Skin topical products

Abstract

The present invention provides a skin external preparation that has an excellent feel, such as a refreshing sensation, at the initial stage of application and can form a good coating film of a non-volatile oil agent, such as an oil-soluble ultraviolet absorber. The skin external preparation comprises: granular gel capsules containing the non-volatile oil agent; and a liquid containing the following component (b1): (b1) a volatile medium, the granular gel capsules being dispersed in the liquid, the non-volatile oil agent content in the granular gel capsules being 1.5% by mass or greater relative to the total mass of the skin external preparation, the non-volatile oil agent content in the liquid being 0% by mass or greater and 14% by mass or less relative to the total mass of the skin external preparation, and the aqueous thickener content in the liquid being 0% by mass or greater and 0.25% by mass or less relative to the total mass of the skin external preparation.

Description

Technical Field

[0001] The present invention relates to a skin external preparation. Background Art

[0002] Conventionally, known topical skin preparations having a UV protection effect include those in which granular gel capsules containing a UV absorber are dispersed in a liquid. For example, a lotion containing PVA microcapsules containing a UV absorber, water, 1.00% by mass of polyoxyethylene hydrogenated castor oil, 0.20% by mass of an (acrylic acid / alkyl acrylate (C10-30)) copolymer, and 0.10% by mass of xanthan gum has been reported as one such topical skin preparation (Patent Document 1).

[0003] (Patent Document 1) Japanese Patent Application Laid-Open No. 2002-37713

[0004] (Patent Document 2) Japanese Patent Application Laid-Open No. 3-193716

[0005] (Patent Document 3) Japanese Patent Application Laid-Open No. 2012-171891

[0006] (Patent Document 4) Japanese Patent Application Laid-Open No. 2012-171892

[0007] (Patent Document 5) Japanese Patent Application Laid-Open No. 2014-91737

[0008] (Patent Document 6) Japanese Patent Application Laid-Open No. 2016-104712 Summary of the Invention

[0009] The present invention provides a skin external preparation comprising: a granular gel capsule containing a non-volatile oil; and a liquid containing the following components (b1): (b1) a volatile medium,

[0010] The granular gel capsules are dispersed in the liquid,

[0011] The content of the non-volatile oil in the granular gel capsule is 1.5% by mass or more relative to the total mass of the external preparation for skin.

[0012] The content of the non-volatile oil in the liquid is 0% by mass or more and 14% by mass or less relative to the total mass of the external preparation for skin,

[0013] The content of the aqueous thickener in the liquid is 0% by mass or more and 0.25% by mass or less relative to the total mass of the external preparation for skin. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is a micrograph of a model plate to which no external skin preparation has been applied.

[0015] Figure 2 This is a fluorescence microscope photograph of a model plate coated with α agent. DETAILED DESCRIPTION

[0016] The lotion described in Patent Document 1 feels heavy to the touch in the initial stage of application, and a refreshing feeling is not easily felt.

[0017] In addition, there are known double-layer tanning cosmetics consisting of a microcapsule layer and a water layer, in which an ultraviolet absorber or the like is dispersed in an aqueous gelatin solution (Patent Document 2), and skin external preparations in which granular gel capsules with an ultraviolet absorber dispersed therein are dispersed in an oil-in-water emulsion composition containing a large amount of an oil-soluble ultraviolet absorber or the like (Patent Documents 3 to 6).

[0018] However, the double-layer tanning cosmetic described in Patent Document 2 has an insufficient UV protection effect. In addition, the skin external preparations described in Patent Documents 3 to 6 tend to have uneven distribution of the UV absorber during application, resulting in insufficient UV protection effect.

[0019] The present invention relates to providing a skin external preparation that has an excellent feel such as a refreshing feeling in the initial stage of application and can form a good coating film of a non-volatile oil such as an oil-soluble ultraviolet absorber.

[0020] The present inventors have discovered that a skin external preparation has an excellent feel such as a refreshing sensation in the initial stage of application and can form a good coating film of a non-volatile oil agent such as an oil-soluble ultraviolet absorber. The skin external preparation comprises: granular gel capsules containing the non-volatile oil agent; and a liquid containing a volatile medium, wherein the granular gel capsules are dispersed in the liquid, the content of the non-volatile oil agent in the granular gel capsules is 1.5% by mass or more relative to the total mass of the skin external preparation, the content of the non-volatile oil agent in the liquid is 0% by mass or more and 14% by mass or less relative to the total mass of the skin external preparation, and the content of an aqueous thickener in the liquid is 0% by mass or more and 0.25% by mass or less relative to the total mass of the skin external preparation, thereby completing the present invention.

[0021] The skin external preparation of the present invention has an excellent feeling of use such as a refreshing feeling in the initial stage of application, and can form a good coating film of a non-volatile oil such as an oil-soluble ultraviolet absorber.

[0022] The skin external preparation of the present invention is characterized in that it contains: granular gel capsules containing a non-volatile oil agent (hereinafter also referred to as component (A)), and a liquid containing the following component (b1): (b1) a volatile medium (hereinafter also referred to as component (B)), the granular gel capsules being dispersed in the liquid, the content of the non-volatile oil agent in the granular gel capsules being 1.5% by mass or more relative to the total mass of the skin external preparation, the content of the non-volatile oil agent in the liquid being 0% by mass or more and 14% by mass or less relative to the total mass of the skin external preparation, and the content of the aqueous thickener in the liquid being 0% by mass or more and 0.25% by mass or less relative to the total mass of the skin external preparation.

[0023] Throughout this specification, oily components are referred to as "oil agents." Oil agents can be solid, semi-solid, or liquid. For example, oil-soluble UV absorbers, amphiphilic solid fats, and oily thickeners are oil agents. The term "non-volatile oil agent" refers to an oily component that is non-volatile at 25°C under 1 atmosphere. For example, non-volatile oil-soluble UV absorbers, non-volatile amphiphilic solid fats, and non-volatile oily thickeners are non-volatile oil agents.

[0024] In this specification, nonvolatile at 25°C at 1 atmosphere is referred to as "nonvolatile," while volatile at 25°C at 1 atmosphere is referred to as "volatile." Specifically, "nonvolatile" means that the evaporation rate at 25°C over 6 hours, as measured by the following method, is less than 20%.

[0025] Measurement method: Place 90 mm diameter filter paper in a 120 mm diameter glass petri dish. Place 1 g of sample on the filter paper and store in a 65% RH room (25°C) for 6 hours. Measure the sample mass before and after storage, and calculate the evaporation amount using the following formula.

[0026] Evaporation amount (%) = (sample mass before storage - sample mass after storage) / sample mass before storage × 100

[0027] "Volatile" means that the evaporation amount at 25°C in 6 hours as measured by the above method is more than 20%.

[0028] The content of the nonvolatile oil in the granular gel capsule is 1.5% by mass or more relative to the total mass of the external skin preparation of the present invention. Setting the content of the nonvolatile oil to 1.5% by mass or more can improve the uniformity of the coating film.

[0029] The content of the non-volatile oil in the granular gel capsule is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 9% by mass or more, and particularly preferably 12% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the perspective of coating uniformity, etc.; furthermore, from the perspective of feel during use, it is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the content is preferably 3% by mass or more and 40% by mass or less, more preferably 6% by mass or more and 35% by mass or less, even more preferably 9% by mass or more and 30% by mass or less, and particularly preferably 12% by mass or more and 25% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0030] <(A) Granular Gel Capsules>

[0031] Granular gel capsules are preferably granular hydrogel capsules. In this specification, "granular hydrogel capsules" refer to granular gel capsules in which an oil phase is dispersed within a hydrogel. Furthermore, "hydrogel" refers to a gel obtained from an encapsulating agent using water as a solvent. The term "granular hydrogel capsule" does not include capsules in which the outer layer (sheath) and the inner layer (core) are concentrically arranged.

[0032] Furthermore, granular hydrogel capsules are preferably those in which an oil phase containing a non-volatile oil is dispersed in a hydrogel. More preferably, they are those in which an oil phase containing an oil-soluble UV absorber is dispersed in a hydrogel. Particularly preferred are granular hydrogel capsules comprising a continuous phase of a non-crosslinked hydrogel and an oil phase dispersed in the continuous phase, wherein the oil phase contains an oil-soluble UV absorber. Furthermore, the oil phase preferably contains an amphiphilic solid fat and an oily thickener along with the oil-soluble UV absorber.

[0033] As used herein, "non-crosslinked hydrogel" refers to a hydrogel that undergoes gelation through the thermoreversibility of the sol-gel process. The dissolution temperature of the non-crosslinked hydrogel in water is preferably 75°C or higher, more preferably 75°C or higher and 90°C or lower. Furthermore, the gelation temperature upon cooling after dissolution in water is preferably 30°C or higher and 45°C or lower.

[0034] From the viewpoints of storage stability (stabilization of the granular gel capsule), a refreshing feeling at the initial stage of application, and a good tight fit at the later stage of application, the granular gel capsule preferably contains one or more selected from the group consisting of (a1) an ultraviolet absorber (preferably an oil-soluble ultraviolet absorber), (a2) an encapsulating agent, (a3) ​​water, (a4) an amphiphilic solid fat, (a5) a thickener (examples of the (a5) thickener include (a5-1) an oily thickener and (a5-2) an aqueous thickener), (a6) a polyol, (a7) a powder, and (a8) a non-volatile oil (excluding oil-soluble ultraviolet absorbers, amphiphilic solid fats, and oily thickeners). More preferably, the granular gel capsule contains (a1) an ultraviolet absorber (preferably an oil-soluble ultraviolet absorber), and in addition to (a1) an ultraviolet absorber ( The composition preferably contains, in addition to the oil-soluble UV absorber, one or more components selected from (a2) an encapsulating agent, (a3) ​​water, (a4) an amphiphilic solid fat, (a5) a thickener, (a6) a polyol, (a7) a powder, and (a8) a non-volatile oil (excluding the oil-soluble UV absorber, the amphiphilic solid fat, and the oily thickener). It further preferably contains components (a1) to (a2), further preferably contains components (a1) to (a3), further preferably contains components (a1) to (a4), further preferably contains components (a1) to (a5), further preferably contains components (a1) to (a5) and one or more components selected from components (a6) and (a7), further preferably contains components (a1) to (a6), and particularly preferably contains components (a1) to (a7).

[0035] When the granular gel capsule contains an encapsulating agent, the granular gel capsule preferably comprises component (a1) dispersed in the gel-like encapsulating agent, more preferably comprises components (a1) and (a3) ​​dispersed in the gel-like encapsulating agent, further preferably comprises components (a1), (a3) ​​and (a4) dispersed in the gel-like encapsulating agent, further preferably comprises component (a1) and components (a3) ​​to (a5) dispersed in the gel-like encapsulating agent, further preferably comprises component (a1), components (a3) ​​to (a5) and one or more selected from components (a6) and (a7) dispersed in the gel-like encapsulating agent, further preferably comprises component (a1) and components (a3) ​​to (a6) dispersed in the gel-like encapsulating agent, and particularly preferably comprises component (a1) and components (a3) ​​to (a7) dispersed in the gel-like encapsulating agent.

[0036] In addition, from the viewpoints of feel in use and UV protection effect, the granular gel capsule preferably contains, as a non-volatile oil agent, at least one selected from the group consisting of (a1) an oil-soluble UV absorber, (a4) an amphiphilic solid fat, (a5-1) an oily thickener, and (a8) a non-volatile oil agent (excluding oil-soluble UV absorbers, amphiphilic solid fats, and oily thickeners). As a non-volatile oil agent, it is more preferred to contain at least (a1) an oil-soluble UV absorber. As a non-volatile oil agent, it is further preferred to contain (a1) an oil-soluble UV absorber and at least one selected from the group consisting of (a4) an amphiphilic solid fat, and (a5-1) an oily thickener. As a non-volatile oil agent, it is particularly preferred to contain (a1) an oil-soluble UV absorber, (a4) an amphiphilic solid fat, and (a5-1) an oily thickener.

[0037] ((a1) Ultraviolet absorber)

[0038] The ultraviolet absorber is preferably an oil-soluble ultraviolet absorber. By incorporating the ultraviolet absorber into the granular gel capsule, the stickiness caused by the ultraviolet absorber in the initial application can be suppressed, and a uniform coating film can be formed during the disintegration of the granular gel capsule, thereby improving the ultraviolet protection effect.

[0039] As the ultraviolet absorber, an organic ultraviolet absorber is preferred from the viewpoints of water resistance, abrasion resistance, and the like.

[0040] Examples of organic UV absorbers include benzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, triazine UV absorbers, and silicone UV absorbers. Among these, one or more selected from benzoic acid UV absorbers, cinnamic acid UV absorbers, and triazine UV absorbers are preferred from the viewpoints of UV protection effect and photostability.

[0041] Examples of benzoic acid-based ultraviolet absorbers include para-aminobenzoic acid (PABA), PABA glyceride, PABA ethyl dihydroxypropyl ester, N-ethoxylated PABA ethyl ester, N-dimethyl PABA ethyl ester, N-dimethyl PABA butyl ester, N-dimethyl PABA pentyl ester, PABA octyl dimethyl ester, and diethylaminohydroxybenzoyl hexyl benzoate.

[0042] Examples of the anthranilic acid-based ultraviolet absorber include homomenthyl-N-acetylanthranilate.

[0043] Examples of salicylic acid-based ultraviolet absorbers include amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropylphenyl salicylate.

[0044] Examples of the cinnamic acid-based ultraviolet absorbers include octyl cinnamate, ethyl 4-isopropyl cinnamate, ethyl 2,4-diisopropyl cinnamate, methyl 2,4-diisopropyl cinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α-cyano-β-phenyl cinnamate, 2-ethylhexyl α-cyano-β-phenyl cinnamate, and glyceryl mono-2-ethylhexanoyl di-p-methoxycinnamate.

[0045] Examples of the benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxybenzophenone, and 4-hydroxy-3-carboxybenzophenone.

[0046] Examples of the triazine ultraviolet absorber include 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, dioctylbutyramidotriazine, and 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine.

[0047] Examples of the silicone ultraviolet absorber include polydimethylsiloxane diethyl benzalkonium malonate and the like.

[0048] Examples of other organic ultraviolet absorbers include 3-(4'-methylbenzylidene)-d1-camphor, 3-benzylidene-d1-camphor, ethyl urocanate, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5-tert-octylphenyl)benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, 5-(3,3-dimethyl-2-norbornylene)-3-pentan-2-one, benzene bis-1,3-dione derivatives described in Japanese Patent Application Laid-Open No. 2-212579, and benzoylpinacolone derivatives described in Japanese Patent Application Laid-Open No. 3-220153.

[0049] Organic UV absorbers can be broadly divided into those that are solid at 25°C under 1 atmosphere and those that are liquid at 25°C under 1 atmosphere. For example, diethylaminohydroxybenzoylhexyl benzoate, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, and 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, listed above, are solid organic UV absorbers at 25°C under 1 atmosphere. Furthermore, isopropyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate, and 2-ethoxyethyl p-methoxycinnamate, listed above, are liquid organic UV absorbers at 25°C under 1 atmosphere.

[0050] Furthermore, the ultraviolet absorber may be used alone or in combination of two or more.

[0051] The content of the ultraviolet absorber (preferably an oil-soluble ultraviolet absorber) in the granular gel capsule is preferably 1.5% by mass or more, more preferably 3% by mass or more, even more preferably 6% by mass or more, even more preferably 9% by mass or more, and particularly preferably 12% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the perspective of ultraviolet protection effects. Furthermore, from the perspective of feel during use, it is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the content is preferably 1.5% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 40% by mass or less, even more preferably 6% by mass or more and 35% by mass or less, even more preferably 9% by mass or more and 30% by mass or less, and particularly preferably 12% by mass or more and 25% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0052] When the content of the ultraviolet absorber in the granular gel capsule is 12% by mass or more, the ultraviolet protection effect is particularly improved.

[0053] Furthermore, the content of the UV absorber (preferably an oil-soluble UV absorber) in the granular gel capsules is preferably 15% by mass or greater, more preferably 17% by mass or greater, even more preferably 19% by mass or greater, and particularly preferably 22% by mass or greater, relative to the total mass of the granular gel capsule, from the perspective of UV protection effectiveness. Furthermore, from the perspective of feel during use and emulsion stability, it is preferably 54% by mass or less, more preferably 48% by mass or less, even more preferably 42% by mass or less, and particularly preferably 40% by mass or less, relative to the total mass of the granular gel capsule. Specifically, the content is preferably 15% by mass or less, more preferably 17% by mass or less and 48% by mass or less, even more preferably 19% by mass or less and 42% by mass or less, and particularly preferably 22% by mass or less and 40% by mass or less, relative to the total mass of the granular gel capsule. Increasing the content of the UV absorber in the granular gel capsules in this manner can further improve the refreshing feeling in the initial stage of application, as well as the moistness and UV protection effectiveness in the initial stage of application. Furthermore, a sticky or astringent sensation can be suppressed.

[0054] In the present invention, the content mass ratio of the ultraviolet absorber (preferably an oil-soluble ultraviolet absorber) in the granular gel capsule of component (a1) to the total amount of ultraviolet absorbers in the external skin preparation [(a1) / (total ultraviolet absorbers)] is preferably 0.6 or more and 1 or less, more preferably 0.85 or more and 1 or less, even more preferably 0.9 or more and 1 or less, even more preferably 0.95 or more and 1 or less, even more preferably 0.99 or more and 1 or less, and particularly preferably 1, from the viewpoints of the fresh feeling at the initial stage of application, the moistness at the initial stage of application, and the ultraviolet protection effect. By increasing the content mass ratio [(a1) / (total ultraviolet absorbers)] in this manner, the fresh feeling at the initial stage of application, the moistness at the initial stage of application, and the ultraviolet protection effect can be further improved. In addition, a sticky or astringent feeling can be suppressed.

[0055] Furthermore, “the total amount of ultraviolet absorbers in the external preparation for skin” means the total amount of ultraviolet absorbers in the granular gel capsule and ultraviolet absorbers outside the granular gel capsule.

[0056] ((a2) Encapsulating agent)

[0057] As an encapsulating agent, it is preferred to contain a water-soluble non-crosslinked polymer. As such a water-soluble non-crosslinked polymer, for example, agar, carrageenan, gelatin, gellan gum, xanthan gum, high methoxyl pectin, etc. can be cited. Among these, as an encapsulating agent, from the viewpoints of a moist and refreshing good feeling of use, storage stability (stabilization of granular gel capsules), it is preferably one or more selected from agar, carrageenan and gelatin, particularly preferably agar. In addition, "agar" in this application refers to a hemicellulose containing galactan composed of 1,3 bonds and 1,4 bonds of galactose.

[0058] The gel strength of agar (Nikkansui method) is preferably 147 kPa (1500 g / cm 2 ) or less, more preferably 19.6 kPa (200 g / cm 2 ) and above 127kPa (1300g / cm 2 )the following.

[0059] The gel strength can be measured by preparing a 1.5% by mass aqueous solution of agar, leaving the aqueous solution at 20°C for 15 hours to solidify into a gel, cutting the gel into a size of 25 mm in length × width × height × 25 mm × 3 mm, applying a load to the cut gel using a Nissin water gel strength tester (manufactured by Kiya Manufacturing Co., Ltd.), and taking the load per 1 cm when the gel is subjected to the load for 20 seconds at 20°C as the gel strength. 2 The maximum mass (g) of the surface area is obtained.

[0060] Examples of commercially available agar include Ina agar PS-84, Z-10, AX-30, AX-100, AX-200, T-1, S-5, M-7, UP-16, CS-16A, CS-420, CS-670, and XY-908 (all manufactured by Ina Food Industry Co., Ltd.).

[0061] Carrageenan is a linear galactan composed of alternating α(1→3) and β(1→4) bonds. Some or all of the β(1→4)-linked galactose units exist as 3,6-anhydro-D-galactose and its sulfate esters. Carrageenan is classified by structure into κ-carrageenan, ι-carrageenan, and λ-carrageenan, and any of these can be used.

[0062] Gelatin is a modified protein made by making collagen, the main component of animal connective tissue, soluble with acid or alkali and then heating it.

[0063] Furthermore, the encapsulating agent may be used alone or in combination of two or more.

[0064] The content of the encapsulating agent in the granular gel capsule is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.15% by mass or more, and particularly preferably 0.2% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the perspectives of storage stability and initial moistness after application. Furthermore, from the perspectives of coating uniformity, UV protection effect, appearance during application, and ease of disintegration, the content is preferably 2% by mass or less, more preferably 1.75% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the content is preferably 0.05% by mass or more and 2% by mass or less, more preferably 0.1% by mass or more and 1.75% by mass or less, even more preferably 0.15% by mass or more and 1.5% by mass or less, and particularly preferably 0.2% by mass or more and 1% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0065] When the content of the encapsulating agent in the granular gel capsule is 1% by mass or less, the coating uniformity and the ultraviolet protection effect are particularly improved.

[0066] The content of the encapsulating agent in the granular gel capsule is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more, relative to the total mass of the granular gel capsule, from the viewpoint of storage stability, etc.; furthermore, from the viewpoint of coating uniformity, UV protection effect, and redispersibility (resistance to agglomeration), relative to the total mass of the granular gel capsule, it is preferably 10% by mass or less, more preferably 7.5% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2.5% by mass or less. Specifically, the content is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7.5% by mass or less, even more preferably 0.2% by mass or more and 5% by mass or less, even more preferably 0.4% by mass or more and 3% by mass or less, and particularly preferably 0.4% by mass or more and 2.5% by mass or less, relative to the total mass of the granular gel capsule.

[0067] When the encapsulating agent content in the granular gel capsules is set to 2.5% by mass or less, redispersibility is particularly improved (caking is less likely to occur), and even when the viscosity of the external skin preparation at 25°C is low, redispersibility (caking is less likely to occur) is good. Furthermore, coating uniformity and UV protection are improved.

[0068] The mass ratio of the encapsulating agent in the granular gel capsules of component (a2) to the ultraviolet absorber (preferably an oil-soluble ultraviolet absorber) in the granular gel capsules of component (a1) [(a2) / (a1)] is preferably 0.001 or more, more preferably 0.003 or more, even more preferably 0.005 or more, and particularly preferably 0.01 or more from the viewpoint of storage stability. Furthermore, from the viewpoints of coating uniformity, ultraviolet protection effect, and feel during use (less prone to dryness and crumbliness, soft and easily disintegrated), it is preferably 0.2 or less, more preferably 0.1 or less, even more preferably 0.08 or less, and particularly preferably 0.06 or less. Specifically, the range is preferably 0.001 or more and 0.2 or less, more preferably 0.003 or more and 0.1 or less, even more preferably 0.005 or more and 0.08 or less, and particularly preferably 0.01 or more and 0.06 or less.

[0069] The mass ratio of the total amount of the non-volatile oil in the granular gel capsule to the content of the encapsulating agent in the granular gel capsule as component (a2) [(total amount of the non-volatile oil in the granular gel capsule) / (a2)] is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, and particularly preferably 20 or more, from the viewpoint of smoothness during coating, etc.; and is preferably 105 or less, more preferably 95 or less, even more preferably 85 or less, and particularly preferably 75 or less, from the viewpoint of storage stability, etc. Specific ranges are preferably 5 or more and 105 or less, more preferably 10 or more and 95 or less, even more preferably 15 or more and 85 or less, and particularly preferably 20 or more and 75 or less.

[0070] ((a3) Water)

[0071] The water content in the granular gel capsule is preferably 5% by mass or more, more preferably 7.5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the viewpoints of a refreshing feel in the initial stage of application, moistness in the initial stage of application, and stability (gel stability). Furthermore, the water content is preferably 65% ​​by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly preferably 50% by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the water content is preferably 5% by mass or more and 65% by mass or less, more preferably 7.5% by mass or more and 60% by mass or less, even more preferably 10% by mass or more and 55% by mass or less, and particularly preferably 15% by mass or more and 50% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0072] The water content in the granular gel capsule is preferably 25% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly preferably 40% by mass or more, relative to the total mass of the granular gel capsule, from the viewpoints of a refreshing feel in the initial stage of application, moistness in the initial stage of application, and stability (gel stability). Furthermore, the water content is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, and particularly preferably 75% by mass or less, relative to the total mass of the granular gel capsule. Specifically, the water content is preferably 25% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 85% by mass or less, even more preferably 35% by mass or more and 80% by mass or less, and particularly preferably 40% by mass or more and 75% by mass or less, relative to the total mass of the granular gel capsule.

[0073] The mass ratio of the water content in the component (a3) ​​granular gel capsule to the ultraviolet absorber (preferably an oil-soluble ultraviolet absorber) in the component (a1) granular gel capsule [(a3) / (a1)] is preferably 0.25 or more, more preferably 0.5 or more, even more preferably 0.75 or more, and particularly preferably 1 or more from the viewpoint of stability (gel stability), etc.; and is preferably 5 or less, more preferably 4.5 or less, even more preferably 4 or less, and particularly preferably 3.5 or less from the viewpoint of coating uniformity, ultraviolet protection effect, emulsion stability, etc. Specifically, it is preferably 0.25 or more and 5 or less, more preferably 0.5 or more and 4.5 or less, even more preferably 0.75 or more and 4 or less, and particularly preferably 1 or more and 3.5 or less.

[0074] ((a4) Amphiphilic solid fat)

[0075] Examples of the amphiphilic solid fat include ceramides, alcohols having 12 to 22 carbon atoms, polyol mono-C12 to 22 fatty acid esters, and polyol mono-C12 to 22 alkyl ethers.

[0076] When the granular gel capsule contains an encapsulating agent and an amphiphilic solid fat, if the granular gel capsule disintegrates during coating, the amphiphilic solid fat forms a uniform coating film with the encapsulating agent as a foothold. When the granular gel capsule further contains an ultraviolet absorber, the ultraviolet protection effect is particularly good.

[0077] Examples of ceramides include one or more ceramides selected from natural ceramides and ceramide-like ceramides. From the perspective of storage stability (stabilization of the granular gel capsule) and lack of roughness, ceramides described in Japanese Patent Application Laid-Open No. 2013-53146 are preferred.

[0078] Specific examples of natural ceramides include ceramides Type 1 to 7 (e.g., J. Lipid Res., 24: 759 (1983)) obtained by amidating sphingosine, dihydrosphingosine, phytosphingosine, or sphingadienol. Figure 2 , and pig and human ceramides as shown in FIG4 of J. Lipid. Res., 35: 2069 (1994)).

[0079] Furthermore, these N-alkyl forms (eg, N-methyl forms) are also included in natural ceramides.

[0080] These ceramides may be used in their natural (D(-) form) optically active form, in their non-natural (L(+) form), or as a mixture of natural and non-natural forms. The relative configuration of the above compounds may be that of the natural form, other non-natural forms, or a mixture thereof.

[0081] Among natural ceramides, preferred are compounds of CERAMIDE 1, CERAMIDE 2, CERAMIDE 3, CERAMIDE 5, and CERAMIDE 6II (all listed in INCI, 8th Edition) and ceramides represented by the following formula.

[0082]

[0083] These may be either naturally derived extracts or synthetic products, and commercially available products may also be used.

[0084] Examples of commercially available natural ceramides include Ceramide I, Ceramide III, Ceramide IIIA, Ceramide IIIB, Ceramide IIIC, and Ceramide VI (all manufactured by COSMO FARM), Ceramide TIC-001 (manufactured by Takasago Fragrance Co., Ltd.), Ceramide II (manufactured by Quest International), DS-Ceramide VI, DS-CLA-phytoceramide, C6-phytoceramide, DS-ceramide Y3S (manufactured by DOOSAN), and Ceramide 2 (manufactured by Sederma).

[0085]

[0086] As the ceramide, from the viewpoint of storage stability (stabilization of the granular gel capsule) and absence of a rough texture, the ceramide represented by the following general formula (1) is preferred.

[0087]

[0088] [In formula (1),

[0089] R 1 represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms, which may be substituted by a hydroxy group, or a hydrogen atom;

[0090] X 1 represents a hydrogen atom, an acetyl group, or a glyceryl group;

[0091] R 2 represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 5 to 22 carbon atoms which may be substituted with a hydroxyl group or an amino group, or a group in which a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms which may be substituted with a hydroxyl group is ester-bonded to the ω terminal of the hydrocarbon group (preferably an alkyl group);

[0092] R 3 represents a hydrogen atom, or represents a hydrocarbon group having a total of 1 to 30 carbon atoms (the hydrocarbon group is preferably an alkyl group) which may be substituted by a hydroxyl group, a hydroxyalkoxy group, an alkoxy group, or an acetoxy group.]

[0093] Among the ceramide analogs, R in the general formula (1) is preferably 1 For hexadecyl, X 1 is a hydrogen atom, R 2 Pentadecyl, R 3 is a ceramide-like compound of hydroxyethyl; R in the general formula (1) 1 For hexadecyl, X 1 is a hydrogen atom, R 2 is nonyl, R 3 is a ceramide-like compound of hydroxyethyl; R in the general formula (1) 1 For hexadecyl, X 1 Glyceryl, R 2 For tridecyl, R 3 is a ceramide-like 3-methoxypropyl group; R in the general formula (1) 1 is a hydrogen atom, X 1 is a hydrogen atom, R 2 Pentadecyl, R 3 is a dodecyl-type ceramide; R in the general formula (1) 1 is a hydrogen atom, X 1 is a hydrogen atom, R 2 is 1-hydroxyheptyl, R 3 It is a lauryl-type ceramide.

[0094] More preferably, R in the general formula (1) 1 For hexadecyl, X 1 is a hydrogen atom, R 2 Pentadecyl, R 3is a ceramide-like compound of hydroxyethyl; R in the general formula (1) 1 For hexadecyl, X 1 is a hydrogen atom, R 2 is nonyl, R 3 is a ceramide-like compound of hydroxyethyl; R in the general formula (1) 1 For hexadecyl, X 1 Glyceryl, R 2 For tridecyl, R 3 It is a ceramide-like substance of 3-methoxypropyl.

[0095] In particular, R in the general formula (1) is preferably 1 For hexadecyl, X 1 is a hydrogen atom, R 2 Pentadecyl, R 3 It is a ceramide-like compound of hydroxyethyl (N-(hexadecyloxyhydroxypropyl)-N-hydroxyethyl hexadecylamide).

[0096]

[0097]

[0098] Furthermore, the alcohol having 12 to 22 carbon atoms is preferably a monohydric alcohol having 12 to 22 carbon atoms, more preferably a monohydric alcohol having 14 to 22 carbon atoms, further preferably a monohydric alcohol having 16 to 22 carbon atoms, and particularly preferably a monohydric alcohol having 16 to 18 carbon atoms. Furthermore, the alcohol having 12 to 22 carbon atoms may be linear or branched; and may be a saturated or unsaturated alcohol, preferably a linear saturated or unsaturated alcohol.

[0099] Examples of the alcohol having 12 to 22 carbon atoms include myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol. Among these, cetyl alcohol and stearyl alcohol are preferred.

[0100] Examples of the polyol mono-C12-22 fatty acid ester include glycerol mono-C12-22 fatty acid ester and sorbitan mono-C12-22 fatty acid ester.

[0101] The fatty acid residue of the polyol mono-C12-22 fatty acid ester is preferably a fatty acid residue having 14 to 22 carbon atoms, more preferably a fatty acid residue having 16 to 22 carbon atoms. The fatty acid residue may be a saturated fatty acid residue or an unsaturated fatty acid residue, and may be a straight-chain fatty acid residue or a branched-chain fatty acid residue.

[0102] Examples of glycerol mono-C12-22 fatty acid esters include glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, glycerol monostearate, glycerol monobehenate, glycerol monooleate, and glycerol monoisostearate. Among these, one or more selected from glycerol monopalmitate, glycerol monostearate, and glycerol monobehenate are preferred.

[0103] Examples of the sorbitan mono-C12-22 fatty acid esters include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monobehenate.

[0104] As the polyol mono-C12-22 alkyl ether, mono-C12-22 alkyl glyceryl ether is preferred, mono-C14-22 alkyl glyceryl ether is more preferred, and mono-C16-22 alkyl glyceryl ether is particularly preferred.

[0105] Examples of the mono-C12-22 alkyl glyceryl ether include monolauryl glyceryl ether, monomyristyl glyceryl ether, monocetyl glyceryl ether, monostearyl glyceryl ether, and monobehenyl glyceryl ether.

[0106] Among these components (a4), from the viewpoint of storage stability (stability of the granular gel capsule) and absence of astringent feeling, preferably, one or more kinds of components are selected from monohydric alcohols having 14 to 22 carbon atoms, glycerol mono-C14-22 fatty acid esters, sorbitan mono-C14-22 fatty acid esters, and mono-C14-22 alkyl glyceryl ethers; more preferably, one or more kinds of components are selected from monohydric alcohols having 16 to 22 carbon atoms, glycerol mono-C16-22 fatty acid esters, sorbitan mono-C16-22 fatty acid esters, and mono-C16-22 alkyl glyceryl ethers; further preferably, one or more kinds of components are selected from monohydric alcohols having 16 to 22 carbon atoms and glycerol mono-C16-22 fatty acid esters; and particularly preferably, one or more kinds of components are selected from cetyl alcohol, stearyl alcohol, and lipophilic glycerol monostearate.

[0107] When these are used as component (a4), the granular gel capsule can adopt an α-gel structure, thereby improving storage stability and further reducing the rough feeling.

[0108] Furthermore, the amphiphilic solid fat may be used alone or in combination of two or more.

[0109] The content of the amphiphilic solid fat in the granular gel capsule is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 1% by mass or more, and particularly preferably 1.25% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the perspectives of coating uniformity, UV protection effect, and storage stability (oil phase leakage). Furthermore, from the perspectives of storage stability and emulsification stability, it is preferably 12% by mass or less, more preferably 9% by mass or less, even more preferably 6% by mass or less, and particularly preferably 3% by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the content is preferably 0.1% by mass or more and 12% by mass or less, more preferably 0.3% by mass or more and 9% by mass or less, even more preferably 1% by mass or more and 6% by mass or less, and particularly preferably 1.25% by mass or more and 3% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0110] The content of the amphiphilic solid lipid in the granular gel capsule is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more, relative to the total mass of the granular gel capsule, from the perspectives of coating uniformity, UV protection effect, and storage stability. Furthermore, from the perspectives of storage stability and emulsion stability, the content is preferably 12.5% ​​by mass or less, more preferably 10% by mass or less, even more preferably 7.5% by mass or less, and particularly preferably 5% by mass or less, relative to the total mass of the granular gel capsule. Specifically, the content is preferably 0.1% by mass or more and 12.5% ​​by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, even more preferably 1% by mass or more and 7.5% by mass or less, and particularly preferably 2% by mass or more and 5% by mass or less, relative to the total mass of the granular gel capsule.

[0111] When the content of the amphiphilic solid fat in the granular gel capsule is 0.1% by mass or more, the coating uniformity can be further improved. When a UV absorber is combined, the distribution of the UV absorber is easily uniformized, and the UV protection effect is particularly improved.

[0112] The mass ratio of the amphiphilic solid fat in the component (a4) granular gel capsule to the ultraviolet absorber (preferably an oil-soluble ultraviolet absorber) in the component (a1) granular gel capsule [(a4) / (a1)] is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.05 or more from the viewpoints of coating uniformity and ultraviolet protection effect. Furthermore, from the viewpoints of emulsion stability and the absence of stickiness during coating, it is preferably 1.2 or less, more preferably 0.9 or less, even more preferably 0.3 or less, and particularly preferably 0.15 or less. Specifically, it is preferably 0.001 or more and 1.2 or less, more preferably 0.005 or more and 0.9 or less, even more preferably 0.01 or more and 0.3 or less, and particularly preferably 0.05 or more and 0.15 or less.

[0113] ((a5) Thickener)

[0114] Thickeners are broadly classified into (a5-1) oil-based thickeners and (a5-2) water-based thickeners.

[0115] Examples of the oily thickener include sugar fatty acid ester oily thickeners such as inulin fatty acid esters and dextrin fatty acid esters, as well as polyglyceryl isostearate, (behenic acid / eicosanedioic acid) glyceryl, and organically modified clay minerals. These may be used alone or in combination of two or more.

[0116] Among these, sugar fatty acid ester-based oily thickeners are preferred from the perspectives of coating uniformity and UV protection. The fatty acid residue in the sugar fatty acid ester-based oily thickener is preferably a linear or branched saturated fatty acid residue. Furthermore, the fatty acid residue preferably has 8 to 24 carbon atoms, more preferably 12 to 22, and particularly preferably 14 to 20 carbon atoms.

[0117] As the sugar fatty acid ester oily thickener, dextrin fatty acid ester is preferred, and specific examples include dextrin myristate, dextrin palmitate, dextrin stearate, dextrin (palmitic acid / 2-ethylhexanoate), and dextrin (palmitic acid / hexyldecanoate).

[0118] Examples of the aqueous thickener include dextrin, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, carboxyvinyl polymer, acrylic acid / alkyl acrylate copolymer, xanthan gum, carboxymethylchitin, and chitosan.

[0119] Among these, from the viewpoint of emulsion stability during production, at least one selected from polyvinyl alcohol and (meth)acrylic acid polymers is preferred, at least one selected from polyvinyl alcohol, carboxyvinyl polymers, and acrylic acid / alkyl acrylate copolymers is more preferred, and at least one selected from polyvinyl alcohol and (acrylic acid / alkyl (C10-30) acrylate) copolymers is particularly preferred.

[0120] Here, the (acrylic acid / alkyl acrylate (C10-30)) ester copolymer is a copolymer of alkyl acrylate (C10-30) ester and acrylic acid, methacrylic acid or these lower alkyl esters, which is cross-linked with allyl ether of sucrose or allyl ether of pentaerythritol. Commercially available products such as Pemulen TR-1 and Pemulen TR-2 (both manufactured by Lubrizol) can be used.

[0121] Acidic aqueous thickeners such as polyacrylic acid, carboxyvinyl polymer, and (acrylic acid / alkyl (C10-30) acrylate) copolymers can also be used as water-soluble or water-dispersible salts using alkali metal hydroxides such as potassium hydroxide and sodium hydroxide as neutralizers.

[0122] Among these components (a5), from the viewpoints of coating uniformity, UV protection effect, storage stability, etc., it is preferred to use at least an oily thickener, more preferably a combination of an aqueous thickener and an oily thickener, further preferably a combination of an aqueous thickener and a sugar fatty acid ester oily thickener, and particularly preferably a combination of one or more selected from polyvinyl alcohol and (meth)propionic acid polymers and a sugar fatty acid ester oily thickener.

[0123] When at least an oily tackifier is used as component (a5), the coating uniformity can be further improved. When a UV absorber is used in combination, the UV absorber is more easily distributed uniformly, and the UV protection effect is particularly improved.

[0124] In addition, when a water-based thickener and an oil-based thickener are used in combination, the mass ratio of the water-based thickener to the oil-based thickener [(water-based thickener) / (oil-based thickener)] is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and particularly preferably 0.3 or more from the perspectives of the emulsification stability and storage stability of the capsule. Furthermore, from the perspectives of the refreshing feeling in the initial stage of application, the moistness in the initial stage of application, and storage stability, it is preferably 1.5 or less, more preferably 1 or less, further preferably 0.75 or less, and particularly preferably 0.5 or less. As a specific range, it is preferably 0.01 or more and 1.5 or less, more preferably 0.05 or more and 1 or less, further preferably 0.1 or more and 0.75 or less, and particularly preferably 0.3 or more and 0.5 or less.

[0125] Furthermore, the thickener may be used alone or in combination of two or more.

[0126] When the granular gel capsules contain an encapsulating agent and an aqueous thickener, if the granular gel capsules disintegrate during application, the encapsulating agent acts as a base, and the aqueous thickener and fixed oil form a uniform coating film, providing a good, tight fit after application. When combined with a UV absorber, the UV protection effect is particularly good.

[0127] The content of the oily thickener in the granular gel capsule is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the perspectives of UV protection and capsule emulsion stability. Furthermore, from the perspectives of a refreshing feel in the initial stage of application and a lack of stickiness during application, the content is preferably 12% by mass or less, more preferably 9% by mass or less, even more preferably 6% by mass or less, and particularly preferably 2% by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the content is preferably 0.05% by mass or more and 12% by mass or less, more preferably 0.1% by mass or more and 9% by mass or less, even more preferably 0.3% by mass or more and 6% by mass or less, and particularly preferably 0.5% by mass or more and 2% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0128] The content of the oily thickener in the granular gel capsule is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 1.5% by mass or more, relative to the total mass of the granular gel capsule, from the perspectives of UV protection and capsule emulsion stability. Furthermore, from the perspectives of a refreshing feel in the initial stage of application and a lack of stickiness during application, the content is preferably 10% by mass or less, more preferably 7.5% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3.5% by mass or less, relative to the total mass of the granular gel capsule. Specifically, the content is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 7.5% by mass or less, even more preferably 1% by mass or more and 5% by mass or less, and particularly preferably 1.5% by mass or more and 3.5% by mass or less, relative to the total mass of the granular gel capsule.

[0129] The mass ratio of the thickener in the component (a5) granular gel capsule to the ultraviolet absorber (preferably an oil-soluble ultraviolet absorber) in the component (a1) granular gel capsule [(a5) / (a1)] is preferably 0.005 or more, more preferably 0.01 or more, even more preferably 0.03 or more, and particularly preferably 0.05 or more, from the viewpoints of the emulsification stability and storage stability of the capsule. Furthermore, from the viewpoints of a refreshing feeling in the initial stage of application and a lack of stickiness during application, it is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.3 or less, and particularly preferably 0.1 or less. Specifically, it is preferably 0.005 or more and 1 or less, more preferably 0.01 or more and 0.5 or less, even more preferably 0.03 or more and 0.3 or less, and particularly preferably 0.05 or more and 0.1 or less.

[0130] The content of the aqueous thickener (including polyvinyl alcohol) in the granular gel capsule is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the perspectives of capsule emulsion stability and gel strength. Furthermore, the content of the aqueous thickener (including polyvinyl alcohol) in the granular gel capsule is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less, from the perspectives of a refreshing feel during initial application and a lack of stickiness during application.

[0131] The content of the aqueous thickener (including polyvinyl alcohol) in the overall skin external preparation is preferably 0.6% by mass or less, more preferably 0.55% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, relative to the total mass of the skin external preparation of the present invention, from the viewpoints of forming a uniform coating film and providing a tight fit after application. Furthermore, the content of the aqueous thickener other than polyvinyl alcohol in the overall skin external preparation is preferably 0.3% by mass or less, more preferably 0.25% by mass or less, even more preferably 0.13% by mass or less, even more preferably 0.06% by mass or less, and even more preferably 0.03% by mass or less, relative to the total mass of the skin external preparation of the present invention, from the viewpoints of forming a uniform coating film and providing a tight fit after application.

[0132] ((a6) Polyol)

[0133] Examples of polyols include glycols and glycerols. Examples of glycols include alkylene glycols such as ethylene glycol, propylene glycol, and 1,3-butylene glycol; dialkylene glycols such as diethylene glycol and dipropylene glycol; and polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Examples of glycerols include glycerol, diglycerol, and polyglycerol.

[0134] Among these, glycerols are preferred, and glycerol is particularly preferred, from the viewpoints of storage stability (stabilization of the granular gel capsules) and smoothness during coating. When glycerols are used as component (a6), even if the content of the non-volatile oil (preferably an oil-soluble ultraviolet absorber) in the granular gel capsules is increased, excellent storage stability can be achieved.

[0135] Furthermore, the polyol may be used alone or in combination of two or more.

[0136] The content of the polyol in the granular gel capsule is preferably 0% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 3% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the perspective of storage stability (stabilization of the granular gel capsule). Furthermore, from the perspective of non-stickiness during application, it is preferably 16% by mass or less, more preferably 14% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the content is preferably 0% by mass or more and 16% by mass or less, more preferably 1% by mass or more and 14% by mass or less, even more preferably 2% by mass or more and 12% by mass or less, and particularly preferably 3% by mass or more and 10% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0137] The content of the polyol in the granular gel capsule is preferably 0% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 10% by mass or more, relative to the total mass of the granular gel capsule, from the viewpoint of storage stability (stabilization of the granular gel capsule). Furthermore, from the viewpoint of non-stickiness during application, it is preferably 30% by mass or less, more preferably 26% by mass or less, even more preferably 22% by mass or less, and particularly preferably 18% by mass or less, relative to the total mass of the granular gel capsule. Specifically, the content is preferably 0% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 26% by mass or less, even more preferably 3% by mass or more and 22% by mass or less, and particularly preferably 10% by mass or more and 18% by mass or less, relative to the total mass of the granular gel capsule.

[0138] The mass ratio of the polyol in the component (a6) granular gel capsule to the ultraviolet absorber (preferably an oil-soluble ultraviolet absorber) in the component (a1) granular gel capsule [(a6) / (a1)] is preferably 0 or more, more preferably 0.02 or more, even more preferably 0.05 or more, and particularly preferably 0.2 or more from the viewpoint of storage stability (stabilization of the granular gel capsule), and preferably 1.8 or less, more preferably 1.4 or less, even more preferably 1 or less, and particularly preferably 0.6 or less from the viewpoint of non-stickiness during application. Specifically, the range is preferably 0 or more and 1.8 or less, more preferably 0.02 or more and 1.4 or less, even more preferably 0.05 or more and 1 or less, and particularly preferably 0.2 or more and 0.6 or less.

[0139] ((a7) Powder)

[0140] Examples of the powder include ultraviolet scattering agents and powders other than ultraviolet scattering agents.

[0141] Among these, the powder contained in the granular gel capsule is preferably an ultraviolet scattering agent from the viewpoint of ultraviolet protection effect and the like.

[0142] Examples of the ultraviolet scattering agent include metal oxides such as titanium oxide, zinc oxide, and cerium oxide; and metals such as silicon and aluminum. Of these, metal oxides are preferred, and titanium oxide is particularly preferred.

[0143] The shape of the ultraviolet scattering agent is not particularly limited, and examples thereof include spherical, plate-like, rod-like, spindle-like, needle-like, and irregular shapes.

[0144] In addition, the average primary particle size of the ultraviolet scattering agent is preferably 0.005 to 0.5 μm, more preferably 0.007 to 0.2 μm, and particularly preferably 0.01 to 0.07 μm. Here, the average primary particle size of the ultraviolet scattering agent can be observed by a transmission electron microscope (TEM) at an observation magnification of 100,000 times, and the maximum minor diameter of 300 primary particles in the observed image is measured, and the number average value thereof is calculated and obtained. Here, the so-called maximum minor diameter refers to the minor diameter with the maximum length among the minor diameters orthogonal to the major diameter when the ultraviolet scattering agent has a shape other than a plate. In addition, when the ultraviolet scattering agent is plate-shaped, it is obtained by measuring the thickness of 300 primary particles in the observed image observed under the same conditions as above and calculating the number average value thereof.

[0145] As the ultraviolet scattering agent, a hydrophobized ultraviolet scattering agent is preferable.

[0146] Examples of hydrophobic treatments include fluorine compound treatments such as perfluoroalkyl phosphate treatment, perfluoroalkyl silane treatment, perfluoropolyether treatment, fluorosilicone treatment, and fluorinated silicone resin treatment; silicone treatments such as methylhydropolysiloxane treatment, dimethylpolysiloxane treatment, and fumed tetramethyltetrahydrocyclotetrasiloxane treatment; silicone resin treatments such as trimethylsiloxysilicic acid treatment; suspension treatment (a method of adding an alkyl chain after fumed silicone treatment); silane coupling agent treatment; titanium coupling agent treatment; silane treatments such as alkylsilane treatment, alkylalkoxysilane treatment (e.g., triethoxyoctylsilane treatment), fluoroalkylalkoxysilane treatment, and alkylsilazane treatment; oil treatment; N-acylated lysine treatment; polyacrylic acid treatment; metal soap treatments such as stearate treatment and myristate treatment; acrylic resin treatment; and metal oxide treatments such as hydrous silica treatment. A plurality of these treatments may also be used in combination. For example, there can be mentioned a method in which the surface of titanium oxide is coated with silane, aluminum oxide, or the like, and then surface-treated with alkylsilane or fatty acid.

[0147] Among these hydrophobic treatments, silicone treatment, silane treatment, metal soap treatment, metal oxide treatment, and the like are preferred.

[0148] Powders other than the ultraviolet scattering agent may be any of organic powders, inorganic powders, and organic-inorganic composite powders. Examples include hydrophobized talc, cellulose, silica (specifically, hydrophilic / hydrophobic, porous / non-porous silica), cross-linked (meth)acrylate resins, and silicone resins. These may be used alone or in combination of two or more.

[0149] The average particle size of the powder other than the ultraviolet scattering agent is preferably 0.1 to 30 μm, more preferably 0.5 to 25 μm, and particularly preferably 1 to 20 μm.

[0150] The average particle size of powders other than the ultraviolet scattering agent refers to the volume-based median particle size measured using a laser diffraction / scattering particle size distribution analyzer LA-960 (manufactured by HORIBA Corporation).

[0151] Furthermore, the powders may be used alone or in combination of two or more.

[0152] The powder content in the granular gel capsules is preferably from 0% to 40% by mass, more preferably from 0% to 30% by mass, even more preferably from 0% to 20% by mass, and particularly preferably from 0% to 10% by mass, relative to the total mass of the granular gel capsules, from the perspectives of a refreshing feel in the initial stage of application, moistness in the initial stage of application, and manufacturing efficiency. Even with such a low powder content in the granular gel capsules, the present invention can provide an excellent UV protection effect.

[0153] ((a8) Non-volatile oil (excluding oil-soluble UV absorbers, amphiphilic solid fats, and oily thickeners))

[0154] Examples of the nonvolatile oil agent of component (a8) include nonvolatile hydrocarbon oils such as hydrogenated polyisobutene, liquid paraffin, and vaseline; nonvolatile silicone oils such as nonvolatile dimethylpolysiloxane; nonvolatile fatty acid ester oils such as isopropyl myristate, isopropyl palmitate, tri(caprylic / capric)glyceryl, isononyl isononanoate, and esters of fatty acids and neopentyl glycol (e.g., neopentyl glycol dicaprate); and alkyl (C12-15) benzoate. Furthermore, nonvolatile animal oils and nonvolatile vegetable oils (e.g., olive oil) are also included in the nonvolatile oil agent.

[0155] The non-volatile oil agent of component (a8) may be used alone or in combination of two or more.

[0156] The content ratio of the non-volatile oil as component (a8) in the granular gel capsule is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 30% by mass or less, further preferably 0% by mass or more and 15% by mass or less, and particularly preferably 0% by mass or more and 5% by mass or less, relative to the total mass of the granular gel capsule.

[0157] Furthermore, in addition to the above-mentioned components, the granular gel capsule may contain an oil (excluding the oil-soluble ultraviolet absorber, amphiphilic solid fat, oily thickener, and component (a8)), a chelating agent, a dispersant, a preservative, and the like. These may be used alone or in combination of two or more.

[0158] The average particle size of the granular gel capsules is preferably 20 μm or greater, more preferably 30 μm or greater, even more preferably 40 μm or greater, even more preferably 60 μm or greater, and particularly preferably 80 μm or greater from the perspectives of storage stability (stabilization of the granular gel capsules), feel during use, manufacturing efficiency, and ease of disintegration of the granular gel capsules during application. Furthermore, from the perspectives of feel during application, it is preferably 350 μm or less, more preferably 300 μm or less, even more preferably 250 μm or less, and particularly preferably 200 μm or less. The specific range of the average particle size is preferably 20 μm or greater and 350 μm or less, more preferably 30 μm or greater and 300 μm or less, even more preferably 40 μm or greater and 300 μm or less, even more preferably 60 μm or greater and 250 μm or less, and particularly preferably 80 μm or greater and 200 μm or less.

[0159] When the average particle size of the granular gel capsules is 60 μm or more, the storage stability (stability of the granular gel capsules) is particularly improved.

[0160] The average particle size of the granular gel capsule refers to the volume-based median particle size with a refractive index of 1.20 measured using a laser diffraction / scattering particle size distribution analyzer LA-960 (manufactured by HORIBA Corporation).

[0161] From the viewpoint of ultraviolet protection effect, etc., the content of the granular gel capsule is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 22.5% by mass or more, even more preferably 27.5% by mass or more, even more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly preferably 40% by mass or more, relative to the total mass of the external skin preparation of the present invention. Furthermore, from the viewpoint of operability and spread during application, etc., the content of the granular gel capsule is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 72.5% by mass or less, and particularly preferably 70% by mass or less, relative to the total mass of the external skin preparation of the present invention. As a specific range, relative to the total mass of the skin external preparation of the present invention, it is preferably 15 mass% or more and 80 mass% or less, more preferably 20 mass% or more and 75 mass% or less, further preferably 22.5 mass% or more and 75 mass% or less, even more preferably 27.5 mass% or more and 72.5 mass% or less, even more preferably 30 mass% or more and 72.5 mass% or less, even more preferably 35 mass% or more and 70 mass% or less, and particularly preferably 40 mass% or more and 70 mass% or less.

[0162] <(B) Liquid>

[0163] The liquid in which the granular gel capsules are dispersed contains (b1) a volatile medium. Even when the granular gel capsules contain a volatile medium, (b1) the volatile medium refers to a volatile medium other than the granular gel capsules.

[0164] Here, in this specification, the phrase “having the granular gel capsules dispersed therein” includes a case where a part or all of the granular gel capsules are precipitated, provided that the granular gel capsules can be partially or entirely redispersed by stirring or shaking.

[0165] ((b1) Volatile medium)

[0166] Examples of the volatile medium (b1) contained in the liquid of component (B) include water and lower alcohols, such as ethanol and isopropyl alcohol.

[0167] The volatile medium may be used alone or in combination of two or more.

[0168] The content of the volatile medium (b1) in the liquid of component (B) is preferably 20% by mass or more, more preferably 23% by mass or more, even more preferably 26% by mass or more, and particularly preferably 30% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the viewpoints of a refreshing feel and moistness at the initial stage of application. Furthermore, the content is preferably 70% by mass or less, more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the content is preferably 20% by mass or more and 70% by mass or less, more preferably 23% by mass or more and 65% by mass or less, even more preferably 26% by mass or more and 60% by mass or less, and particularly preferably 30% by mass or more and 55% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0169] The content of the volatile medium (b1) in the liquid of component (B) is preferably 60% by mass or more, more preferably 75% by mass or more, even more preferably 85% by mass or more, and particularly preferably 95% by mass or more, relative to the total mass of the liquid of component (B), from the perspectives of a refreshing feel and moistness in the initial stage of application. Furthermore, it is preferably 100% by mass or less, relative to the total mass of the liquid of component (B). Specifically, the content is preferably 60% by mass or more and 100% by mass or less, more preferably 75% by mass or more and 100% by mass or less, even more preferably 85% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, relative to the total mass of the liquid of component (B).

[0170] When water is used as component (b1), the water content in the liquid of component (B) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 65% ​​by mass or more, relative to the total mass of the liquid of component (B), from the perspectives of a refreshing feeling in the initial stage of application and the degree of moisture in the initial stage of application. Furthermore, it is preferably 98% by mass or less, more preferably 95% by mass or less, further preferably 92% by mass or less, and particularly preferably 88% by mass or less, relative to the total mass of the liquid of component (B). Specifically, it is preferably 40% by mass or more and 98% by mass or less, more preferably 50% by mass or more and 95% by mass or less, further preferably 55% by mass or more and 92% by mass or less, and particularly preferably 65% ​​by mass or more and 88% by mass or less, relative to the total mass of the liquid of component (B).

[0171] When a lower alcohol is used as component (b1), the content of the lower alcohol in the liquid of component (B) is preferably 2% by mass or more, more preferably 4% by mass or more, further preferably 8% by mass or more, and particularly preferably 10% by mass or more, relative to the total mass of the liquid of component (B), from the viewpoints of a refreshing feel in the initial stage of application and a moistness in the initial stage of application. Furthermore, from the viewpoints of storage stability, etc., it is preferably 46% by mass or less, more preferably 42% by mass or less, further preferably 38% by mass or less, and particularly preferably 35% by mass or less, relative to the total mass of the liquid of component (B). Specifically, the content is preferably 2% by mass or more and 46% by mass or less, more preferably 4% by mass or more and 42% by mass or less, further preferably 8% by mass or more and 38% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less, relative to the total mass of the liquid of component (B).

[0172] ((b2) Cationic polymer)

[0173] The liquid component (B) preferably contains (b2) a cationic polymer in addition to (b1) a volatile medium. Even when the granular gel capsule contains a cationic polymer, (b2) the cationic polymer refers to a cationic polymer other than the granular gel capsule.

[0174] Generally speaking, when a skin external preparation contains silica, although the feeling during use is less likely to be sticky, there is a tendency for caking to occur. However, when the skin external preparation of the present invention contains silica as a powder of component (C) in addition to the granular gel capsule (A) and the liquid (B), and the liquid of component (B) contains the cationic polymer (b2), both the feeling during use and redispersibility (less likely to clumping) can be achieved.

[0175] As the cationic polymer, a silicone cationic polymer is preferably used. Examples thereof include poly(N-acylalkyleneimine)-modified silicones (e.g., oxazoline-modified silicones) and amino-modified silicones. Furthermore, one of these may be used alone or in combination of two or more.

[0176] Among these, poly(N-acylalkyleneimine)-modified silicone is preferred from the viewpoint of being less likely to cause blocking.

[0177] Examples of poly(N-acylalkyleneimine)-modified silicones include organopolysiloxanes in which a poly(N-acylalkyleneimine) segment composed of a repeating unit represented by the following general formula (11) is bonded to at least two silicon atoms of an organopolysiloxane segment constituting the main chain via a cationic divalent linking group (hereinafter, such organopolysiloxane may also be referred to as organopolysiloxane (OX)).

[0178] At least two poly(N-acylalkyleneimine) segments are bonded to any silicon atom constituting the organopolysiloxane segment via a cationic divalent linking group. Preferably, the poly(N-acylalkyleneimine) segments are bonded to one or more silicon atoms other than the two terminals of the organopolysiloxane segment via a cationic divalent linking group. More preferably, the poly(N-acylalkyleneimine) segments are bonded to two or more silicon atoms other than the two terminals via a cationic divalent linking group.

[0179]

[0180] (In formula (11), R 11 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group, or an aryl group, and t represents 2 or 3.

[0181] Furthermore, the cationic divalent linking group functions as a linking group of the poly(N-acylalkyleneimine) segment.

[0182] Examples of the cationic divalent linking group include an alkylene group having 2 to 20 carbon atoms and containing one to three or more cationic groups selected from primary amino groups, secondary amino groups, tertiary amino groups, and quaternary ammonium groups. Specifically, examples include a group represented by any of the following formulae (A1) to (A9), preferably a group represented by any of the formulae (A1) to (A4), and particularly preferably a group represented by the formulae (A1) or (A2).

[0183] Moreover, in the formula, An -represents a counter ion of a quaternary ammonium salt. Examples thereof include halide ions (e.g., chloride ions, iodide ions), sulfate ions, phosphate ions, acetate ions, lactate ions, p-toluenesulfonate ions, perchlorate ions, and monoalkyl nitrate ions (e.g., methylsulfate ions, ethylsulfate ions).

[0184]

[0185] In the N-acylalkyleneimine unit constituting the poly(N-acylalkyleneimine) segment, in the general formula (11), R 11 The number of carbon atoms in the alkyl group is 1 to 22, preferably 1 to 14, more preferably 1 to 6, and particularly preferably 1 to 3. Furthermore, the alkyl group may be linear or branched. Examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, and hexyl.

[0186] As R 11 The aralkyl group represented by is preferably an aralkyl group having 7 to 15 carbon atoms, and examples thereof include benzyl, phenethyl, trityl, naphthylmethyl, and anthracenylmethyl.

[0187] As R 11 The aryl group represented by is preferably an aryl group having 6 to 14 carbon atoms. Examples thereof include phenyl, tolyl, xylyl, naphthyl, biphenylyl, anthracenyl, and phenanthrenyl.

[0188] Among these, as R 11 , preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms.

[0189] In formula (11), t represents 2 or 3, and preferably 2.

[0190] In the organopolysiloxane (OX), the weight average molecular weight (hereinafter also referred to as "MWg") of the organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments is preferably 1,000 to 40,000, more preferably 1,500 to 30,000.

[0191] The molecular weight of the poly(N-acylalkyleneimine) segment can be calculated from the molecular weight of the N-acylalkyleneimine unit and the degree of polymerization, or can be measured by gel permeation chromatography (GPC). In this specification, it refers to the polystyrene-equivalent number average molecular weight (hereinafter also referred to as MNox) measured by GPC under the measurement conditions described below. MNox is preferably 500 to 4000.

[0192] MWg can be determined by the following formula (I) using the content (mass %) of the organopolysiloxane segment constituting the main chain (hereinafter also referred to as Csi).

[0193] MWg=Csi×MNox / (100-Csi)(I)

[0194] The weight average molecular weight (hereinafter also referred to as MWsi) of the organopolysiloxane segment constituting the main chain is preferably 10,000 to 200,000, more preferably 15,000 to 160,000.

[0195] Since the organopolysiloxane segments constituting the main chain share a common skeleton with the modified organopolysiloxane of the raw material compound, their MWsi is substantially the same as the weight-average molecular weight of the modified organopolysiloxane of the raw material compound. The weight-average molecular weight of the modified organopolysiloxane of the raw material compound is the weight-average molecular weight in terms of polystyrene as measured by GPC under the following measurement conditions.

[0196] (Measurement Conditions for Weight Average Molecular Weight of Modified Organopolysiloxane)

[0197] Column: Super HZ4000+Super HZ2000 (manufactured by Tosoh Corporation)

[0198] Eluent: 1 mM triethylamine / THF

[0199] Flow rate: 0.35mL / min

[0200] Column temperature: 40°C

[0201] Detector: UV

[0202] Sample: 50 μL

[0203] The weight average molecular weight (hereinafter also referred to as MWt) of the organopolysiloxane (OX) is preferably 10,000 to 500,000, more preferably 12,000 to 200,000. MWt refers to a value in terms of polystyrene measured by GPC under the measurement conditions described below.

[0204] (Measurement Conditions of MNox and MWt)

[0205] Column: Two K-804L (manufactured by Tosoh Corporation) connected in series

[0206] Eluent: 1 mM dimethyldodecylamine / chloroform

[0207] Flow rate: 1.0 mL / min

[0208] Column temperature: 40°C

[0209] Detector: RI

[0210] Sample: 50 μL

[0211] The mass ratio (a / b) of the organopolysiloxane segment (a) and the poly(N-acylalkyleneimine) segment (b) constituting the main chain is preferably 40 / 60 to 98 / 2, more preferably 45 / 55 to 82 / 18.

[0212] In this specification, the mass ratio (a / b) refers to the mass ratio of 5% by mass of organopolysiloxane (OX) dissolved in deuterated chloroform and analyzed by nuclear magnetic resonance ( 1 H-NMR) analysis, and a value determined from the integrated ratio of the alkyl group or phenyl group in the organopolysiloxane segment to the methylene group in the poly(N-acylalkyleneimine) segment.

[0213] Furthermore, when the poly(N-acylalkyleneimine) segment is a poly(N-propionylethyleneimine) segment, the mass ratio (a / b) is calculated as follows: 1 H-NMR measurement can be performed, for example, under the following conditions.

[0214] ( 1 H-NMR measurement conditions)

[0215] A solution prepared by dissolving 0.5 g of a polymer sample in 2 g of a measuring solvent (deuterated chloroform) was prepared by 1 The measurement was performed using H-NMR (400 MHz, manufactured by Varian), and the ratio of silicone to poly(N-propionylethyleneimine) was calculated from each integrated value.

[0216] PULSE SEQUENCE

[0217] Relaxation time delay (relax.delay): 30 seconds Pulse: 45 degrees Accumulation times: 8 times

[0218] Confirm the peak near 0ppm: methyl group of polydimethylsiloxane,

[0219] Around 3.4 ppm: methylene part of ethyleneimine.

[0220] The organopolysiloxane (OX) may be a synthetic product synthesized according to the methods described in JP-A-2008-143820, JP-A-2009-24114, JP-A-2015-67603, JP-A-2016-204336, etc. For example, it can be produced by reacting an organopolysiloxane modified with a functional group that can induce the above-mentioned cationic bivalent linking group with a terminally reactive poly(N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic imino ether corresponding to the repeating unit represented by general formula (11).

[0221] Specific examples of the poly(N-acylalkyleneimine)-modified silicone include modified silicones prepared according to the description of Synthesis Examples 1 and 2 in JP-A-2008-143820 and modified silicones prepared according to the description of Example 8 in JP-A-2009-24114.

[0222] Furthermore, the cationic polymer may be used alone or in combination of two or more.

[0223] The content of the cationic polymer (b2) in the liquid of component (B) is preferably 0% by mass or more, more preferably 0.005% by mass or more, further preferably 0.01% by mass or more, further more preferably 0.02% by mass or more, and particularly preferably 0.05% by mass or more, relative to the total mass of the external preparation for skin of the present invention, from the viewpoints of redispersibility (low agglomeration) and the durability of the ultraviolet protection effect. Furthermore, from the viewpoint of non-stickiness during application, it is preferably 1% by mass or less, more preferably 0.6% by mass or less, further preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less, relative to the total mass of the external preparation for skin of the present invention. Specifically, the content is preferably 0% by mass or more and 1% by mass or less, more preferably 0.005% by mass or more and 0.6% by mass or less, further preferably 0.01% by mass or more and 0.3% by mass or less, and particularly preferably 0.02% by mass or more and 0.1% by mass or less, relative to the total mass of the external preparation for skin of the present invention.

[0224] The content of the cationic polymer (b2) in the liquid of component (B) is preferably 0% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more, relative to the total mass of the liquid of component (B), from the viewpoints of redispersibility (low agglomeration) and the sustainability of the UV protection effect. Furthermore, from the viewpoint of non-stickiness during application, it is preferably 3% by mass or less, more preferably 1% by mass or less, further preferably 0.75% by mass or less, and particularly preferably 0.5% by mass or less, relative to the total mass of the liquid of component (B). Specifically, the content is preferably 0% by mass or more and 3% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less, further preferably 0.05% by mass or more and 0.75% by mass or less, and particularly preferably 0.1% by mass or more and 0.5% by mass or less, relative to the total mass of the liquid of component (B).

[0225] The liquid of component (B) may contain, in addition to the above-mentioned components, a bactericide, a moisturizer, etc. In addition, these may be used alone or in combination of two or more.

[0226] The total content of the liquid component (B) is preferably 20% by mass or more, more preferably 24% by mass or more, even more preferably 27% by mass or more, and particularly preferably 30% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the viewpoint of operability, etc.; and preferably 85% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the total content is preferably 20% by mass or more and 85% by mass or less, more preferably 24% by mass or more and 75% by mass or less, even more preferably 27% by mass or more and 70% by mass or less, and particularly preferably 30% by mass or more and 65% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0227] The mass ratio of the content of the granular gel capsule of component (A) to the liquid of component (B) [(A) / (B)] is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.4 or more, and particularly preferably 0.5 or more, from the viewpoints of coating uniformity and UV protection effect. Furthermore, from the viewpoints of the refreshing feeling and moistness in the initial stage of application, it is preferably 3.5 or less, more preferably 3 or less, even more preferably 2.5 or less, and particularly preferably 2 or less. Specifically, it is preferably 0.1 or more and 3.5 or less, more preferably 0.2 or more and 3 or less, even more preferably 0.4 or more and 2.5 or less, and particularly preferably 0.5 or more and 2 or less.

[0228] The content of the non-volatile oil in the liquid component (B) is from 0% to 14% by mass relative to the total mass of the external skin preparation of the present invention. By setting the content of the non-volatile oil to from 0% to 14% by mass, a refreshing and smooth feel can be achieved during the initial application.

[0229] The content of the non-volatile oil in the liquid as component (B) is preferably from 0% by mass to 10% by mass, more preferably from 0% by mass to 5% by mass, further preferably from 0% by mass to 1% by mass, and particularly preferably from 0% by mass to 0% by mass, relative to the total mass of the external skin preparation of the present invention, from the viewpoints of a refreshing feel in the initial stage of application and smoothness during application.

[0230] The content of the non-volatile oil in the liquid component (B) is preferably from 0% by mass to 25% by mass, more preferably from 0% by mass to 15% by mass, even more preferably from 0% by mass to 5% by mass, and particularly preferably from 0% by mass to 0% by mass, relative to the total mass of the liquid component (B), from the viewpoints of a fresh feel in the initial stage of application and moistness in the initial stage of application.

[0231] Furthermore, the mass ratio of the total non-volatile oil content in the liquid of component (B) to the total non-volatile oil content in the granular gel capsules [(total non-volatile oil content in the liquid) / (total non-volatile oil content in the granular gel capsules)] is preferably 0 or more and 0.1 or less, more preferably 0 or more and 0.06 or less, even more preferably 0 or more and 0.01 or less, and particularly preferably 0, from the viewpoints of the refreshing feeling in the initial stage of application and the moistness in the initial stage of application.

[0232] Here, the term "non-volatile oil" refers to an oily component that is non-volatile at 25°C under 1 atmosphere. Examples include non-volatile oil-soluble UV absorbers, non-volatile amphiphilic solid fats, and non-volatile oily thickeners. Examples of non-volatile oils include non-volatile hydrocarbon oils such as hydrogenated polyisobutene, liquid paraffin, and petrolatum; non-volatile silicone oils such as non-volatile dimethylpolysiloxane; non-volatile fatty acid ester oils such as isopropyl myristate, isopropyl palmitate, tri(caprylic / capric)glyceryl, isononyl isononanoate, and esters of fatty acids with neopentyl glycol (e.g., neopentyl glycol dicaprate); and C12-15 alkyl benzoates. Non-volatile animal oils and non-volatile vegetable oils (such as olive oil) are also included in non-volatile oils.

[0233] The content of the aqueous thickener in the liquid component (B) is from 0% to 0.25% by mass relative to the total mass of the external skin preparation of the present invention. By setting the content of the aqueous thickener to from 0% to 0.25% by mass, the refreshing feeling and moistness of the product in the initial stage of application can be improved.

[0234] The content of the aqueous thickener in the liquid as component (B) is preferably from 0% by mass to 0.03% by mass, more preferably from 0% by mass to 0.015% by mass, even more preferably from 0% by mass to 0.005% by mass, and particularly preferably 0% by mass, relative to the total mass of the external skin preparation of the present invention, from the viewpoints of the refreshing feeling and moistness in the initial stage of application.

[0235] The content of the aqueous thickener in the liquid of component (B) is preferably from 0% by mass to 0.05% by mass, more preferably from 0% by mass to 0.03% by mass, even more preferably from 0% by mass to 0.01% by mass, and particularly preferably 0% by mass, relative to the total mass of the liquid of component (B), from the viewpoints of a refreshing feel in the initial stage of application and a moistness in the initial stage of application.

[0236] Examples of the "aqueous thickener" include the same aqueous thickeners as those that may be contained in the granular gel capsule.

[0237] The content of the oily thickener in the liquid as component (B) is preferably from 0% by mass to 0.03% by mass, more preferably from 0% by mass to 0.015% by mass, even more preferably from 0% by mass to 0.005% by mass, and particularly preferably 0% by mass, relative to the total mass of the external skin preparation of the present invention, from the viewpoints of UV protection effect, fresh feeling at the initial stage of application, and moistness at the initial stage of application.

[0238] The above-mentioned "oil-based thickener" is a thickener other than the aqueous thickener, and examples thereof include the same oil-based thickeners as those that may be contained in the granular gel capsule.

[0239] The content of the emulsifier in the liquid as component (B) is preferably from 0% by mass to 0.4% by mass, more preferably from 0% by mass to 0.2% by mass, even more preferably from 0% by mass to 0.1% by mass, and particularly preferably 0% by mass, relative to the total mass of the external skin preparation of the present invention, from the viewpoints of the refreshing feeling in the initial stage of application, the moistness in the initial stage of application, the emulsion stability, the water resistance, and the like.

[0240] The content of the emulsifier in the liquid of component (B) is preferably from 0% by mass to 0.8% by mass, more preferably from 0% by mass to 0.4% by mass, even more preferably from 0% by mass to 0.2% by mass, and particularly preferably 0% by mass, relative to the total mass of the liquid of component (B), from the viewpoints of a refreshing feel in the initial stage of application, moistness in the initial stage of application, emulsion stability, water resistance, and the like.

[0241] Examples of the "emulsifier" include various surfactants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc.) such as polyoxyethylene hydrogenated castor oil and sorbitan monostearate.

[0242] The total content of the non-volatile oil, aqueous thickener, and emulsifier in the liquid as component (B) is preferably from 0% by mass to 12% by mass, more preferably from 0% by mass to 5% by mass, further preferably from 0% by mass to 0.001% by mass, and particularly preferably from 0% by mass to 0.001% by mass, relative to the total mass of the external skin preparation of the present invention, from the viewpoints of the fresh feeling in the initial stage of application, the moistness in the initial stage of application, the UV protection effect, the emulsion stability, and the like.

[0243] The nonvolatile oil, aqueous thickener, and emulsifier in the liquid of component (B) refer to the nonvolatile oil, aqueous thickener, and emulsifier in the liquid of component (B) and outside the granular gel capsule, respectively.

[0244] <(C) Powder>

[0245] The skin external preparation of the present invention preferably contains (C) a powder in addition to the granular gel capsule (A) and the liquid (B) from the viewpoint of improving the feel during use. More preferably, the components (A) and (C) are dispersed in the liquid of the component (B).

[0246] The powder of component (C) may be the same powder as that which may be contained in the granular gel capsule from the viewpoint of non-stickiness and smoothness, but is preferably a powder other than the ultraviolet scattering agent, more preferably cellulose or silica, further preferably silica, and particularly preferably porous silica.

[0247] The average particle size of the powder other than the ultraviolet scattering agent is preferably 0.1 to 30 μm, more preferably 0.5 to 25 μm, and particularly preferably 1 to 20 μm from the viewpoints of redispersibility (low agglomeration), ultraviolet protection effect, and lack of stickiness.

[0248] The average particle size of powders other than the ultraviolet scattering agent refers to the volume-based median particle size measured using a laser diffraction / scattering particle size distribution analyzer LA-960 (manufactured by HORIBA Corporation).

[0249] The content of the powder of component (C) is preferably 0.05% by mass or more, more preferably 0.2% by mass or more, further preferably 0.6% by mass or more, and particularly preferably 1% by mass or more, relative to the total mass of the external skin preparation of the present invention, from the viewpoints of non-stickiness and smoothness. Furthermore, from the viewpoints of ultraviolet protection effect and storage stability, it is preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 9% by mass or less, and particularly preferably 6% by mass or less, relative to the total mass of the external skin preparation of the present invention. Specifically, the content is preferably 0.05% by mass or more and 15% by mass or less, more preferably 0.2% by mass or more and 12% by mass or less, further preferably 0.6% by mass or more and 9% by mass or less, and particularly preferably 1% by mass or more and 6% by mass or less, relative to the total mass of the external skin preparation of the present invention.

[0250] In addition, when components (b2) and (C) are used in combination, the mass ratio of the content of the cationic polymer (b2) in the liquid of component (B) to the powder of component (C) [(b2) / (C)] is preferably 0.001 or more, more preferably 0.004 or more, further preferably 0.007 or more, and particularly preferably 0.01 or more from the viewpoints of redispersibility (low agglomeration), storage stability, persistence of the ultraviolet protection effect, and suppression of deterioration of the appearance of the external preparation for skin application by emulsifying the oil exuded from the capsule. Furthermore, from the viewpoints of storage stability and lack of stickiness during application, it is preferably 1 or less, more preferably 0.5 or less, further preferably 0.3 or less, and particularly preferably 0.1 or less. Specific ranges are preferably 0.001 or more and 1 or less, more preferably 0.004 or more and 0.5 or less, further preferably 0.007 or more and 0.3 or less, and particularly preferably 0.01 or more and 0.1 or less.

[0251] The viscosity of the skin external preparation of the present invention at 25°C is preferably 10 mPa·s or higher, more preferably 20 mPa·s or higher, even more preferably 25 mPa·s or higher, and particularly preferably 30 mPa·s or higher, from the perspective of preventing dripping. Furthermore, from the perspective of initial feel (refreshing feeling and moistness) after application, UV protection effect, and spread during application, it is preferably 10,000 mPa·s or lower, more preferably 5,000 mPa·s or lower, even more preferably 1,000 mPa·s or lower, and particularly preferably 500 mPa·s or lower. Specifically, the viscosity is preferably 10 mPa·s or higher and 10,000 mPa·s or lower, more preferably 20 mPa·s or higher and 5,000 mPa·s or lower, even more preferably 25 mPa·s or higher and 1,000 mPa·s or lower, and particularly preferably 30 mPa·s or higher and 500 mPa·s or lower.

[0252] When the viscosity at 25° C. is 10,000 mPa·s or less, the feeling of use (refreshing feeling and moistness) is improved particularly in the initial stage of application.

[0253] The viscosity at 25° C. can be measured with a Brookfield viscometer (B-type viscometer).

[0254] The pH of the skin external preparation of the present invention at 25°C is preferably 4 to 10, more preferably 4.5 to 9, and particularly preferably 5 to 8, from the viewpoint of storage stability (stabilization of the granular gel capsule).

[0255] When the pH at 25° C. is set to 4.5 or higher, storage stability is particularly improved.

[0256] Examples of the liquid form of the skin external preparation of the present invention and component (B) include emulsified compositions (oil-in-water emulsified compositions, water-in-oil emulsified compositions) and aqueous compositions. From the viewpoint of feel during use, aqueous compositions are preferred.

[0257] The external preparation for skin of the present invention can be produced by appropriately combining the methods described in JP-A-2012-171891, JP-A-2012-171892, JP-A-2014-91737, JP-A-2016-104712, and the like.

[0258] For example, when producing a granular gel capsule for external use on the skin containing an encapsulating agent and water in addition to a non-volatile oil, the following method can be used. Specifically, the encapsulating agent and water are mixed, heated to a temperature above the dissolution temperature of the encapsulating agent to prepare an aqueous phase component. This aqueous phase component is then mixed with a separately prepared oil phase component containing a non-volatile oil to prepare a mixed solution. The resulting mixed solution is then added dropwise, sprayed, or stirred to produce the granular gel capsule. The resulting granular gel capsule is then mixed with a volatile medium to produce the external use on the skin.

[0259] Furthermore, the skin external preparation of the present invention has an excellent feeling of use such as a refreshing feeling in the initial stage of application, and can form a good coating film of a non-volatile oil such as an oil-soluble ultraviolet absorber.

[0260] The present inventors speculate that the reason for these effects is that by setting the non-volatile oil content in the granular gel capsules to 1.5% by mass or more relative to the total mass of the skin external preparation, setting the non-volatile oil content in the liquid component (B) to 0% to 14% by mass relative to the total mass of the skin external preparation, and setting the aqueous thickener content in the liquid component (B) to 0% to 0.25% by mass relative to the total mass of the skin external preparation, a good refreshing feeling is achieved in the initial stage of application. Furthermore, the distribution of the non-volatile oil, such as an oil-soluble UV absorber, is easily uniformed. When the non-volatile oil in the granular gel capsules contains an oil-soluble UV absorber, an excellent UV protection effect is achieved. Furthermore, since the granular gel capsules disintegrate during application to form a coating film, a good, close-fitting feel is easily achieved even in the later stages of application, resulting in a characteristic feel of freshness in the initial stage of application and a good, close-fitting feel in the later stages of application.

[0261] Therefore, the skin preparation of the present invention is useful as a cosmetic (e.g., sunscreen, foundation, primer, lotion), and is particularly useful as a sunscreen. The skin preparation of the present invention can be applied to the skin (preferably skin other than the scalp, more preferably the face, body, hands, feet, etc.) using a method appropriate to the dosage form and used as a sunscreen. While the method of application is not particularly limited, application is preferably by hand or with an applicator.

[0262] Furthermore, the aforementioned "refreshing feeling" refers to a water-like, refreshing feeling upon application. For example, if a skin external preparation is applied to the skin and spreads smoothly with the hands, for example, and a refreshing feeling is achieved, the initial feeling of freshness can be considered excellent. Furthermore, if the skin external preparation exhibits a water-drop-like appearance due to a large contact angle with the skin when applied to the skin, this refreshing feeling is further enhanced.

[0263] Furthermore, the tight fit at the end of application can be confirmed by detecting whether the angular velocity Gx in the twisting direction of the finger significantly increases during application using an inertial sensor such as that described in Japanese Patent Application Laid-Open No. 2018-109599.

[0264] Regarding the above-mentioned embodiment, the present invention further discloses the following external skin preparations and the like.

[0265] <1> A skin external preparation comprising a granular gel capsule containing a non-volatile oil and a liquid containing the following components (b1): (b1) a volatile medium,

[0266] The granular gel capsules are dispersed in the liquid,

[0267] The content of the non-volatile oil in the granular gel capsule is 1.5% by mass or more relative to the total mass of the external preparation for skin application.

[0268] The content of the non-volatile oil in the liquid is 0% by mass or more and 14% by mass or less relative to the total mass of the external preparation for skin,

[0269] The content of the aqueous thickener in the liquid is 0% by mass or more and 0.25% by mass or less relative to the total mass of the external preparation for skin.

[0270] <2> like <1> In the aforementioned external preparation for skin, the granular gel capsule is preferably a granular hydrogel capsule, more preferably a granular hydrogel capsule in which an oil phase containing a non-volatile oil agent is dispersed in a hydrogel, further preferably a granular hydrogel capsule in which an oil phase containing an oil-soluble ultraviolet absorber is dispersed in a hydrogel, and particularly preferably a granular hydrogel capsule comprising a continuous phase of a non-crosslinked hydrogel and an oil phase dispersed in the continuous phase, wherein the oil phase contains an oil-soluble ultraviolet absorber.

[0271] <3> like <1> or <2> The above-mentioned external preparation for skin, wherein the granular gel capsule preferably contains one or more selected from the group consisting of (a1) an ultraviolet absorber (preferably an oil-soluble ultraviolet absorber), (a4) an amphiphilic solid fat, (a5-1) an oily thickener, and (a8) a non-volatile oil agent (excluding oil-soluble ultraviolet absorbers, amphiphilic solid fats, and oily thickeners) as the non-volatile oil agent, more preferably contains at least (a1) an oil-soluble ultraviolet absorber as the non-volatile oil agent, further preferably contains (a1) an oil-soluble ultraviolet absorber and one or more selected from (a4) an amphiphilic solid fat, and (a5-1) an oily thickener as the non-volatile oil agent, and particularly preferably contains (a1) an oil-soluble ultraviolet absorber, (a4) an amphiphilic solid fat, and (a5-1) an oily thickener as the non-volatile oil agent.

[0272] <4> like <3> The skin external preparation, wherein component (a1) is preferably one or more selected from benzoic acid ultraviolet absorbers, anthranilic acid ultraviolet absorbers, salicylic acid ultraviolet absorbers, cinnamic acid ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers and silicone ultraviolet absorbers, more preferably one or more selected from benzoic acid ultraviolet absorbers, cinnamic acid ultraviolet absorbers and triazine ultraviolet absorbers, further preferably selected from para-aminobenzoic acid (para-aminobenzoic acid PABA), PABA glyceride, PABA ethyl dihydroxypropyl ester, N-ethoxylated PABA ethyl ester, N-dimethyl PABA ethyl ester, N-dimethyl PABA butyl ester, N-dimethyl PABA amyl ester, PABA octyl dimethyl ester, diethylamino hydroxybenzoyl hexyl benzoate, octyl cinnamate, 4-isopropyl ethyl cinnamate, 2,4-diisopropyl ethyl cinnamate, 2,4-diisopropyl methyl cinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, p-methoxycinnamate One or more of 2-ethylhexyl cinnamate, 2-ethoxyethyl p-methoxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α-cyano-β-phenyl cinnamate, 2-ethylhexyl α-cyano-β-phenyl cinnamate, glycerol mono-2-ethylhexanoyl di-p-methoxycinnamate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, dioctylbutyramidotriazinone, and 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine.

[0273] <5> like <3> or <4> The skin external preparation, wherein the content of component (a1) (preferably an oil-soluble ultraviolet absorber) is preferably 1.5 mass% or more, more preferably 3 mass% or more, further preferably 6 mass% or more, further more preferably 9 mass% or more, and particularly preferably 12 mass% or more, relative to the total mass of the skin external preparation; and further, relative to the total mass of the skin external preparation, is preferably 40 mass% or less, more preferably 35 mass% or less, further preferably 30 mass% or less, and particularly preferably 25 mass% or less.

[0274] <6> like <3> ~ <5> The skin external preparation described in any one of the preceding claims, wherein the content of component (a1) (preferably an oil-soluble ultraviolet absorber) is preferably 1.5% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 40% by mass or less, further preferably 6% by mass or more and 35% by mass or less, further more preferably 9% by mass or more and 30% by mass or less, and particularly preferably 12% by mass or more and 25% by mass or less, relative to the total mass of the skin external preparation.

[0275] <7> like <3> ~ <6> The skin external preparation according to any one of the preceding claims, wherein the content ratio of component (a1) (preferably an oil-soluble ultraviolet absorber) is preferably 15 mass% or more, more preferably 17 mass% or more, further preferably 19 mass% or more, and particularly preferably 22 mass% or more, relative to the total mass of the granular gel capsule; and is preferably 54 mass% or less, more preferably 48 mass% or less, further preferably 42 mass% or less, and particularly preferably 40 mass% or less, relative to the total mass of the granular gel capsule.

[0276] <8> like <3> ~ <7> The skin external preparation according to any one of the preceding claims, wherein the content mass ratio of the ultraviolet absorber (preferably an oil-soluble ultraviolet absorber) in the granular gel capsule of component (a1) to the total ultraviolet absorbers in the skin external preparation [(a1) / (total ultraviolet absorbers)] is preferably 0.6 or more and 1 or less, more preferably 0.85 or more and 1 or less, further preferably 0.9 or more and 1 or less, further more preferably 0.95 or more and 1 or less, further more preferably 0.99 or more and 1 or less, and particularly preferably 1.

[0277] <9> like <1> ~ <8> The skin external preparation according to any one of the preceding claims, wherein the granular gel capsule preferably contains one or more selected from the group consisting of (a1) an ultraviolet absorber (preferably an oil-soluble ultraviolet absorber), (a2) an encapsulating agent, (a3) ​​water, (a4) an amphiphilic solid fat, (a5) a thickener (as the thickener (a5), there are (a5-1) an oily thickener and (a5-2) an aqueous thickener), (a6) a polyol, (a7) a powder, and (a8) a non-volatile oil (excluding oil-soluble ultraviolet absorbers, amphiphilic solid fats, and oily thickeners). It is more preferred that the granular gel capsule contains (a1) an ultraviolet absorber (preferably an oil-soluble ultraviolet absorber). It is further preferred that the granular gel capsule contains, in addition to the (a1) ultraviolet absorber (preferably an oil-soluble ultraviolet absorber), The composition comprises one or more components selected from (a2) an encapsulating agent, (a3) ​​water, (a4) an amphiphilic solid fat, (a5) a thickener, (a6) a polyol, (a7) a powder, and (a8) a non-volatile oil (excluding an oil-soluble ultraviolet absorber, an amphiphilic solid fat, and an oily thickener). It further preferably contains components (a1) to (a2), further more preferably contains components (a1) to (a3), further more preferably contains components (a1) to (a4), further more preferably contains components (a1) to (a5), further more preferably contains components (a1) to (a5) and one or more components selected from (a6) and (a7), further more preferably contains components (a1) to (a6), and particularly preferably contains components (a1) to (a7).

[0278] <10> like <9> The above-mentioned external preparation for skin, wherein the granular gel capsule preferably comprises component (a1) dispersed in a gel-like encapsulating agent, more preferably comprises components (a1) and (a3) ​​dispersed in a gel-like encapsulating agent, further preferably comprises components (a1), (a3) ​​and (a4) dispersed in a gel-like encapsulating agent, further more preferably comprises component (a1) and components (a3) ​​to (a5) dispersed in a gel-like encapsulating agent, further more preferably comprises component (a1), components (a3) ​​to (a5) and one or more selected from components (a6) and (a7) dispersed in a gel-like encapsulating agent, further more preferably comprises component (a1) and components (a3) ​​to (a6) dispersed in a gel-like encapsulating agent, and particularly preferably comprises component (a1) and components (a3) ​​to (a7) dispersed in a gel-like encapsulating agent.

[0279] <11> like <9> or <10> In the aforementioned external skin preparation, the encapsulating agent as component (a2) is preferably one or more selected from agar, carrageenan, and gelatin, and more preferably agar.

[0280] <12> like <9> ~ <11> The skin external preparation described in any one of the preceding claims, wherein the content of component (a2) is preferably 0.05 mass % or more, more preferably 0.1 mass % or more, further preferably 0.15 mass % or more, and particularly preferably 0.2 mass % or more, relative to the total mass of the skin external preparation; and further, preferably 2 mass % or less, more preferably 1.75 mass % or less, further preferably 1.5 mass % or less, and particularly preferably 1 mass % or less, relative to the total mass of the skin external preparation.

[0281] <13> like <9> ~ <12> The skin external preparation described in any one of the preceding claims, wherein the content ratio of component (a2) is preferably 0.05 mass% or more, more preferably 0.1 mass% or more, further preferably 0.2 mass% or more, and particularly preferably 0.4 mass% or more, relative to the total mass of the granular gel capsule; and further, preferably 10 mass% or less, more preferably 7.5 mass% or less, further preferably 5 mass% or less, further more preferably 3 mass% or less, and particularly preferably 2.5 mass% or less, relative to the total mass of the granular gel capsule.

[0282] <14> like <9> ~ <13> The skin external preparation described in any one of the preceding claims, wherein the content mass ratio [(a2) / (a1)] of the encapsulating agent in the component (a2) granular gel capsule to the ultraviolet absorber (preferably an oil-soluble ultraviolet absorber) in the component (a1) granular gel capsule is preferably 0.001 or more, more preferably 0.003 or more, further preferably 0.005 or more, and particularly preferably 0.01 or more; and is preferably 0.2 or less, more preferably 0.1 or less, further preferably 0.08 or less, and particularly preferably 0.06 or less.

[0283] <15> like <9> ~ <14> The skin external preparation described in any one of the preceding claims, wherein the mass ratio of the total non-volatile oil in the granular gel capsule to the encapsulating agent in the component (a2) granular gel capsule [(total non-volatile oil in the granular gel capsule) / (a2)] is preferably 5 or more, more preferably 10 or more, further preferably 15 or more, and particularly preferably 20 or more; and is preferably 105 or less, more preferably 95 or less, further preferably 85 or less, and particularly preferably 75 or less.

[0284] <16> like <3> ~ <15> The skin external preparation according to any one of the preceding claims, wherein the component (a4) is preferably one or more selected from the group consisting of ceramides, alcohols having 12 to 22 carbon atoms, polyol mono-C12-22 fatty acid esters, and polyol mono-C12-22 alkyl ethers, more preferably one or more selected from the group consisting of alcohols having 12 to 22 carbon atoms, polyol mono-C12-22 fatty acid esters, and polyol mono-C12-22 alkyl ethers, and further preferably one or more selected from the group consisting of monohydric alcohols having 14 to 22 carbon atoms, glycerol mono-C14-22 fatty acid esters, sorbitan mono-C14 More preferably, it is one or more kinds selected from monohydric alcohols having 16 to 22 carbon atoms, glycerol mono-C16-22 fatty acid esters, sorbitan mono-C16-22 fatty acid esters and mono-C16-22 alkyl glyceryl ethers. More preferably, it is one or more kinds selected from monohydric alcohols having 16 to 22 carbon atoms and glycerol mono-C16-22 fatty acid esters, and particularly preferably, it is one or more kinds selected from cetyl alcohol, stearyl alcohol and lipophilic glycerol monostearate.

[0285] <17> like <3> ~ <16> The skin external preparation described in any one of the preceding claims, wherein the content of component (a4) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 1% by mass or more, and particularly preferably 1.25% by mass or more, relative to the total mass of the skin external preparation; and further, preferably 12% by mass or less, more preferably 9% by mass or less, further preferably 6% by mass or less, and particularly preferably 3% by mass or less, relative to the total mass of the skin external preparation.

[0286] <18> like <3> ~ <17> The skin external preparation described in any one of the preceding claims, wherein the content ratio of component (a4) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 2% by mass or more, relative to the total mass of the granular gel capsule; and is preferably 12.5% ​​by mass or less, more preferably 10% by mass or less, further preferably 7.5% by mass or less, and particularly preferably 5% by mass or less, relative to the total mass of the granular gel capsule.

[0287] <19> like <9> ~ <18> In any one of the external preparations for skin, component (a5) is preferably one or more selected from aqueous thickeners and oily thickeners.

[0288] <20> like <19> The described external skin preparation, wherein the aqueous thickener is preferably one or more selected from dextrin, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, carboxyvinyl polymer, acrylic acid / alkyl acrylate copolymer, xanthan gum, carboxymethyl chitin, and chitosan, more preferably one or more selected from polyvinyl alcohol and (meth)acrylic acid polymers, further preferably one or more selected from polyvinyl alcohol, carboxyvinyl polymer and acrylic acid / alkyl acrylate copolymer, particularly preferably one or more selected from polyvinyl alcohol and (acrylic acid / alkyl (C10-30) acrylate copolymer.

[0289] <21> like <3> ~ <20> The skin external preparation described in any one of the preceding claims, wherein the oily thickener is preferably one or more selected from sugar fatty acid ester oily thickeners, polyglyceryl isostearate, (behenic acid / eicosandioic acid) glyceryl ester, and organically modified clay minerals, more preferably a sugar fatty acid ester oily thickener, further preferably a dextrin fatty acid ester, particularly preferably one or more selected from dextrin myristate, dextrin palmitate, dextrin stearate, dextrin (palmitic acid / 2-ethylhexanoic acid) ester, and dextrin (palmitic acid / hexyldecanoic acid) ester.

[0290] <22> like <3> ~ <21> The skin external preparation described in any one of the preceding claims, wherein the content of the oily thickener in the granular gel capsule is preferably 0.05 mass % or more, more preferably 0.1 mass % or more, further preferably 0.3 mass % or more, and particularly preferably 0.5 mass % or more, relative to the total mass of the skin external preparation; and is preferably 12 mass % or less, more preferably 9 mass % or less, further preferably 6 mass % or less, and particularly preferably 2 mass % or less, relative to the total mass of the skin external preparation.

[0291] <23> like <3> ~ <22> The skin external preparation according to any one of the preceding claims, wherein the content of the oily thickener in the granular gel capsule is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 1.5% by mass or more, relative to the total mass of the granular gel capsule; and is preferably 10% by mass or less, more preferably 7.5% by mass or less, further preferably 5% by mass or less, and particularly preferably 3.5% by mass or less, relative to the total mass of the granular gel capsule.

[0292] <24> like <19> ~ <23> The skin external preparation according to any one of the preceding claims, wherein the content of the aqueous thickener (including polyvinyl alcohol) in the entire skin external preparation is preferably 0.6% by mass or less, more preferably 0.55% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, relative to the total mass of the skin external preparation. Furthermore, the content of the aqueous thickener other than polyvinyl alcohol in the entire skin external preparation is preferably 0.3% by mass or less, more preferably 0.25% by mass or less, even more preferably 0.13% by mass or less, even more preferably 0.06% by mass or less, and even more preferably 0.03% by mass or less, relative to the total mass of the skin external preparation.

[0293] <25> like <9> ~ <24> The skin external preparation described in any one of the preceding claims, wherein component (a6) is preferably one or more species selected from glycols and glycerols, more preferably glycerols, further preferably one or more species selected from glycerol, diglycerol, and polyglycerols, and particularly preferably glycerol.

[0294] <26> like <9> ~ <25> The skin external preparation according to any one of the preceding claims, wherein the content ratio of the (a7) powder in the granular gel capsule is preferably from 0 mass % to 40 mass % inclusive, more preferably from 0 mass % to 30 mass % inclusive, further preferably from 0 mass % to 20 mass % inclusive, and particularly preferably from 0 mass % to 10 mass % inclusive, relative to the total mass of the granular gel capsule.

[0295] <27> like <1> ~ <26> The skin external preparation described in any one of the preceding claims, wherein the average particle size of the granular gel capsule is preferably 20 μm or more, more preferably 30 μm or more, further preferably 40 μm or more, further more preferably 60 μm or more, and particularly preferably 80 μm or more; and is preferably 350 μm or less, more preferably 300 μm or less, further preferably 250 μm or less, and particularly preferably 200 μm or less.

[0296] <28> like <1> ~ <27> The skin external preparation described in any one of the preceding claims, wherein the content of the granular gel capsules is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 22.5% by mass or more, further more preferably 27.5% by mass or more, further more preferably 30% by mass or more, further more preferably 35% by mass or more, and particularly preferably 40% by mass or more, relative to the total mass of the skin external preparation; and further, is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 72.5% by mass or less, and particularly preferably 70% by mass or less, relative to the total mass of the skin external preparation.

[0297] <29> like <1> ~ <28> In any one of the external skin preparations, component (b1) is preferably one or more selected from water and lower alcohols, and more preferably one or more selected from water, ethanol, and isopropyl alcohol.

[0298] <30> like <1> ~ <29> In any one of the external skin preparations, the liquid preferably further contains (b2) a cationic polymer.

[0299] <31> like <30> The skin external preparation, wherein component (b2) is preferably a silicone cationic polymer, more preferably one or more selected from poly(N-acylalkyleneimine)-modified silicone and amino-modified silicone, further preferably poly(N-acylalkyleneimine)-modified silicone, and particularly preferably oxazoline-modified silicone.

[0300] <32> like <30> or <31> The skin external preparation, wherein the content of component (b2) is preferably 0 mass% or more, more preferably 0.005 mass% or more, further preferably 0.01 mass% or more, further more preferably 0.02 mass% or more, and particularly preferably 0.05 mass% or more, relative to the total mass of the skin external preparation; in addition, it is preferably 1 mass% or less, more preferably 0.6 mass% or less, further preferably 0.3 mass% or less, and particularly preferably 0.1 mass% or less, relative to the total mass of the skin external preparation.

[0301] <33> like <1> ~ <32> The skin external preparation described in any one of the preceding claims, wherein the content mass ratio of the granular gel capsule of component (A) to the liquid of component (B) [(A) / (B)] is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.4 or more, and particularly preferably 0.5 or more; and is preferably 3.5 or less, more preferably 3 or less, further preferably 2.5 or less, and particularly preferably 2 or less.

[0302] <34> like <1> ~ <33> The skin external preparation described in any one of the preceding claims, wherein the content of the non-volatile oil agent in the liquid is preferably from 0 mass % to 10 mass % inclusive, more preferably from 0 mass % to 5 mass % inclusive, further preferably from 0 mass % to 1 mass % inclusive, and particularly preferably from 0 mass % to 0 mass % inclusive, relative to the total mass of the skin external preparation.

[0303] <35> like <1> ~ <34> The skin external preparation according to any one of the preceding claims, wherein the mass ratio of the total non-volatile oil in the liquid to the total non-volatile oil in the granular gel capsules [(total non-volatile oil in the liquid) / (total non-volatile oil in the granular gel capsules)] is preferably 0 or more and 0.1 or less, more preferably 0 or more and 0.06 or less, further preferably 0 or more and 0.01 or less, and particularly preferably 0.

[0304] <36> like <1> ~ <35> The skin external preparation according to any one of the preceding claims, wherein the content of the aqueous thickener in the liquid is preferably from 0 mass % to 0.03 mass % inclusive, more preferably from 0 mass % to 0.015 mass % inclusive, further preferably from 0 mass % to 0.005 mass % inclusive, and particularly preferably from 0 mass % to 0.005 mass % inclusive, relative to the total mass of the skin external preparation.

[0305] <37> like <1> ~ <36> The skin external preparation according to any one of the preceding claims, wherein the content of the oily thickener in the liquid is preferably from 0 mass % to 0.03 mass % inclusive, more preferably from 0 mass % to 0.015 mass % inclusive, further preferably from 0 mass % to 0.005 mass % inclusive, and particularly preferably from 0 mass % to 0.005 mass % inclusive, relative to the total mass of the skin external preparation.

[0306] <38> like <1> ~ <37> The skin external preparation described in any one of the preceding claims, wherein the content of the emulsifier in the liquid is preferably 0% by mass or more and 0.4% by mass or less, more preferably 0% by mass or more and 0.2% by mass or less, further preferably 0% by mass or more and 0.1% by mass or less, and particularly preferably 0% by mass, relative to the total mass of the skin external preparation.

[0307] <39> like <1> ~ <38> The skin external preparation according to any one of the preceding claims, wherein the total content of the non-volatile oil agent, the aqueous thickener, and the emulsifier in the liquid is preferably 0% by mass or more and 12% by mass or less, more preferably 0% by mass or more and 5% by mass or less, further preferably 0% by mass or more and 0.001% by mass or less, and particularly preferably 0% by mass, relative to the total mass of the skin external preparation.

[0308] <40> like <1> ~ <39> The skin external preparation according to any one of the preceding claims, further comprising (C) a powder outside the granular gel capsule.

[0309] <41> like <40> In the above-mentioned external preparation for skin, component (C) is preferably a powder other than an ultraviolet scattering agent, more preferably at least one selected from cellulose and silica, further preferably silica, and particularly preferably porous silica.

[0310] <42> like <40> or <41> The skin external preparation, wherein the content of component (C) is preferably 0.05 mass% or more, more preferably 0.2 mass% or more, further preferably 0.6 mass% or more, and particularly preferably 1 mass% or more, relative to the total mass of the skin external preparation; in addition, it is preferably 15 mass% or less, more preferably 12 mass% or less, further preferably 9 mass% or less, and particularly preferably 6 mass% or less, relative to the total mass of the skin external preparation.

[0311] <43> like <1> ~ <42> The skin external preparation described in any one of the foregoing, wherein the viscosity at 25°C is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, further preferably 25 mPa·s or more, and particularly preferably 30 mPa·s or more; in addition, it is preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less, further preferably 1,000 mPa·s or less, and particularly preferably 500 mPa·s or less.

[0312] <44> like <1> ~ <43> The skin external preparation according to any one of the preceding claims, wherein the pH at 25° C. is preferably 4 to 10, more preferably 4.5 to 9, and particularly preferably 5 to 8.

[0313] <45> like <1> ~ <44> The external skin preparation according to any one of the preceding claims, wherein the liquid is an aqueous composition.

[0314] <46> like <1> ~ <45> The skin external preparation according to any one of the preceding claims is preferably a cosmetic, and more preferably a sunscreen.

[0315] Example

[0316] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in the present Examples, various measurements and evaluations were performed by the following methods.

[0317] ·Measurement method and evaluation method

[0318] (1) Average particle size of granular gel capsules

[0319] The volume-based median particle size of each granular gel capsule was measured using a laser diffraction / scattering particle size distribution analyzer LA-960 (manufactured by HORIBA Corporation) under the condition of a refractive index of 1.20.

[0320] (2) Viscosity

[0321] Each external skin preparation was filled into a glass bottle with a lid, and the viscosity at 25°C was measured the day after preparation. The viscosity was measured using a B-type viscometer (TVB-10M) manufactured by Toki Sangyo Co., Ltd. After stirring the contents of the glass bottle, the viscosity was measured using a No. 2 rotor, a rotation speed of 30 rpm, and a measurement time of 1 minute. If measurement was not possible under these conditions, the No. 4 rotor was used.

[0322] (3) Fresh feeling at the initial stage of application

[0323] Each topical skin preparation was evaluated for its light, refreshing feel upon initial application (spreading smoothly like water on the skin, or a watery feel upon application). Three panelists applied the topical skin preparation to the inner forearm and performed a sensory evaluation on a 10-point scale, with 10 representing "very refreshing feeling upon initial application" and 1 representing "no refreshing feeling upon initial application." The average of the scores was calculated.

[0324] (4) Ultraviolet protection effect (UVPE)

[0325] To become 2mg / cm 2 Each topical skin preparation was evenly applied to a 3 cm x 3 cm area on the inner forearm and allowed to dry in a cool, dark place for 15 minutes. After drying, UV protection efficacy (UVPE) was derived using the MUPRIS (Ultraviolet Polarized Reflectance Image Measurement System) according to the method described in the literature (Nishino et al., Skin Research and Technology, 2019, Volume 25, Issue 5, pp. 639-652) and evaluated according to the following criteria.

[0326] (Evaluation criteria for UV protection effect)

[0327] AA: UVPE is above 60

[0328] A: UVPE is 50 or more and less than 60

[0329] B: UVPE is 40 or more and less than 50

[0330] C: UVPE less than 40

[0331] (Preparation Example 1 Granular Gel Capsule C1)

[0332] Granular gel capsules C1 were prepared to have the composition shown in Table 1, and the average particle size was measured.

[0333] The granular gel capsules were prepared as follows. Specifically, agar, (acrylic acid / alkyl (C10-30) acrylate) copolymer, polyvinyl alcohol, sodium hydroxide, and purified water were mixed and heated to 90°C to prepare a mixed solution I. Subsequently, 2-ethylhexyl p-methoxycinnamate, diethylaminohydroxybenzoyl hexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, dextrin palmitate, and glyceryl stearate were heated and mixed at 80°C to dissolve and prepare a dissolved solution II. Next, mixed solution I and dissolved solution II were mixed and stirred using a homogenizer to prepare an oil-in-water dispersion. The resulting oil-in-water dispersion was maintained at 80°C and sprayed into a 25°C gas phase using a two-fluid spray nozzle (SUE45B manufactured by Spraying Systems Co.). The mixture was allowed to stand until the oil-in-water dispersion droplets cooled and solidified, yielding granular gel capsules.

[0334] (Preparation Examples 2 to 12 Granular Gel Capsules C2 to C12)

[0335] Granular gel capsules C2 to C12 having the compositions shown in Tables 1 and 2 were prepared according to Preparation Example 1, and the average particle diameter was measured. The results are shown in Tables 1 and 2.

[0336] [Table 1]

[0337]

[0338] [Table 2]

[0339]

[0340] (External skin preparations of Examples 1 to 19 and Comparative Examples 1 to 3)

[0341] The skin external preparations of Examples 1 to 19 and Comparative Examples 1 to 3 were prepared by conventional methods according to the formulations shown in Tables 3 and 4, and the viscosity, initial refreshing feeling after application, and ultraviolet protection effect (UVPE) were measured and evaluated. The results are shown in Tables 3 and 4.

[0342]

[0343]

[0344] The symbols in the table are as follows.

[0345] *1: PEMULEN TR-2 (manufactured by Lubrizol Advanced Materials, Inc.)

[0346] *2: GOHSENOL EG-05 (Mitsubishi Chemical Corporation)

[0347] *3: UVINUL MC-80 (manufactured by BASF)

[0348] *4: UVINUL A PLUS GRANULAR (manufactured by BASF)

[0349] *5: TINOSORB S (manufactured by BASF)

[0350] *6: UVINUL T150 (manufactured by BASF)

[0351] *7: Rheopearl KL2 (manufactured by Chiba Flour Milling Co., Ltd.)

[0352] *8: MONTEX A (manufactured by Miyoshi Oil & Fat Co., Ltd.)

[0353] *9: MT-100Z (manufactured by TAYCA)

[0354] *10: SALACOS HS-6C (manufactured by The Nisshin OilliO Group Ltd.)

[0355] *11: SUNSPHERE H-121 (manufactured by AGC Si-Tech Co., Ltd.)

[0356] *12: Preparation prepared according to the description of Synthesis Example 1 in JP-A-2008-143820

[0357] *13: PEMULEN TR-1 (manufactured by Lubrizol Advanced Materials, Inc.)

[0358] *14: EMULGEN 1620G (manufactured by Kao Corporation)

[0359] *15: PARLEAM EX (manufactured by NOF Corporation)

[0360] (5) Redispersibility

[0361] The external skin preparations of Examples 1 and 14 were also evaluated for redispersibility.

[0362] Specifically, 50 mL of the skin topical preparation of Example 1 or Example 14 was placed in a 50 mL glass bottle. A stainless steel stirring ball with a diameter of 5 mm was added to the bottle. After standing at room temperature for 72 hours, the mixture was stirred with the stainless steel stirring ball and the number of shakes required to achieve uniformity was measured. The results are shown in Table 5. The fewer the number of shakes, the higher the redispersibility.

[0363] [Table 5]

[0364]

[0365] (6) Storage stability (viscosity when stored at low temperatures)

[0366] The external skin preparations of Examples 1 and 2 were also evaluated for their storage stability (viscosity) when stored at low temperatures.

[0367] Specifically, the skin topical preparations of Example 1 or Example 2 were stored at 5°C for 6 months, then returned to room temperature and shaken until homogeneous. Storage stability was then evaluated based on changes in viscosity before and after storage. The viscosity after storage was measured in the same manner as the viscosity on the day after preparation, and the rate of increase (%) in viscosity after storage relative to the viscosity before storage was calculated. The results are shown in Table 6. The smaller the rate of increase, the higher the storage stability.

[0368] [Table 6]

[0369] Example 1 Example 2 Storage stability 138％ 190％

[0370] (Examples 20 to 22 Skin external preparations)

[0371] The skin external preparations of Examples 20 to 22 were prepared in the same manner as in Example 1 except that the contents of water, porous silica, and poly(N-propionylethyleneimine)-modified silicone were set to the values ​​shown in Table 7, and the viscosity was measured.

[0372] (7) Storage stability (appearance when stored at high temperature)

[0373] The external skin preparations of Examples 1, 14, and 20 to 22 were evaluated for their storage stability when stored at high temperatures.

[0374] Specifically, the external preparations for skin application shown in Table 7 were stored at 50° C. for one month. The external preparations for skin application after storage were visually observed and evaluated according to the following criteria. The results are shown in Table 7.

[0375] (Evaluation criteria for stability (appearance) during high-temperature storage)

[0376] A: No oil separation was observed in the supernatant before shaking.

[0377] B: Separation of oil was observed in the supernatant before shaking, but the appearance remained the same as before storage as long as shaking was continued.

[0378] [Table 7]

[0379]

[0380] (8) Tight fit after coating

[0381] To become 2mg / cm 2 After dripping the skin external preparations of Examples 1, 19, and Comparative Example 2 onto the inner side of the forearm, a finger equipped with an inertial sensor (described in Japanese Patent Application Publication No. 2018-109599) was moved back and forth at a fixed application speed (27 cm / s), and the sensor value Gx was obtained at a sampling interval of 1 ms while the application was continued until a sense of stopping (absorption) was felt. After converting the obtained Gx to an absolute value, the maximum value per 1 s was taken, and the time rate of change of the above maximum value from the time point when absorption began to the time point when absorption ended was taken as the change in tactile sensation (ΔG x ).

[0382] The results are shown in Table 8. ΔG x The larger the value of , the more pronounced the angular velocity Gx in the finger twisting direction is during application, resulting in a sense of tight adhesion in the later stages of application. Furthermore, the change in tactile sensation allows one to actually feel the completion of application. Furthermore, the shorter the time from the start of application to the perceived completion of absorption, the more rapidly the topical preparation for skin application is absorbed into the skin.

[0383] [Table 8]

[0384] Example Example Comparative Example 1 19 2 Start absorption time (s) 21 21 20 Absorption end time (s) 27 29 33 <![CDATA[Inertial sensor ΔG x > 13.3 9.3 6.3

[0385] (Preparation Example 13 Granular Gel Capsules C13)

[0386] According to Preparation Example 1, granular gel capsules C13 having the composition shown in Table 9 were prepared.

[0387] [Table 9]

[0388]

[0389] The symbols in the table are as follows.

[0390] *2: GOHSENOL EG-05 (Mitsubishi Chemical Corporation)

[0391] *7: Rheopearl KL2 (manufactured by Chiba Flour Milling Co., Ltd.)

[0392] *8: MONTEX A (manufactured by Miyoshi Oil & Fat Co., Ltd.)

[0393] *15: PARLEAM EX (manufactured by NOF Corporation)

[0394] *16: SIMULGEL EG QD (manufactured by SEPPIC)

[0395] *17: EXCEPARL IPP (manufactured by Kao Corporation)

[0396] *18: FINSOLV TN (manufactured by Innospec Performance Chemicals)

[0397] *19: ESTEMOL N-01 (manufactured by The Nisshin OilliO Group, Ltd.)

[0398] *20: SALACOS 99 (manufactured by The Nisshin OilliO Group, Ltd.)

[0399] *21: CROPURE OL-LQ-(JP) (Made by CRODA JAPAN KK)

[0400] *22:SUPER WHITE PROTOPET(Sonneborn,LCC)

[0401] (Example 23 Skin external preparation)

[0402] The skin external preparation of Example 23 was prepared by a conventional method using the formulation shown in Table 10, and the refreshing feeling at the initial stage of application was evaluated. The results are shown in Table 10.

[0403] [Table 10]

[0404]

[0405] (9) Uniformity of coating

[0406] Granular gel capsule C13-1 was prepared by replacing 0.01% by mass of water with 0.01% by mass of Nile red (manufactured by Tokyo Chemical Industry Co., Ltd.) as a fluorescent dye to prepare a non-volatile oil dyed with Nile red. The dermatological preparation of Example 23 was prepared by replacing granular gel capsule C13 with the α-agent of C13-1. The α-agent was added to a model plate (HELIOPLATE HD6 manufactured by Helioscreen Co., Ltd.) at a density of 2 mg / cm. 2 Apply the α agent in a certain manner.

[0407] The coating films of the model plate to which the external skin preparation was not applied and the model plate to which the α agent was applied were observed using a fluorescence microscope (BZ-X810 manufactured by KEYENCE Corporation).

[0408] Figure 1 This is a microscopic photograph of a model plate without applying a skin external preparation. Figure 2 Microscopic photograph showing the model plate coated with α agent ( Figure 2In the microscope photograph of the model plate coated with the α agent, the color is uniformly developed regardless of the surface unevenness of the model plate, and the concentration difference of the color developed in the entire area is small. Figures 1 and 2 The results shown confirmed that the non-volatile oil agent that was stained with Nile red and developed fluorescence was uniformly present in the concave and convex portions of the surface of the model plate, that is, the coating film had uniformity.

Claims

1. A skin external preparation, wherein: contain: A granular gel capsule comprising a fixed oil, (a2) one or more encapsulating agents selected from agar, carrageenan, and gelatin, and (a5-2) one or more aqueous thickeners selected from polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, and acrylic acid / alkyl acrylate copolymers; and A liquid comprising the following component (b1): (b1) one or more volatile media selected from the group consisting of water, ethanol, and isopropyl alcohol; and one or more nonvolatile oil agents selected from the group consisting of nonvolatile oil-soluble ultraviolet absorbers, nonvolatile amphiphilic solid fats, nonvolatile oily thickeners, and nonvolatile hydrocarbon oils, wherein the nonvolatile oil agent is present in an amount of 0% by mass to 14% by mass based on the total mass of the external preparation for skin. The granular gel capsules are dispersed in the liquid, The granular gel capsule contains (a4) a polyol mono-C12-22 fatty acid ester and (a5-1) a sugar fatty acid ester oily thickener as the non-volatile oil. The content of the non-volatile oil in the granular gel capsule is 1.5% by mass or more relative to the total mass of the external preparation for skin. The content of the aqueous thickener in the liquid is 0% by mass relative to the total mass of the external preparation for skin. The content mass ratio of the total nonvolatile oil in the liquid to the total nonvolatile oil in the granular gel capsules [(total nonvolatile oil in the liquid) / (total nonvolatile oil in the granular gel capsules)] is 0 or more and 0.1 or less.

2. A skin external preparation, wherein: contain: A granular gel capsule comprising a fixed oil, (a2) one or more encapsulating agents selected from agar, carrageenan, and gelatin, and (a5-2) one or more aqueous thickeners selected from polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, and acrylic acid / alkyl acrylate copolymers; and A liquid comprising the following components (b1) and (b2); and one or more nonvolatile oil agents selected from a nonvolatile oil-soluble ultraviolet absorber, a nonvolatile amphiphilic solid fat, a nonvolatile oily thickener, and a nonvolatile hydrocarbon oil, wherein the nonvolatile oil agent is contained in an amount of 0% by mass to 14% by mass based on the total mass of the external preparation for skin, (b1) one or more volatile media selected from water, ethanol and isopropanol; (b2) cationic polymers, The granular gel capsules are dispersed in the liquid, The granular gel capsule contains (a4) a polyol mono-C12-22 fatty acid ester and (a5-1) a sugar fatty acid ester oily thickener as the non-volatile oil. The content of the non-volatile oil in the granular gel capsule is 1.5% by mass or more relative to the total mass of the external preparation for skin. The content of the aqueous thickener in the liquid was 0% by mass relative to the total mass of the external preparation for skin.

3. The external skin preparation according to claim 1 or 2, wherein The granular gel capsule further contains one or more selected from (a1) an oil-soluble UV absorber and (a8) a non-volatile oil as the non-volatile oil, wherein the (a8) non-volatile oil does not include an oil-soluble UV absorber, an amphiphilic solid fat, and an oily thickener.

4. The external skin preparation according to claim 1 or 2, wherein The granular gel capsule further contains (a1) an oil-soluble ultraviolet absorber as the non-volatile oil agent.

5. The external skin preparation according to claim 4, wherein The content mass ratio of the component (a1) to the total amount of the ultraviolet absorbers in the external skin preparation [(a1) / (total ultraviolet absorbers)] is 0.85 or more and 1 or less.

6. The external skin preparation according to claim 1 or 2, wherein The content of the component (a4) is 0.1% by mass or more relative to the total mass of the granular gel capsule.

7. The external skin preparation according to claim 1 or 2, wherein The content of the component (a5-1) is 0.1% by mass or more based on the total mass of the granular gel capsule.

8. The external skin preparation according to claim 1 or 2, wherein The granular gel capsule may contain (a7) powder, and the content ratio of the (a7) powder is 0% by mass or more and 30% by mass or less relative to the total mass of the granular gel capsule.

9. The external skin preparation according to claim 1 or 2, wherein The average particle size of the granular gel capsule is 60 μm or more and 350 μm or less.

10. The external skin preparation according to claim 1 or 2, wherein The content of the granular gel capsule is 27.5% by mass or more based on the total mass of the external preparation for skin.

11. The external skin preparation according to claim 1 or 2, wherein The content of the oily thickener in the liquid is 0% by mass or more and 0.005% by mass or less relative to the total mass of the external preparation for skin.

12. The external skin preparation according to claim 1 or 2, wherein The liquid may contain an emulsifier, and the content of the emulsifier is 0% by mass or more and 0.4% by mass or less relative to the total mass of the external preparation for skin.

13. The external skin preparation according to claim 1 or 2, wherein The granular gel capsule further contains powder outside.

14. The external skin preparation according to claim 13, wherein The powder outside the granular gel capsule is silicon dioxide.

15. The external skin preparation according to claim 1 or 2, wherein The viscosity at 25°C is 10,000 mPas or less.

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