object of the present invention is to provide an emulsified composition for topical use that has good ultraviolet absorbing properties.

As a result of intensive research, the present inventors have found that an emulsified topical composition containing porous silica encapsulating an ultraviolet absorber and diethylaminohydroxybenzoylhexyl benzoate, or an emulsified topical composition containing porous silica encapsulating an ultraviolet absorber and a nonionic surfactant, can provide excellent ultraviolet absorbing ability and a good feeling of use, and have completed the present invention.

That is, in a first aspect of the present invention, there is provided the following emulsified composition for external use.
[1]
An emulsion composition for external use comprising (C1) diethylaminohydroxybenzoylhexyl benzoate, and (A1) porous silica encapsulating an ultraviolet absorber,
The average particle size of the porous silica is 1.4 to 40 μm,
The emulsified composition for external use, wherein the porous silica is porous silica encapsulating an ultraviolet absorber that is solid at 25°C.
[2]
The emulsified topical composition according to [1], wherein the UV absorber encapsulated in component (A1) is at least one selected from the group consisting of diethylamino hydroxybenzoyl hexyl benzoate, bisethylhexyloxyphenol methoxyphenyl triazine, methylene bisbenzotriazolyl tetramethylbutylphenol, terephthalylidene discamphorsulfonic acid, terephthalylidene dicamphorsulfonic acid, drometrizole trisiloxane, ethylhexyl triazone, and phenylbenzimidazole sulfonic acid.
[3]
The emulsified composition for external use according to [1] or [2], wherein an encapsulation rate of the ultraviolet absorber relative to the porous silica is 30 to 50%.

The present invention further provides the following method.
[4]
A method for enhancing the ultraviolet absorbing ability of an emulsion composition for topical use, comprising allowing the emulsion composition for topical use to contain diethylaminohydroxybenzoylhexyl benzoate and (A1) porous silica encapsulating an ultraviolet absorbing agent.
[5]
A method for producing an emulsion composition for external use containing (C1) diethylaminohydroxybenzoylhexyl benzoate and (A1) porous silica encapsulating an ultraviolet absorber, comprising the steps of:
The method includes a step of mixing (C1) diethylaminohydroxybenzoylhexyl benzoate and (A1) porous silica containing an ultraviolet absorber,
The average particle size of the porous silica is 1.4 to 40 μm,
The method for producing an emulsified topical composition, wherein the porous silica is porous silica encapsulating an ultraviolet absorber that is solid at 25°C.

In a second aspect of the present invention, there is provided an emulsified composition for external use in the following emulsion form.
[6]
(A2) porous silica encapsulating an ultraviolet absorber, and (B) a nonionic surfactant;
An emulsified topical composition comprising:
The average particle size of the porous silica is 1.4 to 40 μm,
The porous silica contains an ultraviolet absorber that is solid at 25° C.
The emulsified composition for external use has an encapsulation rate of the ultraviolet absorber relative to the porous silica of 30 to 50%.
[7]
The emulsified topical composition according to [6], wherein the nonionic surfactant has an HLB value of 5.0 to 20.
[8]
The emulsified topical composition according to [6] or [7], further comprising (C3) an ultraviolet absorber.
[9]
The emulsified topical composition according to claim [8], wherein the (C3) ultraviolet absorber is diethylaminohydroxybenzoylhexyl benzoate.
[10]
The emulsified topical composition according to any one of [6] to [9], wherein the ultraviolet absorber encapsulated in the component (A2) is bis-ethylhexyloxyphenol methoxyphenyl triazine.
[11]
(A2) porous silica encapsulating an ultraviolet absorber, and (B) a nonionic surfactant;
A method for producing an emulsified topical composition comprising the steps of: (A2) mixing porous silica containing an ultraviolet absorber; and (B) a nonionic surfactant;
The average particle size of the porous silica is 1.4 to 40 μm,
The porous silica contains an ultraviolet absorber that is solid at 25° C.
A method for producing an emulsified composition for external use, wherein the encapsulation rate of the ultraviolet absorber relative to the porous silica is 30 to 50%.

The emulsion composition for topical use of the present invention can achieve excellent UV absorption ability and a good feeling when used.

In this specification, the UVA region refers to wavelengths of 320 nm or more and less than 400 nm, and the UVB region refers to wavelengths of 280 nm or more and less than 320 nm.

In this specification, "excellent ultraviolet absorption ability" refers to having at least one of the following: excellent absorption ability for ultraviolet light of a specific wavelength, or the ability to absorb ultraviolet light of a wide range of wavelengths.

More specifically, the ability to absorb ultraviolet light over a wide range of wavelengths can be indicated by the spectral integration value of the emulsified topical composition of the present invention at wavelengths of 280 nm to 400 nm (hereinafter sometimes referred to as the "spectral integration value").

In this specification, the spectral integrated value at wavelengths of 280 nm to 400 nm refers to a value calculated by integrating the absorbance in the wavelength range of 280 to 400 nm in the absorption spectrum of the emulsified topical composition.

In this specification, "good feel when used" is not particularly limited, but includes, for example, a feeling of adhesion or moistness to the touch, and/or a feeling of freshness, and preferably means having all of these.

In this specification, the term "salt" is not particularly limited as long as it is medicamentarily, pharmacologically, or physiologically acceptable. Specific examples include basic salts such as salts with inorganic bases, such as alkali metal salts and alkaline earth metal salts, and salts with organic bases, and examples of such salts include salts with sodium, potassium, calcium, magnesium, ammonium, diethanolamine, or ethylenediamine. In addition, salts may be salts of amines, such as ammonia, methylamine, dimethylamine, trimethylamine, dicyclohexylamine, tris(hydroxymethyl)aminomethane, N,N-bis(hydroxyethyl)piperazine, 2-amino-2-methyl-1-propanol, ethanolamine, N-methylglucamine, and L-glucamine; and salts with basic amino acids, such as lysine, δ-hydroxylysine, and arginine. Furthermore, it may be a salt with an inorganic acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, or phosphoric acid; a salt with an organic acid such as methanesulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid, acetic acid, propionic acid, tartaric acid, fumaric acid, maleic acid, malic acid, oxalic acid, succinic acid, citric acid, benzoic acid, mandelic acid, cinnamic acid, lactic acid, glycolic acid, glucuronic acid, ascorbic acid, nicotinic acid, salicylic acid, gluconic acid, or palmitic acid; or a salt with an acidic amino acid such as aspartic acid or glutamic acid. The above "salt" includes solvates and hydrates of the salt.

In this specification, "encapsulating" an ultraviolet absorber includes not only the case where the ultraviolet absorber is present in the pores of the porous silica, but also the case where the ultraviolet absorber is supported.

[First aspect: Emulsion composition for external use]
In a first aspect of the present invention,
An emulsion composition for external use comprising (C1) diethylaminohydroxybenzoylhexyl benzoate, and (A1) porous silica encapsulating an ultraviolet absorber,
The average particle size of the porous silica is 1.4 to 40 μm,
The present invention relates to an emulsified composition for external use, wherein the porous silica is porous silica encapsulating an ultraviolet absorber that is solid at 25°C.

Diethylamino hydroxybenzoyl hexyl benzoate (DHHB) (CAS Registry Number 5809-23-4) is also known as 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester.

In one aspect of the present invention, a new means is provided that ensures freedom in the design of the formulation and form of an emulsified topical composition regardless of the DHHB content, and that allows the composition to exhibit good UV absorption efficacy.

The emulsified topical composition in this embodiment is characterized by containing (C1) diethylaminohydroxybenzoylhexyl benzoate and (A1) porous silica containing an ultraviolet absorber.

((C1) Diethylamino hydroxybenzoyl hexyl benzoate)
Diethylaminohydroxybenzoylhexyl benzoate (DHHB) has a maximum absorption wavelength at 354 nm and can absorb ultraviolet rays, particularly in the UVA region. DHHB is not particularly limited as long as it can be used in external compositions, and for example, Uvinul A Plus Granular (manufactured by BASF) and the like can be used as commercially available DHHB.

Here, diethylaminohydroxybenzoylhexyl benzoate may be encapsulated in a carrier such as porous silica that is different from component (A1), but it is preferable that it is not encapsulated or supported on a carrier.

The content of (C1) diethylaminohydroxybenzoylhexyl benzoate is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.7% by mass or more, based on the total amount of the emulsified topical composition, from the viewpoint of exhibiting a more pronounced ultraviolet absorbing effect, and may be, for example, 10% by mass or less, 5% by mass or less, or 3% by mass or less, from the viewpoint of usability.

The content of (C1) diethylaminohydroxybenzoyl hexyl benzoate may be preferably 0.3 to 10% by mass, more preferably 0.3 to 5% by mass, and even more preferably 0.7 to 3% by mass, based on the total amount of the emulsion composition for topical use.

((A1) Porous silica containing an ultraviolet absorber)
In the component (A1), the ultraviolet absorber is not particularly limited as long as it is an ultraviolet absorber that is solid at 25°C and can be used in a topical composition, and one type of compound can be used alone, or two or more types of compounds can be used in combination. Such an ultraviolet absorber is preferably at least one selected from the group consisting of triazine derivative ultraviolet absorbers, benzylidene camphor ultraviolet absorbers, phenylbenzotriazole ultraviolet absorbers, salicylic acid ultraviolet absorbers, cinnamic acid ultraviolet absorbers, benzoylmethane ultraviolet absorbers, benzoic acid ester derivative ultraviolet absorbers, benzalmalonate derivative ultraviolet absorbers, octocrylene ultraviolet absorbers, imidazole sulfonic acid derivative ultraviolet absorbers, and benzophenone derivative ultraviolet absorbers, and more preferably at least one selected from the group consisting of triazine derivative ultraviolet absorbers, benzylidene camphor ultraviolet absorbers, and phenylbenzotriazole ultraviolet absorbers.

Specific examples of such ultraviolet absorbers include, preferably, bisethylhexyloxyphenol methoxyphenyl triazine (BEMT) (also known as 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine), methylene bisbenzotriazolyl tetramethylbutylphenol (also known as 2,2'-methylene bis[6-(2H-benzotriazol-2yl)-4-(1,1,3,3-tetramethylbutyl)phenol]), terephthalidenedicamphorsulfonic acid, terephthalidenedicamphorsulfonic acid, drometrizole trisiloxane, ethylhexyl triazone (also known as 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]1,3,5-triazine), phenylbenzimidazole sulfonic acid,
4-tert-Butyl-4'-methoxydibenzoylmethane (also known as t-butyl methoxydibenzoylmethane, also known as avobenzone), dimethoxybenzylidene dioxoimidazolidinepropionate 2-ethylhexyl, dihydroxydimethoxybenzophenone disulfonate sodium, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts, dihydroxydimethoxybenzophenone, dihydroxybenzophenone, tetrahydroxybenzophenone (oxybenzone-2), dihydroxybenzophenone, ferulic acid,
Octyl salicylate (2-ethylhexyl salicylate), homomenthyl salicylate, tris(biphenyl)triazine, methyl 2,5-diisopropylcinnamate, glyceryl di-paramethoxycinnamate mono-2-ethylhexanoate, 2-ethylhexyl paramethoxycinnamate (also known as ethylhexyl methoxycinnamate), cinoxate, isopropyl paramethoxycinnamate/diisopropyl cinnamate mixture, dimethicone diethyl benzalmalonate, 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester (also known as octocrylene), 2-phenyl at least one selected from the group consisting of benzimidazole-5-sulfonic acid, para-aminobenzoic acid (hereinafter abbreviated as "PABA") or a derivative thereof (e.g., ethyl PABA, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA, glyceryl PABA), 4-(2-β-glucopyranosyloxy)propoxy-2-hydroxybenzophenone, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, bis(trimethylsiloxy)silylisopentyl methyl trimethoxycinnamate, and amyl paradimethylaminobenzoate;
More preferably, it is at least one selected from the group consisting of bisethylhexyloxyphenol methoxyphenyl triazine, methylene bisbenzotriazolyl tetramethylbutylphenol, terephthalidene dicamphor sulfonic acid, drometrizole trisiloxane, ethylhexyl triazone, and phenylbenzimidazole sulfonic acid.

Diethylaminohydroxybenzoylhexyl benzoate (DHHB) may also be included.

In particular, from the viewpoint of achieving the effect of this embodiment more significantly, the ultraviolet absorber in component (A1) is preferably one that has a maximum absorption wavelength in the wavelength region of 300 nm or more, and more preferably one that has a maximum absorption wavelength in the wavelength region of 310 nm or more. It is even more preferable that the ultraviolet absorber also has a maximum absorption wavelength in the UVB region.

In component (A1), the porous silica encapsulating the ultraviolet absorbent is not particularly limited as long as it has pores capable of encapsulating the ultraviolet absorbent, and one or more types of porous silica can be used. The shape of the porous silica is preferably spherical or granular in order to improve the feel when used.

The size of the porous silica can be preferably 1.4 μm or more, more preferably 2 μm or more, as the average particle diameter of the porous silica. From the viewpoint of improving the feeling of use, the average particle diameter of the porous silica can be preferably 40 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, and even more preferably 10 μm or less. The average particle diameter of the porous silica can be preferably 1.4 μm to 40 μm, more preferably 2 μm to 30 μm. Here, the average particle diameter represents the average particle diameter in the volume-based particle size distribution measured using a laser diffraction scattering type particle size distribution measuring device.

The oil absorption of the porous silica is not particularly limited, but is preferably 80 mL/100 g or more, more preferably 90 mL/100 g or more, even more preferably 100 mL/100 g or more, and is preferably 400 mL/100 g or less, more preferably 350 mL/100 g, and even more preferably 200 mL/100 g. For example, it is not limited, but is preferably 90 mL/100 g to 350 mL/100 g, more preferably 100 mL/100 g to 300 mL/100 g, and even more preferably 100 mL/100 g to 200 mL/100 g. The oil absorption can be confirmed by the oil absorption according to JIS K 5101-13-1 General test method for measuring oil absorption of pigments and extender pigments.

Commercially available porous silica products that can be used include Sunsphere (manufactured by AGC Si-Tech Co., Ltd.), Cosme Silica (manufactured by Fuji Silysia Chemical Co., Ltd.), Mizupearl (manufactured by Mizusawa Industrial Chemicals Co., Ltd.), SILICA MICRO BEAD (manufactured by JGC Catalysts and Chemicals Co., Ltd.), Pulsea SIT-40, Pulsea SIZ-30 (manufactured by Suzuki Oil Industries Co., Ltd.), Godball B-25C, Godball D-25C (manufactured by Suzuki Oil Industries Co., Ltd.), etc.

The surface of the porous silica may be treated with inorganic fine particles such as metal oxides, for example titanium oxide and zinc oxide. The coating layer may be about 10 to 40 mass % of the porous silica.

(A1) Porous silica containing an ultraviolet absorber can be produced, for example, by adding porous silica to a solution in which an ultraviolet absorber is dissolved in a solvent, impregnating the porous silica with the ultraviolet absorber, and removing the solvent. The type and number of components of the solvent are not limited as long as the solvent dissolves the ultraviolet absorber, and a known solvent can be used. In the solution in which an ultraviolet absorber is dissolved in a solvent, a solvent that uniformly disperses the porous silica is more preferable. The solvent is not limited, but examples include toluene, cyclohexane, hexane, xylene, ethyl acetate, and butyl acetate, and toluene is preferred. The solvent used here is preferably, for example, one that does not contain or substantially does not contain methanol (for example, 1 mass% or less), but is not limited thereto. The ultraviolet absorber can be impregnated into the porous silica by stirring and mixing using a known method. For example, as a stirring method, a magnetic stirrer, a mixer, an ultrasonic wave, a homogenizer, a high-pressure homogenizer, a dispersing mixer, a bead mill, a colloid mill, a roller mill, a three-roller mill, a stamp mill, a rod mill, a ball mill, a jaw crusher, a kneader, a planetary mixer, etc. can be used, but is not particularly limited. The method for removing the solvent is not limited, but includes a method of heating to a temperature higher than the boiling point of the solvent, a method of reducing pressure, a method of applying pressure, or a combination of these. After removing the solvent, it is also possible to obtain a powder by adopting a known method such as drying.
The physicochemical state of the obtained porous silica containing the ultraviolet absorbent can be evaluated by a method such as scanning electron microscope, powder X-ray diffraction measurement, and differential scanning calorimetry. In addition, a dissolution profile can be created by a dissolution test to confirm whether or not the ultraviolet absorbent contained in the porous silica has been dissolved. The average particle size of the obtained porous silica containing the ultraviolet absorbent can be measured by a known method such as a light scattering photometer and a transmission electron microscope.

The amount of ultraviolet absorber contained in the porous silica is preferably, for example, 30 to 50% by mass, and more preferably 35 to 45% by mass.

The component (A1) may be, for example, one type of porous silica containing multiple ultraviolet absorbents; a first porous silica containing a first ultraviolet absorbent and a second porous silica containing a different second ultraviolet absorbent; or a combination of a first porous silica containing one type of ultraviolet absorbent and a second porous silica containing the same ultraviolet absorbent, where the first porous silica and the second porous silica have different parameters (for example, the average particle size of the porous silica, the encapsulation rate of the ultraviolet absorbent).

The (A1) component may be surface-treated after incorporating an ultraviolet absorber. There are no particular limitations on the type or concentration of the surface treatment. Examples of types of surface treatments include silica, alginic acid, aluminum oxide (alumina), POE/dimethicone copolymer, polyethylene glycol, aluminum hydroxide, amino acids, metal soaps, perfluoroalkylethyl phosphate ester diethanolamine acid, fluoroalkyl acrylate/polyalkylene glycol acrylate polymer, perfluoropolyether phosphate, anionic or cationic polymers having perfluoropolyether chains, hydrogenated lecithin, acylated amino acids, α-tocopherol phosphate ester acid, methylhydrogenpolysiloxane, α-monoalkoxypolydimethylsiloxane, α-dialkoxypolydimethylsiloxane, triethoxysilylethyl polydimethylsiloxyethyl dimethicone, amodimethicone, triethoxycaprylylsilane, aminopropyltriethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctyltriethoxysilane, etc., and multiple surface treatments may be performed.

The content of the porous silica encapsulating the ultraviolet absorber (A1) in the emulsified topical composition in this embodiment is, from the viewpoint of achieving the effect of this embodiment more significantly, preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more, based on the total amount of the composition, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

In the emulsified topical composition of this embodiment, the content of the (A1) component per 1 part by mass of the (C1) component is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, even more preferably 0.01 parts by mass or more, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 1 part by mass or less, from the viewpoint of significantly achieving the effect of this embodiment.

((B) Nonionic Surfactant)
The emulsified topical composition of this embodiment may further contain one or more nonionic surfactants as component (B) in order to more significantly exhibit the effects of this embodiment. The nonionic surfactant is not particularly limited as long as it can be used in the emulsified topical composition. Although it should not be limited to a specific mechanism, it is presumed that the nonionic surfactant improves the dispersibility of component (A1), which makes it easier to interact with component (C1), thereby contributing to the improvement of the ultraviolet absorbing effect.

Nonionic surfactants include, for example, sorbitan fatty acid esters (e.g., sorbitan isostearate (HLB = 5.0), sorbitan laurate (HLB = 8.5), sorbitan palmitate (HLB = 6.7), sorbitan stearate (HLB = 4.7), diglycerol sorbitan penta-2-ethylhexyl acid, diglycerol sorbitan tetra-2-ethylhexyl acid, etc.); propylene glycol fatty acid esters (e.g., propylene glycol monostearate (HLB = 3.5), etc.); hydrogenated castor oil derivatives (e.g., polyoxyethylene hydrogenated castor oil, hydrogenated castor oil 40 (HLB=12.5), polyoxyethylene hydrogenated castor oil 50 (HLB=13.5), polyoxyethylene hydrogenated castor oil 60 (HLB=14.0), polyoxyethylene hydrogenated castor oil 80 (HLB=15.0), etc.); polyoxyethylene sorbitan fatty acid esters (e.g., polyoxyethylene (20) sorbitan laurate (polysorbate 20), polyoxyethylene (20) sorbitan stearate (polysorbate 60) (HLB=15.0), polyoxyethylene (20) sorbitan oleate (polysorbate 80) (HLB=15.0), polyoxyethylene (20) sorbitan isostearate (HLB=15.0), etc.); glycerin derivatives (e.g., glyceryl stearate (HLB=3.0), polyglyceryl-10 pentaisostearate (HLB=3.5), polyglyceryl-10 stearate (HLB=12.0), polyglyceryl-10 isostearate (HLB=12.0), coconut oil PEG-7 glyceryl (HLB=13.0), glycerin stearate alkyl ether); polyoxyalkylene alkyl ethers (e.g., polyoxyethylene lauryl ether (HLB=12.0), etc.); Silicone surfactants (e.g., polyoxyethylene-methylpolysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone (HLB=3.0), PEG-9 polydimethylsiloxyethyl dimethicone (HLB=4.0), bisPEG-18 methyl ether dimethylsilane (HLB=17.0), etc.); polyethylene glycol fatty acid esters (e.g., PEG-10 stearate (HLB=11.0), PEG-25 stearate (HLB=15.0), PEG-40 stearate (HLB=17.5); alkyl glucosides; etc.

From the viewpoint of more significantly achieving the effects of the present embodiment, the HLB value of the nonionic surfactant is preferably 2 to 20, more preferably 4 to 19. Examples of nonionic surfactants having an HLB value of 2 or more and less than 4 include compounds selected from the group consisting of propylene glycol monostearate, glyceryl stearate, polyglyceryl-10 pentaisostearate, and lauryl PEG-9 polydimethylsiloxyethyl dimethicone, either alone or in combination of two or more.
Examples of the nonionic surfactant having an HLB of 4 or more and less than 6 include compounds selected from the group consisting of sorbitan isostearate, sorbitan stearate, and PEG-9 polydimethylsiloxyethyl dimethicone, which may be used alone or in combination of two or more.
Examples of the nonionic surfactant having an HLB of 6 or more and less than 9 include compounds selected from the group consisting of sorbitan laurate and sorbitan palmitate, which may be used alone or in combination of two or more kinds.
Examples of nonionic surfactants having an HLB of 9 or more and less than 14 include compounds selected from the group consisting of polyoxyethylene hydrogenated castor oil 20, polyoxyethylene hydrogenated castor oil 40, polyoxyethylene hydrogenated castor oil 50, polyglyceryl-10 stearate, polyglyceryl-10 isostearate, polyoxyethylene monococonut oil fatty acid PEG-7 glyceryl, polyoxyethylene lauryl cetyl ether, and PEG-6 stearate, which may be used alone or in combination of two or more.
Examples of nonionic surfactants having an HLB of 14 or more and less than 18 include compounds selected from the group consisting of polyoxyethylene hydrogenated castor oil 60, polyoxyethylene hydrogenated castor oil 80, polyoxyethylene (20) sorbitan stearate, polyoxyethylene (20) sorbitan oleate, polyoxyethylene (20) sorbitan isostearate, bisPEG-18 methyl ether dimethylsilane, PEG-25 stearate, PEG-40 stearate, PEG-55 stearate, and PEG-25 isostearate, either alone or in combination.

In this specification, the HLB value is not particularly limited and may be a calculated value or an experimentally determined value. The calculated value may be, for example, a value calculated based on the Griffin method (20 x sum of formula weights of hydrophilic moieties/molecular weight).

The content of the nonionic surfactant in the emulsified topical composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, based on the total amount of the composition, from the viewpoint of more prominently exhibiting the effect of this embodiment, and is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less.

((C2) Other UV absorbers)
The emulsified topical composition of this embodiment may further contain an ultraviolet absorber as component (A1) in a form that is not encapsulated in silica particles. Examples of such ultraviolet absorbers include at least one selected from the ultraviolet absorbers that can be used in the above-mentioned component (A1).

The content of component (C2) in the emulsified topical composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, based on the total amount of the composition, from the viewpoint of more prominently exhibiting the effect of this embodiment, and is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less.

(effect)
As shown in the examples, the emulsified topical composition of this embodiment has an improved ultraviolet absorbing effect in the presence of the (C1) component and the (A1) component. Although it should not be limited to a specific mechanism, it is presumed that such an improvement in the ultraviolet absorbing effect is due to the transfer of energy or particles (e.g., electrons) between the (C1) component and the ultraviolet absorber of the (A1) component via the porous silica.

Furthermore, the emulsified topical composition of this embodiment has good ultraviolet light absorption efficiency as a result of the improved ultraviolet light absorption efficiency of component (C1). For example, the rate of change in absorbance of ultraviolet light at a wavelength of 310 nm of the emulsified topical composition of this embodiment relative to a comparative composition may be preferably 5% or more, more preferably 10% or more, even more preferably 15% or more, and even more preferably 20% or more, from the viewpoint of more significantly exerting the effect of this embodiment. A larger rate of change indicates a higher ultraviolet light absorption effect.

In addition, the emulsified topical composition of this embodiment allows the amount of component (C1) used to be controlled, allowing for a high degree of freedom in formulation and form, making it possible to produce a good composition. Furthermore, as shown in the examples, the emulsified topical composition of this embodiment can have a better feel when used than a composition in which the UV absorber is not encapsulated in the porous silica.

[Method for enhancing ultraviolet absorption capacity]
Another aspect relates to a method for enhancing the ultraviolet absorbing ability of an emulsion composition for external use, which is characterized by comprising (C1) diethylamino hydroxybenzoyl hexyl benzoate and (A1) porous silica containing an ultraviolet absorbing agent in the emulsion composition for external use.Here, the porous silica containing an ultraviolet absorbing agent is preferably porous silica containing an ultraviolet absorbing agent other than diethylamino hydroxybenzoyl hexyl benzoate.For example, porous silica containing bisethylhexyloxyphenol methoxyphenyl triazine is preferable.

The state in which the (C1) and (A1) components are coexistent is similar to the emulsified composition for topical use described above in the section [First embodiment: Emulsified composition for topical use]. The types and contents of the (C1) and (A1) components and other components in the above method, as well as other specific aspects, are similar to those described above in the section [First embodiment: Emulsified composition for topical use].

[Second embodiment: Emulsion composition for external use]
In a second aspect of the present invention,
(A2) porous silica encapsulating an ultraviolet absorber and (B) a nonionic surfactant,
An emulsified topical composition comprising:
The average particle size of the porous silica is 1.4 to 40 μm,
The porous silica is porous silica containing an ultraviolet absorber that is solid at 25° C.,
The present invention relates to an emulsified composition for external use, in which the encapsulation rate of the ultraviolet absorber relative to the porous silica is 30 to 50%.
An emulsified topical composition having such a constitution can achieve both excellent ultraviolet absorbing ability and a good feeling when used.

((A2) Porous silica containing an ultraviolet absorber)
In the (A2) component, the ultraviolet absorber is not particularly limited as long as it is a solid at 25°C and can be used in a topical composition, and one type of compound can be used alone or two or more types of compounds can be used in combination. Such an ultraviolet absorber is preferably at least one selected from the group consisting of triazine derivative ultraviolet absorbers, benzylidene camphor ultraviolet absorbers, phenylbenzotriazole ultraviolet absorbers, salicylic acid ultraviolet absorbers, cinnamic acid ultraviolet absorbers, benzoylmethane ultraviolet absorbers, benzoic acid ester derivative ultraviolet absorbers, benzalmalonate derivative ultraviolet absorbers, octocrylene ultraviolet absorbers, imidazole sulfonic acid derivative ultraviolet absorbers and benzophenone derivative ultraviolet absorbers, and more preferably at least one selected from the group consisting of triazine derivative ultraviolet absorbers, benzylidene camphor ultraviolet absorbers and phenylbenzotriazole ultraviolet absorbers.

Specific examples of such ultraviolet absorbers include, but are not limited to, bisethylhexyloxyphenol methoxyphenyl triazine (BEMT) (also known as 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), methylhexyl triazone, methylene bisbenzotriazolyl tetramethyl ether, etc. It may be selected from the group consisting of phenylbutylphenol (also known as 2,2'-methylenebis[6-(2H-benzotriazole-2yl)-4-(1,1,3,3-tetramethylbutyl)phenol]), terephthalidenedichamnosulfonic acid, drometrizole trisiloxane, ethylhexyl triazone (also known as 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]1,3,5-triazine), and phenylbenzimidazole sulfonic acid.

Here, the more preferred component (A2) is porous silica containing diethylaminohydroxybenzoylhexylbenzoate (DHHB), t-butylmethoxydibenzoylmethane (BM-DBM), or bisethylhexyloxyphenol methoxyphenyl triazine (BEMT).

In component (A2), the porous silica encapsulating the ultraviolet absorbent is not particularly limited as long as it has pores capable of encapsulating the ultraviolet absorbent, and one or more types of porous silica can be used. The shape of the porous silica is preferably spherical or granular in order to improve the feel when used.

The surface of the porous silica may be treated with inorganic fine particles such as metal oxides, such as titanium oxide and zinc oxide. The coating layer may be about 10 to 40 mass % of the porous silica.

(A2) Porous silica containing an ultraviolet absorber can be produced, for example, by adding porous silica to a solution in which an ultraviolet absorber is dissolved in a solvent, impregnating the porous silica with the ultraviolet absorber, and removing the solvent. The type and number of components of the solvent are not limited as long as the solvent dissolves the ultraviolet absorber, and a known solvent can be used. In the solution in which an ultraviolet absorber is dissolved in a solvent, a solvent that uniformly disperses the porous silica is more preferable. The solvent is not limited, but examples include toluene, cyclohexane, hexane, xylene, ethyl acetate, and butyl acetate, and toluene is preferable. The solvent used here is preferably, for example, one that does not contain or substantially does not contain methanol (for example, 1 mass% or less), but is not limited thereto. The ultraviolet absorber can be impregnated into the porous silica by stirring and mixing using a known method. For example, as a stirring method, a magnetic stirrer, a mixer, an ultrasonic wave, a homogenizer, a high-pressure homogenizer, a dispersing mixer, a bead mill, a colloid mill, a roller mill, a three-roller mill, a stamp mill, a rod mill, a ball mill, a jaw crusher, a kneader, a planetary mixer, etc. can be used, but is not particularly limited. The method for removing the solvent is not limited, but includes a method of heating to a temperature higher than the boiling point of the solvent, a method of reducing pressure, a method of applying pressure, or a combination of these. After removing the solvent, it is also possible to obtain a powder by adopting a known method such as drying.
The physicochemical state of the obtained porous silica containing the ultraviolet absorbent can be evaluated by a method such as scanning electron microscope, powder X-ray diffraction measurement, and differential scanning calorimetry. In addition, a dissolution profile can be created by a dissolution test to confirm whether or not the ultraviolet absorbent contained in the porous silica has been dissolved. The average particle size of the obtained porous silica containing the ultraviolet absorbent can be measured by a known method such as a light scattering photometer and a transmission electron microscope.

The amount of ultraviolet absorber contained in the porous silica (A2) is 30 to 50% by mass, and preferably 35 to 45% by mass. By adding a nonionic surfactant (B) to the porous silica having such an amount of ultraviolet absorber contained therein, it is possible to obtain a sufficient ultraviolet absorbing effect.

The (A2) component may be, for example, one type of porous silica containing multiple ultraviolet absorbents; a first porous silica containing a first ultraviolet absorbent and a second porous silica containing a different second ultraviolet absorbent; or a combination of a first porous silica containing one type of ultraviolet absorbent and a second porous silica containing the same ultraviolet absorbent, where the first porous silica and the second porous silica have different parameters (for example, the average particle size of the porous silica, the encapsulation rate of the ultraviolet absorbent).

The content of the porous silica encapsulating the ultraviolet absorber in the emulsified topical composition is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more, relative to the total amount of the composition, from the viewpoint of more prominently exhibiting the effect of this embodiment, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

((B) Nonionic Surfactant)
The emulsified topical composition in the second aspect of this embodiment further contains one or more nonionic surfactants as component (B). The nonionic surfactant is not particularly limited as long as it can be used in topical compositions. Although it should not be limited to a specific mechanism, the nonionic surfactant can improve dispersibility and contribute to improving ultraviolet absorbing effect.

From the viewpoint of more significantly achieving the effects of this embodiment, the HLB value of the nonionic surfactant is preferably 2 to 20, more preferably 4 to 19, even more preferably 8 to 18, and even more preferably 9.5 to 18. Examples of nonionic surfactants having an HLB value of 2 or more and less than 4 include compounds selected from the group consisting of propylene glycol monostearate, glyceryl stearate, polyglyceryl-10 pentaisostearate, and lauryl PEG-9 polydimethylsiloxyethyl dimethicone, either alone or in combination of two or more.
Examples of the nonionic surfactant having an HLB of 4 or more and less than 6 include compounds selected from the group consisting of sorbitan isostearate, sorbitan stearate, and PEG-9 polydimethylsiloxyethyl dimethicone, which may be used alone or in combination of two or more.
Examples of the nonionic surfactant having an HLB of 6 or more and less than 9 include compounds selected from the group consisting of sorbitan laurate and sorbitan palmitate, which may be used alone or in combination of two or more kinds.
Examples of nonionic surfactants having an HLB of 9 or more and less than 14 include compounds selected from the group consisting of polyoxyethylene hydrogenated castor oil 20, polyoxyethylene hydrogenated castor oil 40, polyoxyethylene hydrogenated castor oil 50, polyglyceryl-10 stearate, polyglyceryl-10 isostearate, polyoxyethylene monococonut oil fatty acid PEG-7 glyceryl, polyoxyethylene lauryl cetyl ether, and PEG-6 stearate, which may be used alone or in combination of two or more.
Examples of nonionic surfactants having an HLB of 14 or more and less than 18 include compounds selected from the group consisting of polyoxyethylene hydrogenated castor oil 60, polyoxyethylene hydrogenated castor oil 80, polyoxyethylene (20) sorbitan stearate, polyoxyethylene (20) sorbitan oleate, polyoxyethylene (20) sorbitan isostearate, bisPEG-18 methyl ether dimethylsilane, PEG-25 stearate, PEG-40 stearate, PEG-55 stearate, and PEG-25 isostearate, either alone or in combination.

The content of the nonionic surfactant in the emulsified topical composition of this embodiment is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, based on the total amount of the composition, from the viewpoint of more prominently exhibiting the effect of this embodiment, and is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less.

The content ratio of the porous silica encapsulating the ultraviolet absorber (A2) and the nonionic surfactant (B) in the emulsified topical composition of this embodiment is preferably 10 to 1,000 parts by mass, more preferably 20 to 1,000 parts by mass, and even more preferably 50 to 1,000 parts by mass of the nonionic surfactant (B) per 1 part by mass of the porous silica encapsulating the ultraviolet absorber (A2).

((C3) Other UV absorbers)
The emulsion composition for topical use in the second aspect of the present invention may further contain, as the component (C3), for example, an ultraviolet absorber other than the ultraviolet absorber encapsulated in the porous silica (A2). Although there are no limitations on such an ultraviolet absorber, it is preferable that, for example, the ultraviolet absorber is present in the emulsion composition for topical use without being encapsulated in the silica particles. Examples of such ultraviolet absorbers include bisethylhexyloxyphenol methoxyphenyl triazine (BEMT) (also known as 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine), methylene bisbenzotriazolyl tetramethylbutylphenol (also known as 2,2'-methylene bis[6-(2H-benzotriazol-2yl)-4-(1,1,3,3-tetramethylbutyl)phenol]), terephthalidene dicamphor sulfonic acid, drometrizole trisiloxane, ethylhexyl triazone (also known as 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]1,3,5-triazine), phenylbenzimidazole sulfonic acid,
4-tert-Butyl-4'-methoxydibenzoylmethane (also known as t-butyl methoxydibenzoylmethane, also known as Avobenzone), dimethoxybenzylidene dioxoimidazolidinepropionate 2-ethylhexyl, dihydroxydimethoxybenzophenone disulfonate sodium, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts, dihydroxydimethoxybenzophenone, dihydroxybenzophenone, tetrahydroxybenzophenone (oxybenzone-2), dihydroxybenzophenone, ferulic acid, octyl salicylate (2-ethylhexyl salicylate), homomenthyl salicylate, trisbiphenyl triazine, methyl 2,5-diisopropylcinnamate, glyceryl di-paramethoxycinnamate mono-2-ethylhexanoate, 2-ethylhexyl paramethoxycinnamate (also known as Met ethylhexyl methoxycinnamate), cinoxate, a mixture of isopropyl paramethoxycinnamate and diisopropyl cinnamate, dimethicodimethyl benzalmalonate, 2-ethylhexyl 2-cyano-3,3-diphenylprop-2-enoate (also known as octocrylene), 2-phenylbenzimidazole-5-sulfonic acid, para-aminobenzoic acid (hereinafter abbreviated as "PABA") or a derivative thereof (ethyl PABA, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA, glyceryl PABA, etc.), 4-(2-β-glucopyranosyloxy)propoxy-2-hydroxybenzophenone, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, bis(trimethylsiloxy)silylisopentyl methyl trimethoxycinnamate, and amyl paradimethylaminobenzoate,
More preferably, it may be at least one selected from the group consisting of bisethylhexyloxyphenol methoxyphenyl triazine, methylene bisbenzotriazolyl tetramethylbutylphenol, terephthalylidene discamphorsulfonic acid, terephthalylidene dicamphorsulfonic acid, drometrizole trisiloxane, ethylhexyl triazone, and phenylbenzimidazole sulfonic acid.

The content of component (C3) in the emulsified topical composition is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, based on the total amount of the composition, from the viewpoint of achieving a more pronounced effect of this embodiment, and is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less.

(effect)
As shown in the examples, the emulsified topical composition of this embodiment can achieve both enhanced ultraviolet absorbing ability and a good feeling when used. In particular, for example, in the presence of the (A2) component and the (B) component, the ultraviolet absorbing ability is significantly increased.

[Optional components and production method etc. common to the first and second embodiments]
(D) Ultraviolet Scattering Component)
The composition of the present invention may further contain an ultraviolet ray scattering component as component (D).The ultraviolet ray scattering component may be, for example, inorganic compounds such as zinc oxide, titanium oxide, iron oxide, cerium oxide, zirconium oxide, titanium silicate, zinc silicate, anhydrous silicic acid, cerium silicate, and hydrous silicic acid, those coated with inorganic powder such as hydrous silicic acid, aluminum hydroxide, mica, or talc, those composited with resin powder such as polyamide, polyethylene, polyester, polystyrene, or nylon, and those treated or coated with silicone oil, fatty acid aluminum salt, etc.

Among these, inorganic compounds such as zinc oxide, titanium oxide, and iron oxide, and inorganic compounds treated or coated with inorganic powders such as aluminum hydroxide, hydrous silicic acid, mica, and talc, or with silicone oil, are preferred.

(E) Active Ingredients
The composition of the present invention may further contain an active ingredient as component (E) in order to impart a medicinal effect. The active ingredient is not limited, and may be one or more of various ingredients such as brightening ingredients, anti-inflammatory ingredients, antibacterial ingredients, cell activating ingredients, astringent ingredients, antioxidant ingredients, acne treatment ingredients, anti-aging ingredients, keratin softening ingredients, ingredients for promoting the synthesis of biological ingredients such as collagen, blood circulation promoting ingredients, moisturizing ingredients, etc.

Among these, it is preferable that the composition of the present invention contains at least a brightening functional ingredient. Examples of the brightening functional ingredient include at least one ingredient selected from the group consisting of tocopherol, ascorbic acid and/or salts thereof, tranexamic acid, ascorbic acid derivatives, arbutin, 4-alkylresorcinol and/or salts thereof, 4-methoxysalicylic acid, hydroquinone, kojic acid, placenta extract, and plant ingredients having a whitening effect (e.g. extracts of Phellodendron Bark, Saxifrage, Aloe, etc.).

The anti-inflammatory ingredients include glycyrrhizinic acid, glycyrrhizinic acid derivatives, azulene, ingredients derived from plants (e.g., comfrey), zinc oxide, tocopherol acetate, allantoin, aminocaproic acid, and hydrocortisone.

The antibacterial components include chlorhexidine, salicylic acid, benzalkonium chloride, acrinol, benzethonium chloride, cresol, gluconic acid and its derivatives, povidone-iodine, potassium iodide, iodine, isopropylmethylphenol, triclocarban, triclosan, photosensitizer No. 101, photosensitizer No. 201, paraben, phenoxyethanol, 1,2-pentanediol, alkyldiaminoglycine hydrochloride, piroctoolamine, miconazole, etc.

The cell activation components include amino acids such as γ-aminobutyric acid and ε-aminocaproic acid; vitamins such as retinol, thiamine, riboflavin, pyridoxine hydrochloride, and pantothenic acids; α-hydroxy acids such as glycolic acid and lactic acid; tannins, flavonoids, saponin, and photosensitizer No. 301.

The astringent ingredients include zinc oxide, zinc sulfate, aluminum chloride, zinc sulfocarbonate, and tannic acid.

The antioxidant components include, for example, components derived from plants (e.g., grapes, ginseng, comfrey, etc.); proanthocyanidin, tocopherol and its derivatives, ascorbic acid and its derivatives, hesperidin and its derivatives, ergothioneine, sodium bisulfite, erythorbic acid and its salts, flavonoids, glutathione, etc.

The anti-aging ingredients include pangamic acid, kinetin, ursolic acid, turmeric extract, sphingosine derivatives, silicon, silicic acid, N-methyl-L-serine, mevalonolactone, etc.

The keratin softening ingredients include lactic acid, salicylic acid, salicylic acid glycolic acid, gluconic acid, citric acid, malic acid, fruit acid, phytic acid, urea, sulfur, etc.

The blood circulation promoting ingredients include ingredients derived from plants (e.g., ginseng, angelica, arnica, ginkgo, fennel, linden, Dutch oak, chamomile, Roman chamomile, carrot, gentian, burdock, rice, hawthorn, shiitake mushroom, ginger, European hawthorn, European juniper, cnidium rhizome, Swertia japonica, thyme, clove, tangerine peel, red pepper, angelica tree, tonin, spruce, carrot, garlic, butcher's broom, grape, peony, horse chestnut, melissa, yuzu, coix seed, ryokucha, rosemary, rose hip, tangerine peel, angelica tree, spruce, peach, apricot, walnut, corn), etc.

The moisturizing ingredients include, for example, diglycerin trehalose; polymeric compounds such as sodium hyaluronate, heparinoids, sodium chondroitin sulfate, collagen, elastin, keratin, chitin, and chitosan; amino acids such as glycine, aspartic acid, and arginine; natural moisturizing factors such as sodium lactate, urea, and sodium pyrrolidone carboxylate; lipids such as ceramide, cholesterol, and phospholipids; and plant extracts such as chamomile extract, witch hazel extract, tea extract, and perilla extract.

(Other ingredients)
In addition to the above components (A) to (E), the composition of the present invention may contain various components that can be used as components of pharmaceuticals, quasi-drugs, or external preparations in the field of cosmetics, as necessary, within a quantitative and qualitative range that does not impair the effects of the present invention, such as scrubbing agents, vitamins, peptides or derivatives thereof, amino acids or derivatives thereof, cleaning components, irritation reducing agents, thickeners, preservatives, colorants, dispersants, pH adjusters, fragrances, etc. These components may be contained alone or in combination of two or more. Water may also be contained.

(Manufacturing method, form, physical properties)
The emulsified topical composition of the present invention can be prepared in various desired forms such as emulsion, paste, foam, gel, liquid, cream, sheet (supported on a substrate), aerosol, spray, etc. by mixing the above-mentioned optional components with the above-mentioned components (A) to (E) as necessary, further mixing with other solvents and bases for topical agents commonly used as necessary, and adjusting the pH as necessary. These can be prepared by methods commonly used in the art.

Specifically, the method for preparing the emulsified topical composition of the present invention is not particularly limited, and may be appropriately performed by heating, mixing, dispersing, etc., depending on the components to be blended. For example, a method may be used in which an oil phase uniformly dissolved by heating and an aqueous phase uniformly dissolved by heating are mixed, thoroughly stirred with a homogenizer, and then cooled to room temperature.
Furthermore, the step of dispersing component (A) may be carried out either before or after the emulsification step, and when aggregation is likely to occur, it may be carried out after the emulsification step.

The emulsified topical composition of the present invention is preferably in the form of an oil-in-water emulsified topical composition, and may be, for example, a milky or semi-solid composition. Although not limited thereto, the content of the aqueous phase in the composition may be preferably 40 to 90% by mass, more preferably 50 to 90% by mass, and most preferably 60 to 90% by mass. The aqueous phase is the total amount of the aqueous solvent, and may be, for example, the total amount of the aqueous solvent including water, polyhydric alcohol, and ethanol, without being limited thereto.

The pH of the emulsified topical composition of the present invention is preferably 4 to 9, more preferably 4 to 8, and even more preferably 5 to 7, from the viewpoint of reducing irritation to the skin and mucous membranes and providing a good feeling of use.

The viscosity of the emulsified topical composition of the present invention is not particularly limited, but from the viewpoint of providing a good feel on the skin, the viscosity measured at 25°C using an E-type viscometer is, for example, 1 to 100,000 mPa·s, preferably 1 to 50,000 mPa·s, more preferably 1 to 40,000 mPa·s, and even more preferably 1 to 30,000 mPa·s. More specifically, the viscosity measurement method is similar to the measurement method using a B-type viscometer (measurement time 60 minutes).

In this specification, the spectral integrated value at wavelengths of 280 nm to 400 nm refers to the value calculated by integrating the absorbance in the wavelength range of 280 to 400 nm in the absorption spectrum of the emulsified topical composition.

In this specification, the method for measuring the UV absorption effect of an emulsified topical composition is in accordance with the method described in the Examples.

(Application)
The emulsion composition for external use of the present invention is a medicine, a quasi-drug, or a cosmetic, and can be used, for example, to expect ultraviolet blocking effect and sunburn prevention effect.The emulsion composition for external use of the present invention is particularly suitable for use in preventing and reducing photodegradation and photoaging, such as preventing and reducing the occurrence of age spots and freckles caused by sunburn, as well as for use in preventing sunburn.It can also be used for anti-inflammation, anti-aging, anti-oxidation, acne prevention, etc.

The emulsified topical composition of the present invention can be used, for example, as basic cosmetics such as sunscreens, beauty serums, lotions, emulsions, creams, gel creams, makeup bases, lotions, oils, and packs; makeup cosmetics such as foundations, lipsticks, lip balms, mascaras, eye shadows, eyeliners, eyebrow inks, and nail polish; and cleansers such as face washes, cleansers, and body washes. The emulsified topical composition of the present invention can be preferably a skin care product such as a sunscreen, beauty serum, lotion, emulsion, cream, or gel cream.

(Dosage and Administration)
The emulsified topical composition of the present invention can be applied to the skin, hair, and nails, and is preferably applied to the skin. The emulsified topical composition of the present invention can be used in a known or commonly used manner and dosage, from once to several times a day, depending on the purpose.

In a first aspect of the present invention, the following emulsified composition for external use can be provided.
[1]
An emulsion composition for external use comprising (C1) diethylaminohydroxybenzoylhexyl benzoate, and (A1) porous silica encapsulating an ultraviolet absorber,
The average particle size of the porous silica is 1.4 to 40 μm,
The emulsified composition for external use, wherein the porous silica is porous silica encapsulating an ultraviolet absorber that is solid at 25°C.
[2]
The emulsified topical composition according to [1], wherein the UV absorber encapsulated in component (A1) is at least one selected from the group consisting of diethylamino hydroxybenzoyl hexyl benzoate, bisethylhexyloxyphenol methoxyphenyl triazine, methylene bisbenzotriazolyl tetramethylbutylphenol, terephthalylidene discamphorsulfonic acid, terephthalylidene dicamphorsulfonic acid, drometrizole trisiloxane, ethylhexyl triazone, and phenylbenzimidazole sulfonic acid.
[3]
The emulsified composition for external use according to [1] or [2], wherein an encapsulation rate of the ultraviolet absorber relative to the porous silica is 30 to 50%.
[4]
The emulsified composition for external use according to any one of [1] to [3], wherein the content of the (A1) component per 1 part by mass of the (C1) component is from 0.0001 parts by mass to 10 parts by mass.
[5]
The emulsified composition for external use according to any one of [1] to [4], further comprising a nonionic surfactant.
[6]
The emulsified composition for external use according to any one of [1] to [5], wherein the nonionic surfactant is a sorbitan fatty acid ester or a polyethylene glycol fatty acid ester.
[7]
(C1) The emulsified composition for external use according to any one of [1] to [6], wherein the content of diethylaminohydroxybenzoylhexyl benzoate is 0.5% by mass or more and 10% by mass or less.
[8]
The emulsified composition for external use according to any one of [1] to [7], wherein the content of the component (A1) is from 0.0001% by mass to 10% by mass.

In a second aspect of the present invention, there can be provided an emulsified composition for external use in the following emulsion form.
[9]
(A2) porous silica encapsulating an ultraviolet absorber, and (B) a nonionic surfactant;
An emulsified topical composition comprising:
The average particle size of the porous silica is 1.4 to 40 μm,
The porous silica is porous silica containing an ultraviolet absorber that is solid at 25° C.,
The emulsified composition for external use has an encapsulation rate of the ultraviolet absorber relative to the porous silica of 30 to 50%.
[10]
The emulsified composition for external use according to [9], wherein the nonionic surfactant has an HLB value of 5.0 to 20.
[11]
The emulsified topical composition according to [6] or [7], further comprising (C3) an ultraviolet absorber.
[12]
The emulsion composition for external use according to claim [11], wherein the (C3) ultraviolet absorber is diethylaminohydroxybenzoylhexyl benzoate.
[13]
The emulsified composition for external use according to any one of [9] to [12], wherein the ultraviolet absorber encapsulated in the component (A2) is bis-ethylhexyloxyphenol methoxyphenyl triazine.
[14]
The emulsified composition for external use according to any one of [9] to [13], wherein the nonionic surfactant is a sorbitan fatty acid ester or a polyethylene glycol fatty acid ester.
[15]
The emulsified composition for external use according to any one of [9] to [14], wherein the content of the component (C3) is 5% by mass or more and 25% by mass or less.
[16]
The emulsified composition for external use according to any one of [9] to [15], wherein the content of the component (A2) is from 0.0001% by mass to 10% by mass.

Next, the present invention will be specifically explained using examples and test examples, but the present invention is not limited to the following examples and test examples. Unless otherwise specified, the units of each component are mass %.

The porous silica used in the following examples is as follows:
Silica A (average particle size 2.2 μm, oil absorption 150 mL/100 g)
Silica B (average particle size 3 μm, oil absorption 120 mL/100 g)
Silica C (average particle size 3 μm, oil absorption 300 mL/100 g)
Silica D (average particle size 6.3 μm, oil absorption 110 mL/100 g)
Silica E (average particle size 11 μm, oil absorption 140 mL/100 g)

The oil-in-water emulsified topical compositions shown in each table were prepared by a conventional method. The porous silica containing an ultraviolet absorber was prepared by adding bisethylhexyloxyphenol methoxyphenyl triazine to a toluene solvent and stirring the mixture to prepare a solution of bisethylhexyloxyphenol methoxyphenyl triazine. It was confirmed that the solid bisethylhexyloxyphenol methoxyphenyl triazine was not present and the mixture was completely dissolved. The porous silica was added to the prepared solution and stirred. Next, the mixture was heated to a temperature higher than the boiling point of the toluene solvent to remove the toluene solvent, and dried to prepare porous silica containing an ultraviolet absorber (A). It was confirmed by gas chromatography that the toluene solvent was 500 ppm or less and substantially no residue was present in the dried component (A). The encapsulation rate of the ultraviolet absorber in the component (A) can be calculated from the amount of ultraviolet absorber used and the amount of porous silica used in the process of preparing the component (A). Furthermore, the BEMT-containing silica and the silica used as the mother powder were observed and compared using a scanning electron microscope, and it was also confirmed that BEMT was encapsulated by appearance observation. It was also confirmed by an elution test that the ultraviolet absorber encapsulated in the porous silica did not dissolve.
Next, the oil phase which had been uniformly heated and dissolved and the aqueous phase which had been uniformly heated and dissolved were mixed and thoroughly stirred with a homogenizer, and then cooled to room temperature to prepare compositions of the examples and comparative examples.

[Test Example 1. UV protection evaluation test]
(Evaluation of the rate of change of the spectrum integrated value)
The composition for external use was uniformly applied to a square PMMA (polymethyl methacrylate) plate (HelioScreen's "Helioplate SB6") to an application amount of 1.3 mg/ ^cm2 , and allowed to dry naturally for 15 minutes to prepare a measurement sample. Each sample was irradiated with ultraviolet light from the same distance using an SPF analyzer (Labsphere's "UV-2000S SPF analyzer"). The spectral transmittance in the wavelength range of 280 to 400 nm was determined at nine points for one sample, and a spectrum was obtained by averaging these. The area value of the absorption spectrum at wavelengths of 280 nm to 400 nm, that is, the value calculated by integrating the absorbance in the wavelength range of 280 nm to 400 nm, was taken as the spectral integrated value. The rate of change in the spectral integrated value of the example composition relative to the comparative example composition was calculated using formula 1. The higher the rate of change, the higher the ultraviolet absorption effect.
[Formula 1] Rate of change in spectrum integrated value=(Spectral integrated value of Example/Spectral integrated value of Comparative Example)×100(%)

(Evaluation of the rate of change in absorbance at a wavelength of 310 nm)
The topical composition was uniformly applied to a square PMMA (polymethyl methacrylate) plate (HelioScreen's "Helioplate SB6") to an application amount of 1.3 mg/ ^cm2 , and allowed to dry naturally for 15 minutes to prepare a measurement sample. Each sample was irradiated with ultraviolet light from the same distance using an SPF analyzer (Labsphere's "UV-2000S SPF Analyzer"). The absorbance at a wavelength of 310 nm was measured at nine points for each sample. The average value was taken as the absorbance at a wavelength of 310 nm of the topical composition. The rate of change in absorbance at a wavelength of 310 nm of the example composition relative to the comparative example composition was calculated using formula 2. The higher the rate of change, the higher the ultraviolet absorption effect.
[Formula 2] Rate of change in absorbance at a wavelength of 310 nm=(Absorbance at a wavelength of 310 nm in the Example/Absorbance at a wavelength of 310 nm in the Comparative Example)×100(%)

[Test Example 2. Usability evaluation test]
In addition, the sensation of use of each topical composition when applied in equal amounts to the arm was evaluated by a panel of three cosmetic evaluation experts based on the following criteria.
<Usability evaluation criteria: Stickiness>
◎: Very good, no stickiness at all. ◯: Good, almost no stickiness. △: Slightly sticky, but not unpleasant. ×: Sticky and unpleasant.

<Usage sensation evaluation criteria: adhesion or moist feeling>
◎: Both the feeling of adhesion and the feeling of moisture are good. ◯: Feels of adhesion and moisture. △: Feels of adhesion and moisture slightly. ×: Does not feel of adhesion or moisture.

<Usability evaluation standard: freshness>
◎: Feels very fresh 〇: Feels fresh △: Feels slightly fresh ×: Does not feel fresh

The compositions shown in Table 1 were used to evaluate the above Test Examples 1 and 2. The rate of change in the spectral integrated value was calculated by calculating the ratio of the integrated value of the compositions of Comparative Examples 1-2 to 1-4 and the integrated value of the compositions of Examples 1-1 to 1-3 relative to the integrated value of the composition of Comparative Example 1-1, and the results are shown in Table 1. The composition of each Example had a significantly increased rate of change in the spectral integrated value compared to the corresponding Comparative Example. In addition, in the Examples, the increase in the rate of change in the spectral integrated value with an increase in the DHHB content was greater than in the Comparative Examples, which revealed that the ultraviolet absorbing effect of the composition was significantly enhanced by the coexistence of BEMT in a state encapsulated in porous silica in the composition compared to the case where BEMT coexists in a state where it is not encapsulated in porous silica.

In addition, the composition of the example had a better feel when used than the composition of the comparative example, and the feel was good even when the DHHB content was increased.

The above Test Examples 1 and 2 were evaluated using the compositions shown in Table 2. The rate of change in absorbance at a wavelength of 310 nm was calculated as the ratio of the absorbance of the composition of Example 2-1 to the absorbance of the composition of Comparative Example 2-1, and the results are shown in Table 2. The composition of each Example had a significantly increased rate of change in absorbance compared to the corresponding Comparative Example. Furthermore, in the Examples, the increase in the rate of change in absorbance with an increase in DHHB content was greater than in the Comparative Examples, which revealed that the UV absorption effect of the emulsion topical composition is significantly enhanced by the coexistence of BEMT encapsulated in porous silica in the composition compared to the case where BEMT is not encapsulated in porous silica and coexists in the composition.

The compositions shown in Table 3 were used to perform the evaluations of Test Examples 1 and 2. For the rate of change in absorbance at a wavelength of 310 nm, the ratio of the absorbance of the compositions of Comparative Examples 3-2 to 3-3 and Examples 3-1 to 3-5 to the absorbance of the composition of Comparative Example 3-1 was calculated, and the results are shown in Table 3. For the rate of change in spectrum integrated value, the integrated values of the compositions of Comparative Examples 3-1 to 3-3 and Examples 3-1 to 3-5 to the integrated value of the composition of Comparative Example 3-1 were calculated, and the results are shown in Table 3.
The compositions of the Examples showed a significant increase in the rate of change in absorbance at a wavelength of 310 nm and the rate of change in the spectrum integrated value, compared to the corresponding compositions of the Comparative Examples. It was revealed that the ultraviolet absorbing effect is enhanced in the presence of a surfactant and porous silica encapsulating an ultraviolet absorbing agent.

In addition, the compositions of the examples had a better feel when used than the compositions of the comparative examples. In other words, the compositions of the examples had a good feel when used, including stickiness, a feeling of adhesion, a feeling of moisture, and a feeling of freshness.

The compositions shown in Table 4 were used to carry out the evaluations of Test Examples 1 and 2. The rate of change in absorbance at a wavelength of 310 nm was calculated by dividing the absorbance of the compositions of Examples 4-1 to 4-10 by the absorbance of the composition of Comparative Example 4-1, and the results are shown in Table 4.
The emulsified topical compositions of each Example showed a significant increase in the rate of change in absorbance at a wavelength of 310 nm compared to the corresponding Comparative Example. It was revealed that the ultraviolet absorbing effect is enhanced in the presence of a surfactant and porous silica encapsulating an ultraviolet absorbing agent.

The compositions shown in Table 5 were used to evaluate Test Examples 1 and 2. The rate of change in absorbance at a wavelength of 310 nm was calculated for the corresponding Example with the same number relative to the Comparative Example, and the results are shown in Table 5. Similarly, the rate of change in spectrum integrated value was calculated for the corresponding Example with the same number relative to the Comparative Example, and the results are shown in Table 5. For example, the value of Example 5-1 is shown as the rate of change in comparison with Comparative Example 5-1, and the value of Example 5-2 is shown as the rate of change in comparison with Comparative Example 5-2.
The compositions of the Examples showed a significantly increased rate of change in absorbance at a wavelength of 310 nm compared to the corresponding compositions of the Comparative Examples. It became clear that the ultraviolet absorbing effect was enhanced in the presence of a surfactant and porous silica encapsulating an ultraviolet absorbing agent.

Furthermore, the compositions of the Examples had a better feel when used than the compositions of the Comparative Examples, that is, the compositions of the Examples had a good feel when used in terms of all of stickiness, adhesion or moistness, and freshness.

Next, the compositions shown in Table 6 were used to perform the evaluations of Test Examples 1 and 2. The rate of change in absorbance at a wavelength of 310 nm was calculated by calculating the ratio of the absorbance of the compositions of Examples 6-1 to 6-5 to the absorbance of the composition of Comparative Example 6-1, and the results are shown in Table 6.
The compositions of the Examples showed a significantly increased rate of change in absorbance at a wavelength of 310 nm compared to the corresponding compositions of the Comparative Examples. It became clear that the ultraviolet absorbing effect was enhanced in the presence of a surfactant and porous silica encapsulating an ultraviolet absorbing agent.

Moreover, the compositions of the Examples generally had a good feel when used, i.e., the compositions of the Examples had a good feel when used in terms of all of stickiness, adhesion or moistness, and freshness.

Next, the compositions shown in Table 7 were used to perform the evaluations of Test Examples 1 and 2. The rate of change in absorbance at a wavelength of 310 nm was calculated by calculating the ratio of the absorbance of the compositions of Examples 7-1 to 7-3 to the absorbance of the composition of Comparative Example 7-1, and the results are shown in Table 7.
The composition of each Example had an increased rate of change in absorbance at a wavelength of 310 nm compared to the corresponding composition of the Comparative Example. It was revealed that the ultraviolet absorbing effect is enhanced in the presence of a surfactant and porous silica encapsulating an ultraviolet absorber.

Furthermore, the compositions of the examples had a good feel when used, i.e., the compositions of the examples had a good feel when used in terms of all of stickiness, adhesion, moistness, and freshness.

Next, the compositions shown in Table 8 were used to perform the evaluations of Test Examples 1 and 2. The rate of change in absorbance at a wavelength of 310 nm was calculated as the ratio of the absorbance of the compositions of Examples 8-1 to 8-3 to the absorbance of the composition of Comparative Example 8-1, and the results are shown in Table 8.
The emulsified external use composition of each Example has a significantly increased absorbance change rate at 310 nm compared with its corresponding Comparative Example.It is clear that the ultraviolet absorbing effect is enhanced under the coexistence of the porous silica that contains ultraviolet absorbing agent and surfactant.In addition, the composition of each Example has a generally good feeling when used.

Claims

A composition for external use comprising (A) porous silica containing an ultraviolet absorber,
The average particle size of the porous silica is 1.4 to 40 μm,
The emulsified composition for external use, wherein the porous silica is porous silica encapsulating an ultraviolet absorber that is solid at 25°C.
The emulsified topical composition according to claim 1, wherein the ultraviolet absorber encapsulated in component (A) is at least one selected from the group consisting of diethylaminohydroxybenzoylhexylbenzoate, bisethylhexyloxyphenol methoxyphenyl triazine, methylenebisbenzotriazolyltetramethylbutylphenol, terephthalylidene dicamphorsulfonic acid, terephthalylidene dicamphorsulfonic acid, drometrizole trisiloxane, ethylhexyl triazone, and phenylbenzimidazole sulfonic acid.
The emulsified composition for external use according to claim 1, wherein the encapsulation rate of the ultraviolet absorber in the porous silica is 30 to 50%.
A method for enhancing the ultraviolet absorbing ability of diethylaminohydroxybenzoylhexylbenzoate, comprising causing diethylaminohydroxybenzoylhexylbenzoate to coexist with porous silica containing an ultraviolet absorbing agent (A).
A method for producing an emulsion composition for external use containing diethylaminohydroxybenzoylhexyl benzoate and (A) porous silica encapsulating an ultraviolet absorber, comprising the steps of:
The method includes a step of mixing diethylaminohydroxybenzoylhexyl benzoate and (A) porous silica containing an ultraviolet absorber,
The average particle size of the porous silica is 1.4 to 40 μm,
The method for producing an emulsified topical composition, wherein the porous silica is porous silica encapsulating an ultraviolet absorber that is solid at 25°C.