Silica composite particles

Abstract

Provided are: silica composite particles [1] in which a non-volatile component including ceramides is supported on porous silica particles, wherein the pore volume of the porous silica particles is not less than 0.5 mL / g, and the ratio to pore volume (the volume ratio of the content of the non-volatile component to the volume of pore portions of the porous silica particles) is not more than 110%; granulated particles [2] which comprise the silica composite particles [1]; a method [3] for producing the silica composite particles [1] which comprises, in the following order, a step 1 for obtaining a suspension and a step 2 for drying; and a method [4] for producing the granulated particles [2] which comprises, in the following order, a step 1' for obtaining a suspension and a step 2' for spray drying.

Description

Composite Silica Particles

[0001] The present invention relates to composite silica particles, granulated particles of composite silica particles, and methods for producing the same.

[0002] Ceramides exist as components of intercellular lipids in the stratum corneum, which covers the outermost layer of the skin, and play an important role in maintaining the skin's inherent function as a barrier membrane between the body and the outside world. It is widely known that when such ceramides are incorporated into topical preparations or cosmetics and applied to the skin, they are effective in improving moisturizing effects and improving skin care effects such as preventing or improving rough skin.

[0003] As a method for using ceramides in cosmetics and the like, for example, Japanese Patent Laid-Open Publication No. 2001-158717 (Patent Document 1) discloses a solid powder cosmetic containing (A) 60 to 75 wt % of a powder component containing 0.1 to 20 wt % of a porous inorganic powder in the total composition, and (B) 25 to 40 wt % of an oil component containing 0.1 to 15 wt % of a moisturizing component in the total composition, and ceramides are disclosed as the moisturizing component.

[0004] The present invention relates to composite silica particles in which a nonvolatile component including a ceramide is supported on a porous silica particle, wherein the porous silica particle has a pore volume of 0.5 mL / g or more, the nonvolatile component has a boiling point (1013 hPa) of 150° C. or more, and the pore volume ratio calculated by the following calculation formula (1) is 110% or less: (pore volume ratio (%)) = (total amount (mL) of nonvolatile components supported on porous silica particles) / {(amount (g) of porous silica particles) × (pore volume of porous silica particles (mL / g))} × 100 (1)

[0005] The solid powder cosmetic preparation of Patent Document 1 provides both a moist feeling and a smooth feeling when used, but the amount of moisturizing ingredients (particularly ceramides) released into sebum has not been studied, and there are cases where the ceramides cannot be used sufficiently effectively. The present invention relates to composite silica particles and granulated particles of composite silica particles that can easily release ceramides upon contact with oleic acid, a major component of sebum, as well as methods for producing these.

[0006] The present inventors have found that the above-mentioned problems can be solved by supporting a non-volatile component containing ceramides on porous silica particles having a certain pore volume, in a fixed amount relative to the pore volume of the porous silica. The present invention relates to the following [1] to [4]. [1] Composite silica particles comprising porous silica particles supporting a non-volatile component containing ceramides, wherein the pore volume of the porous silica particles is 0.5 mL / g or more, the boiling point (1013 hPa) of the non-volatile component is 150°C or more, and the pore volume ratio calculated by the following calculation formula (1) is 110% or less: (pore volume ratio (%)) = (total amount (mL) of non-volatile components supported on porous silica particles) / {(amount (g) of porous silica particles) × (pore volume of porous silica particles (mL / g))} × 100 (1). [2] Granulated particles comprising the composite silica particles according to [1]. [3] A method for producing composite silica particles according to [1], comprising the following steps 1 and 2 in this order: Step 1: mixing an emulsion or solution containing a non-volatile component including ceramides with the porous silica particles to obtain a suspension; Step 2: drying the suspension obtained in step 1. [4] A method for producing granulated particles according to [2], comprising the following steps 1' and 2' in this order: Step 1': mixing an emulsion or solution containing a non-volatile component including ceramides with porous silica particles and a water-soluble polymer to obtain a suspension; Step 2': spray-drying the suspension obtained in step 1'.

[0007] According to the present invention, it is possible to provide composite silica particles and granulated particles containing composite silica particles and a water-soluble polymer, which can easily release ceramides upon contact with oleic acid, a major component of sebum, as well as methods for producing these.

[0008] [Composite Silica Particles] The composite silica particles of the present invention are porous silica particles carrying nonvolatile components including ceramides, wherein the porous silica particles have a pore volume of 0.5 mL / g or more, the boiling point of the nonvolatile components (atmospheric pressure: 1013 hPa) is 150°C or more, and the pore volume ratio calculated by the following calculation formula (1) is 110% or less: (pore volume ratio (%)) = (total amount (mL) of nonvolatile components carried on porous silica particles) / {(amount (g) of porous silica particles) × (pore volume of porous silica particles (mL / g))} × 100 (1)

[0009] The composite silica particles of the present invention can easily release ceramides contained in the pores of the porous silica particles upon contact with oleic acid, a major component of sebum. The reason for this is unclear, but is thought to be as follows. The composite silica particles of the present invention support non-volatile components, including ceramides, in the pores of the porous silica particles, which is thought to maintain the ceramides in an amorphous state. The amorphous state of the ceramides is thought to shorten the time it takes for the ceramides to dissolve in oleic acid compared to when the ceramides are in a crystalline state. Therefore, the composite silica particles of the present invention are thought to increase the amount of ceramides released upon contact with oleic acid present on the skin. Furthermore, the pore volume of the porous silica particles of the composite silica particles of the present invention is 0.5 mL / g or more, which allows sufficient amounts of non-volatile components, including ceramides, to be supported in the pores. Furthermore, in the composite silica particles of the present invention, by making the pore volume ratio (the volume ratio of the content of the nonvolatile components to the volume of the pores of the porous silica particles) 110% or less, it means that the amount of ceramides that crystallize outside the pores of the porous silica particles can be suppressed, and the blocking of the entrances to the pores can be suppressed.As a result, it is thought that the decrease in the release amount of ceramides when contacted with oleic acid, which is a major component of sebum, can be suppressed.In addition, a pore volume ratio of 110% means that, in addition to 100% inside the pores of the porous silica particles, at least 10% of the nonvolatile components are present attached to the surface outside the pores of the porous silica particles.

[0010] In this specification, the pore volume ratio calculated by the above-mentioned formula (1) represents the volume ratio of the content of the non-volatile components to the volume of the pores of the porous silica particles.In the composite silica particles of the present invention, the pore volume ratio calculated by the above-mentioned formula (1) is 110% or less, preferably 100% or less, more preferably 80% or less, even more preferably 70% or less, and even more preferably 60% or less, from the viewpoint of suppressing the decrease in the amount of ceramides released into oleic acid, which is the main component of sebum.And from the viewpoint of increasing the amount of ceramides carried and further improving the amount of ceramides released into oleic acid, which is the main component of sebum, it is preferably 5% or more, more preferably 10% or more, even more preferably 25% or more, and even more preferably 35% or more.From these viewpoints, it is preferably 5% or more and 110% or less, more preferably 10% or more and 100% or less, even more preferably 25% or more and 80% or less, even more preferably 35% or more and 70% or less, and even more preferably 35% or more and 60% or less.

[0011] <Porous Silica Particles> In the present invention, the pore volume of the porous silica particles is 0.5 mL / g or more from the viewpoint of supporting non-volatile components including ceramides in the pores.The pore volume of the porous silica particles is 0.5 mL / g or more from the viewpoint of maintaining ceramides in an amorphous state in the pores, preferably 1.0 mL / g or more, more preferably 1.2 mL / g or more, even more preferably 1.4 mL / g or more, and from the viewpoint of ensuring the strength of the particles, preferably 8.0 mL / g or less, more preferably 5.0 mL / g or less, even more preferably 3.0 mL / g or less, even more preferably 2.0 mL / g or less, and from these viewpoints, preferably 0.5 mL / g or more and 8.0 mL / g or less, preferably 1.0 mL / g or more and 5.0 mL / g or less, even more preferably 1.2 mL / g or more and 3.0 mL / g or less, even more preferably 1.4 mL / g or more and 2.0 mL / g or less.

[0012] The pore volume of the porous silica particles is obtained by drying a sample to be measured at 200°C for 3 hours or more under a vacuum of 1 kPa or less, obtaining an adsorption isotherm only on the nitrogen adsorption side at liquid nitrogen temperature, and analyzing the isotherm by the BJH method (Barrett, E.P.; Joyner, L.G.; Halenda, P.P., J. Am. Chem. Soc., 73, 373 (1951)) (hereinafter also referred to as "BJH pore volume"). The pores measured by this method are pores with a radius of 1 to 100 nm, and the integrated value of the volume of pores in this range is the pore volume in the present invention.

[0013] The specific surface area of ​​the porous silica particles measured by the BET method (BET specific surface area) is preferably 200 m from the viewpoint of supporting nonvolatile components and maintaining ceramides in an amorphous state. ２ / g or more, more preferably 300m ２ / g or more, more preferably 500m ２ / g or more, and from the viewpoint of ensuring the strength of the particles, it is preferably 1500 m ２ / g or less, more preferably 1000m ２ / g or less, more preferably 850m ２ / g or less, and from these viewpoints, it is preferably 200m ２ / g or more 1500m ２ / g or less, more preferably 300m ２ / g or more 1000m ２ / g or less, more preferably 500m ２ / g or more 850m ２ The specific surface area measured by the BET method is a value determined by drying a sample to be measured at 200°C for 3 hours or longer under a vacuum of 1 kPa or less, obtaining an adsorption isotherm only on the nitrogen adsorption side at liquid nitrogen temperature, and analyzing the resulting adsorption isotherm by the BET method.

[0014] The average particle size of the porous silica particles is preferably 1.0 μm or more, more preferably 2.0 μm or more, even more preferably 3.0 μm or more, and even more preferably 5.0 μm or more from the viewpoint of the feel when used in cosmetics and the like, and is preferably 50.0 μm or less, more preferably 30.0 μm or less, even more preferably 20.0 μm or less, and even more preferably 15.0 μm or less from the viewpoint of the feel when used in cosmetics and the like, and from these viewpoints, it is preferably 1.0 μm or more and 50.0 μm or less, more preferably 2.0 μm or more and 30.0 μm or less, even more preferably 3.0 μm or more and 20.0 μm or less, and even more preferably 5.0 μm or more and 15.0 μm or less. The average particle size of the porous silica particles is determined by the median diameter D in the particle size distribution of volume frequency measured by laser diffraction type measurement. ５０ (Hereinafter, this may also be simply referred to as the "median diameter"), and is specifically measured by the method described in the Examples.

[0015] The oil absorption of the porous silica particles is preferably 100 mL / 100 g or more, more preferably 150 mL / 100 g or more, and even more preferably 200 mL / 100 g or more, from the viewpoint of supporting non-volatile components, and is preferably 800 mL / 100 g or less, more preferably 700 mL / 100 g or less, and even more preferably 600 mL / 100 g or less, from the viewpoint of particle strength. The oil absorption of the porous silica particles is a value measured by the method described in JIS K5101-13-1 "Refined Linseed Oil Method." This measurement method also includes the amount of oil retained between particles.

[0016] The shape of the porous silica particles is not particularly limited, but from the viewpoint of the feel when used in cosmetics and the like, spherical is preferred. The shape of the porous silica particles is not particularly limited, and may be amorphous, spherical, ellipsoidal, polyhedral, prismatic, etc., and is usually spherical or ellipsoidal. Two or more different shapes may also be used. The shape of the porous silica particles is not particularly limited, but from the viewpoint of the feel when used in cosmetics and the like, spherical is preferred.

[0017] <Non-volatile component> The composite silica particles of the present invention contain a non-volatile component including ceramides. In the present invention, the non-volatile component refers to a component having a boiling point (normal pressure: 1013 hPa) of 150°C or higher. The boiling point of the non-volatile component is 150°C or higher, preferably 180°C or higher, and more preferably 200°C or higher, from the viewpoint of suppressing evaporation from the composite silica particles. The upper limit of the boiling point of the non-volatile component is not particularly limited, but is preferably 1000°C or lower. The molecular weight of the nonvolatile component is preferably 80 or more, more preferably 100 or more, from the viewpoint of increasing the boiling point, and is preferably 6000 or less, more preferably 3000 or less, even more preferably 2000 or less, still more preferably 1500 or less, and still more preferably 1000 or less, from the viewpoint of being supported in the pores of the porous silica particles. From these viewpoints, the molecular weight is preferably 80 or more and 6000 or less, more preferably 100 or more and 3000 or less, even more preferably 100 or more and 2000 or less, still more preferably 100 or more and 1500 or less, and still more preferably 100 or more and 1000 or less.

[0018] (Ceramides) In the present invention, as the ceramides, one or more types selected from natural ceramides and pseudo-ceramides can be preferably used.

[0019] Preferred examples of natural ceramides include glycoceramide, ceramide EOS, ceramide EOP, ceramide NS, ceramide NG, ceramide NP, ceramide EOH, ceramide AS, ceramide AG, and ceramide AP. Commercially available natural ceramides include Ceramide I, Ceramide III, Ceramide IIIB, and Ceramide VI (all manufactured by Evonik), Ceramide TIC-001 (manufactured by Takasago International Corporation), CERAMIDE II (manufactured by Croda Corporation), DS-Ceramide VI, C6-Phytoceramide, DS-ceramide Y3S (manufactured by Doosan Corporation), and CERAMIDE 2 (manufactured by Croda Corporation).

[0020] The pseudo-ceramide is preferably a pseudo-ceramide represented by the following general formula (1):

[0021]

[0022] In general formula (1), R １ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms which may be substituted with a hydroxyl group, or a hydrogen atom; X １ represents a hydrogen atom, an acetyl group, or a glyceryl group; R ２ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms which may be substituted with a hydroxyl group or an amino group, or a hydrocarbon group to 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-terminus of the hydrocarbon group; R ３ represents a hydrogen atom or an alkyl group having a total of 1 to 30 carbon atoms which may be substituted with a hydroxyl group, a hydroxyalkoxy group, an alkoxy group or an acetoxy group.

[0023] R ２ Preferred examples thereof include nonyl, tridecyl, pentadecyl, an undecyl group having linoleic acid ester-bonded at the ω-position, a pentadecyl group having linoleic acid ester-bonded at the ω-position, a pentadecyl group having 12-hydroxystearic acid ester-bonded at the ω-position, and an undecyl group having methyl-branched isostearic acid amide-bonded at the ω-position.

[0024] R １ When is a hydrogen atom, R ３ represents an alkyl group having a total of 10 to 30 carbon atoms, preferably 12 to 20 carbon atoms, which may be substituted with a hydroxyl group, a hydroxyalkoxy group, an alkoxy group, or an acetoxy group; R １ is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms which may be substituted with a hydroxyl group, R ３ R preferably represents a hydrogen atom or an alkyl group having a total of 1 to 8 carbon atoms which may be substituted with a hydroxyl group, a hydroxyalkoxy group, an alkoxy group, or an acetoxy group. ３ The hydroxyalkoxy group or alkoxy group preferably has 1 to 7 carbon atoms.

[0025] The pseudo-ceramide represented by general formula (1) is preferably one or more selected from N-(hexadecyloxyhydroxypropyl)-N-hydroxyethylhexadecanamide, N-(2-hydroxy-3-hexadecyloxypropyl)-N-2-hydroxyethylhexadecanamide, N-(2-hydroxy-3-hexadecyloxypropyl)-N-2-hydroxyethyldecanamide, and N-(tetradecyloxyhydroxypropyl)-N-hydroxyethyldecanamide, and more preferably N-(hexadecyloxyhydroxypropyl)-N-hydroxyethyldecanamide.

[0026] In the present invention, ceramides are supported within the pores of the porous silica particles and therefore exist in an amorphous state within the composite silica particles. That is, in the composite silica particles of the present invention, the ceramides are preferably in an amorphous state. Because the ceramides are in an amorphous state, they are more easily soluble in oleic acid and the like compared to when they are in a crystalline state. Therefore, the composite silica particles of the present invention can easily release the ceramides upon contact with oleic acid, a major component of sebum. In the present invention, the crystalline state of the ceramides in the composite silica particles is determined by the presence or absence of an endothermic peak of 1.0 J / g or more when measured using a differential scanning calorimeter under conditions of a temperature range of 25 to 90°C and a heating time of 1°C / min. If an endothermic peak of 1.0 J / g or more is present, it is determined that the ceramides are crystalline. On the other hand, if an endothermic peak of 1.0 J / g or more is not present, it is determined that the ceramides are not crystalline (i.e., the ceramides are in an amorphous state). The crystallinity of ceramides can be confirmed by the method described in the Examples.

[0027] In the present invention, the content of ceramides in the non-volatile components is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 12% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of increasing the amount of ceramides carried and further improving the amount of ceramides released into oleic acid, which is the main component of sebum; and from the viewpoint of suppressing crystallization of ceramides due to excessive carrying of ceramides, it is preferably 100% by mass or less, more preferably 80% by mass or less, even more preferably 50% by mass or less, and even more preferably 30% by mass or less. From these viewpoints, it is preferably 5% by mass or more and 100% by mass or less, more preferably 10% by mass or more and 80% by mass or less, even more preferably 12% by mass or more and 50% by mass or less, and even more preferably 15% by mass or more and 30% by mass or less.

[0028] In the present invention, the content of ceramides in the composite silica particles is preferably 3% by mass or more, more preferably 4% by mass or more, even more preferably 5% by mass or more, and even more preferably 6% by mass or more, from the viewpoint of increasing the amount of ceramides carried and further improving the amount of ceramides released into oleic acid, which is the main component of sebum; and from the viewpoint of suppressing crystallization of ceramides due to excessive carrying of ceramides, the content is preferably 80% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, and even more preferably 10% by mass or less. From these viewpoints, the content is preferably 3% by mass or more and 80% by mass or less, more preferably 4% by mass or more and 50% by mass or less, even more preferably 5% by mass or more and 30% by mass or less, and even more preferably 6% by mass or more and 10% by mass or less.

[0029] (Alcohol) The non-volatile component in the composite silica particles of the present invention preferably contains an alcohol. The amount of alcohol dissolved in 100 g of water (25°C, normal pressure: 1013 hPa) is preferably more than 1 g. For measuring the amount of alcohol dissolved, see, for example, Journal of the Chemical Society of Japan, 1985, No. 11, pp. 2116-2119 and Journal of the Chemical Society of Japan, 1982, No. 11, pp. 1830-1834. Since alcohol has an affinity for ceramides, the amount of ceramides released into oleic acid, the main component of sebum, can be further improved by the composite silica particles of the present invention containing an alcohol.

[0030] The alcohol may have a substituent and a functional group. Examples of the substituent include an alkoxy group or an acetyl group having 1 to 3 carbon atoms. Examples of the functional group include an ether group or an ester group. In the present invention, the alcohol preferably has two or more hydroxyl groups, more preferably has two or three hydroxyl groups, and even more preferably has two hydroxyl groups. That is, in the present invention, the alcohol is preferably a polyhydric alcohol having two or more hydroxyl groups, and is preferably one or more selected from dihydric alcohols and trihydric alcohols, and more preferably a dihydric alcohol. When the alcohol has a substituent, the hydroxyl group may be substituted with an ether group or an ester group.

[0031] The boiling point of the alcohol (normal pressure: 1013 hPa) is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher, from the viewpoint of suppressing volatilization from the composite silica particles. The upper limit of the boiling point of the alcohol is not particularly limited, but is preferably 500°C or lower, more preferably 450°C or lower, and even more preferably 400°C or lower. Furthermore, the melting point of the alcohol (normal pressure: 1013 hPa) is preferably less than 25°C, more preferably 20°C or lower, from the viewpoint of affinity for porous silica.

[0032] The alcohol is preferably one or more selected from glycol-based solvents and glycerin-based solvents, and glycol-based solvents are more preferred from the viewpoint of further improving the amount of ceramides released into oleic acid, which is the main component of sebum, due to their affinity with ceramides.

[0033] From the viewpoint of affinity with ceramides, the number of carbon atoms in the glycol-based solvent is preferably from 2 to 12, more preferably from 3 to 8, and even more preferably from 4 to 7. In addition, the glycol-based solvent may be alkoxylated with a hydrocarbon having from 1 to 3 carbon atoms, or may be acetylated.

[0034] Examples of the glycol-based solvent include monoalkylene glycols such as ethylene glycol (boiling point 197°C), propylene glycol (boiling point 188°C), 1,3-propanediol (boiling point 211°C), 1,3-butylene glycol (1,3-butanediol) (boiling point 203°C), and 1,2-pentanediol (boiling point 206°C); and polyalkylene glycols such as diethylene glycol (boiling point 245°C), dipropylene glycol (boiling point 232°C), triethylene glycol (boiling point 276°C), polyethylene glycol (boiling point 250°C), and polypropylene glycol (boiling point 287°C). The glycol-based solvent may be alkoxylated with a hydrocarbon having from 1 to 3 carbon atoms, and may further be acetylated. Examples include dipropylene glycol monomethyl ether (boiling point 190°C), methoxyethyl carbitol acetate (boiling point 218°C), butyl carbitol (diethylene glycol monobutyl ether) (boiling point 230°C), methoxybutyl acetate (boiling point 171°C), etc. Among these, the glycol-based solvent is preferably one or more selected from monoalkyl glycols and polyalkyl glycols, more preferably polyalkyl glycols, and even more preferably dipropylene glycol (boiling point 232°C).

[0035] Examples of glycerin-based solvents include glycerin (boiling point 290°C), diglycerin (boiling point 265°C), and triglycerin (boiling point 276°C).

[0036] In the present invention, the content of alcohol in the non-volatile component is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 40% by mass or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to its affinity with ceramides, and is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of supporting ceramides, and from these viewpoints, is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 85% by mass or less, and even more preferably 40% by mass or more and 80% by mass or less.Furthermore, in the present invention, the preferred contents of glycol-based solvent in the non-volatile component and dipropylene glycol in the non-volatile component are also in the same ranges as above.

[0037] In the present invention, the mass ratio of alcohol to ceramides (alcohol / ceramides) is preferably 0.1 or more, more preferably 1.0 or more, and even more preferably 2.0 or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to affinity with ceramides, and is preferably 20.0 or less, more preferably 10.0 or less, and even more preferably 6.0 or less, from the viewpoint of supporting ceramides, and from these viewpoints, is preferably 0.1 or more and 20.0 or less, more preferably 1.0 or more and 10.0 or less, and even more preferably 2.0 or more and 6.0 or less. Furthermore, in the present invention, the preferred mass ratios of glycol-based solvent to ceramides and dipropylene glycol to ceramides are also in the same ranges as above.

[0038] In the present invention, the content of alcohol in the composite silica particles is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to its affinity with ceramides, and from the viewpoint of supporting ceramides, it is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, and from these viewpoints, it is preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 35% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less.Furthermore, in the present invention, the preferred content of glycol-based solvent in the composite silica particles is also in the same range as above.

[0039] (Surfactant) In the composite silica particles of the present invention, the non-volatile component preferably contains a surfactant. Since surfactants have affinity for ceramides, the composite silica particles of the present invention contain a surfactant, which can further improve the amount of ceramides released into oleic acid, a main component of sebum. The surfactant preferably has a hydrocarbon group having 8 or more carbon atoms, more preferably 12 or more carbon atoms, and preferably 24 or less carbon atoms, more preferably 22 or less carbon atoms. The surfactant is preferably one or more selected from anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, more preferably one or more selected from anionic surfactants, cationic surfactants, and nonionic surfactants, and even more preferably one or more selected from anionic surfactants and nonionic surfactants.

[0040] Examples of anionic surfactants include fatty acid salts such as sodium laurate, potassium laurate, and potassium palmitate; polyoxyethylene alkyl ether carboxylates such as polyoxyethylene tridecyl ether sodium acetate; alkyl phosphates such as potassium lauryl phosphate, sodium lauryl phosphate, arginine lauryl phosphate, potassium myristyl phosphate, sodium myristyl phosphate, arginine myristyl phosphate, potassium palmityl phosphate, sodium palmityl phosphate, and arginine palmityl phosphate; polyoxyethylene alkyl ether phosphates such as polyoxyethylene oleyl ether sodium phosphate and polyoxyethylene stearyl ether sodium phosphate; alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate; and polyoxyethylene potassium lauryl sulfate. , polyoxyethylene alkyl ether sulfate salts such as polyoxyethylene sodium lauryl sulfate and polyoxyethylene lauryl triethanolamine sulfate; acylated amino acid salts such as sodium lauroyl sarcosinate, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, N-lauroyl glycine triethanolamine, potassium N-coconut oil fatty acid acyl glycine, N-lauroyl-β-alanine triethanolamine, and N-stearoyl-β-alanine triethanolamine; fatty acid amide sulfonates such as sodium N-myristoyl-N-methyl taurate and sodium N-stearoyl-N-methyl taurate; sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate. Among these, fatty acid amide sulfonates are preferred as anionic surfactants, with sodium N-stearoyl-N-methyl taurate being more preferred.

[0041] Examples of cationic surfactants include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salts. The primary amine compounds, secondary amine compounds, and tertiary amine compounds can be salts formed with organic acids and / or inorganic acids. Examples of primary amine compounds include long-chain alkylamines such as laurylamine, myristylamine, and palmitylamine. Examples of secondary amine compounds include dialkylamines having long-chain alkyl groups and short-chain alkyl groups, such as long-chain alkylmethylamine, long-chain alkylethylamine, and long-chain alkylpropylamine, and sphingosines such as 4D-hydroxysphingocanine and 1-(2-hydroxyethylamino)-3-isostearyloxy-2-propanol. Examples of tertiary amine compounds include trialkylamines having a long-chain alkyl group and a short-chain alkyl group, such as long-chain alkyldimethylamines, long-chain alkyldiethylamines, and long-chain alkyldipropylamines; long-chain fatty acid dialkylaminoethylamides and long-chain fatty acid dialkylaminopropylamides, such as stearic acid dimethylaminopropylamide; arachidyloxypropyldimethylamines, such as hexadecyloxypropyldimethylamine, stearoxypropyldimethylamine, stearoxyethyldimethylamine, and octadecyloxypropyldimethylamine (N,N-dimethyl-3-octadecyloxypropylamine); and acyloxyethyldialkylamines and acyloxypropyldialkylamines, such as behenyloxypropyldimethylamine. Examples of quaternary ammonium salts include alkyltrimethylammonium salts such as octyltrimethylammonium, decyltrimethylammonium chloride, lauryltrimethylammonium chloride, and tetradecyltrimethylammonium chloride; and dialkyldimethylammonium salts, such as didecyldimethylammonium chloride and distearyldimethylammonium chloride. Among these, the cationic surfactant is preferably a secondary amine compound, more preferably a sphingosine, and even more preferably 1-(2-hydroxyethylamino)-3-isostearyloxy-2-propanol.

[0042] Examples of inorganic acids when the primary amine compound, secondary amine compound, or tertiary amine compound is used as a salt include phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, and carbonic acid. Examples of organic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and valeric acid; dicarboxylic acids such as succinic acid, phthalic acid, fumaric acid, oxalic acid, malonic acid, and glutaric acid; oxycarboxylic acids such as glycolic acid, citric acid, lactic acid, pyruvic acid, malic acid, and tartaric acid; and amino acids such as L-glutamic acid and aspartic acid. Among these, organic acids are preferred, amino acids are more preferred, and L-glutamic acid is even more preferred.

[0043] Examples of nonionic surfactants include sorbitan fatty acid esters such as sorbitan monostearate, polyglycerin fatty acid esters such as glycerin fatty acid esters and polyglyceryl monoisostearate, polyoxyethylene fatty acid esters such as propylene glycol fatty acid esters and polyethylene glycol monolaurate, sucrose fatty acid esters, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monostearate, and polyoxyethylene coconut oil fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, alkyl polyglucosides, and polyoxyalkylene-modified silicones such as polyoxyethylene-methylpolysiloxane copolymers. Among these, polyoxyethylene hydrogenated castor oil is preferred as the nonionic surfactant.

[0044] Examples of amphoteric surfactants include betaine-based amphoteric surfactants such as lauryldimethylaminoacetic acid betaine, lauroylamide betaine, and lauryl sulfobetaine.

[0045] In the present invention, the content of surfactants (including salts, the same applies hereinafter) in the non-volatile components is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to affinity with ceramides, and is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of supporting ceramides; from these viewpoints, it is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 40% by mass or less, and even more preferably 5% by mass or more and 30% by mass or less.

[0046] In the present invention, the mass ratio of surfactant to ceramides (surfactant / ceramides) is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and even more preferably 0.3 or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to affinity with ceramides; and from the viewpoint of supporting ceramides, it is preferably 10.0 or less, more preferably 5.0 or less, even more preferably 3.0 or less, and even more preferably 1.0 or less; from these viewpoints, it is preferably 0.01 or more and 10.0 or less, more preferably 0.05 or more and 5.0 or less, even more preferably 0.1 or more and 3.0 or less, and even more preferably 0.3 or more and 1.0 or less.

[0047] In the present invention, the content of the surfactant in the composite silica particles is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to the affinity with ceramides, and is preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 6% by mass or less, from the viewpoint of supporting ceramides; from these viewpoints, the content is preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 12% by mass or less, and even more preferably 2% by mass or more and 6% by mass or less.

[0048] (Oil) In the composite silica particles of the present invention, the non-volatile component preferably contains an oil. Because oils have affinity for ceramides, the inclusion of an oil in the composite silica particles of the present invention can further increase the amount of ceramides released into oleic acid, a major component of sebum. In view of affinity with ceramides, the oil is preferably a compound that is poorly soluble in water. Therefore, the solubility of the oil in 100 g of water (25°C, normal pressure: 1013 hPa) is preferably 1 g or less, more preferably 0.1 g or less, and even more preferably 0.001 g or less. For measuring the solubility, see, for example, Journal of the Chemical Society of Japan, 1985, No. 11, pp. 2116-2119 and Journal of the Chemical Society of Japan, 1982, No. 11, pp. 1830-1834. Examples of oils include liquid oils and solid oils. Preferably, one or more selected from liquid oils and solid oils are used, with solid oils being preferred. In the present invention, the oil does not include the alcohols whose solubility in 100 g of water (at 25° C. and normal pressure: 1013 hPa) exceeds 1 g.

[0049] [Liquid Oil] Examples of liquid oils include hydrocarbon oils, ether oils, ester oils, which have a melting point (at normal pressure: 1013 hPa) of less than 25°C, other alcohols excluding the alcohols whose solubility in 100 g of water (at 25°C, normal pressure: 1013 hPa) exceeds 1 g, silicone oils, and fluorine oils. Specific examples of liquid oils include hydrocarbon oils such as liquid paraffin, squalane, and petrolatum; ether oils such as cetyl dimethyl butyl ether, ethylene glycol dioctyl ether, and glycerol monooleyl ether; ester oils such as octyldodecyl myristate, isopropyl palmitate, butyl stearate, di-2-ethylhexyl adipate, neopentyl glycol dicaprate, trioctanoin, and vegetable oils such as olive oil; alcohols such as oleyl alcohol and 2-octyldodecan-1-ol; silicone oils such as dimethylpolysiloxane, cyclic dimethylpolysiloxane, methylphenylpolysiloxane, amino-modified silicone, carboxy-modified silicone, alcohol-modified silicone, alkyl-modified silicone, polyether-modified silicone, and fluorine-modified silicone; and fluorine-based oils such as perfluoroalkylethyl phosphate, perfluoroalkylpolyoxyethylene phosphate, perfluoropolyether, and polytetrafluoroethylene.

[0050] [Solid Oil] The melting point of the solid oil (normal pressure: 1013 hPa) is 25°C or higher. Examples of solid oils include higher alcohols (including sterols) excluding the above-mentioned alcohols, higher fatty acids, and hydrocarbon oils such as petrolatum. Among these, sterols are preferred from the viewpoint of further improving the release amount of ceramides into oleic acid, which is the main component of sebum, due to their affinity with ceramides. Examples of sterols include animal-derived sterols and plant-derived sterols. Examples of animal-derived sterols include cholesterol, dihydrocholesterol, cholesterol succinate, and the like. Examples of plant-derived sterols include sitosterol, stigmasterol, campesterol, and the like. Among these, animal-derived sterols are preferred, and cholesterol is more preferred.

[0051] In the present invention, the content of the oil in the non-volatile components is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to its affinity with ceramides; and from the viewpoint of supporting ceramides, it is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less; from these viewpoints, it is preferably 0.5% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, even more preferably 3% by mass or more and 20% by mass or less, and even more preferably 5% by mass or more and 10% by mass or less.

[0052] In the present invention, the mass ratio of oil to ceramides (oil / ceramides) is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to affinity with ceramides; and from the viewpoint of supporting ceramides, it is preferably 10.0 or less, more preferably 5.0 or less, and even more preferably 1.0 or less; from these viewpoints, it is preferably 0.01 or more and 10.0 or less, more preferably 0.05 or more and 5.0 or less, and even more preferably 0.1 or more and 1.0 or less.

[0053] In the present invention, the content of the oil in the composite silica particles is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to affinity with ceramides, and is preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 6% by mass or less, from the viewpoint of supporting ceramides; from these viewpoints, the content is preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 12% by mass or less, and even more preferably 2% by mass or more and 6% by mass or less.

[0054] In the present invention, the mass ratio of the nonvolatile components to the porous silica particles (nonvolatile components / porous silica particles) is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and even more preferably 0.15 or more, from the viewpoint of supporting the nonvolatile components including ceramides, and is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1.5 or less, from the viewpoint of containing the nonvolatile components including ceramides in the porous portions. From these viewpoints, it is preferably 0.01 or more and 4 or less, more preferably 0.05 or more and 3 or less, even more preferably 0.1 or more and 2 or less, and even more preferably 0.15 or more and 1.5 or less.

[0055] <Water-soluble polymer> The composite silica particles of the present invention preferably further contain a water-soluble polymer. The water-soluble polymer has good affinity with porous silica particles. Therefore, the surface of the composite silica particles of the present invention can be modified, and when the composite silica particles are used in cosmetics, etc., they blend better with the skin and have an improved feel. Furthermore, modifying the surface of the porous silica particles with a water-soluble polymer makes it easier for ceramides to elute from the composite silica particles, thereby further improving the amount of ceramides released into oleic acid, which is the main component of sebum. Furthermore, when producing granulated particles containing the composite silica particles described below, the water-soluble polymer acts as a granulating agent, allowing granulated particles to be obtained more efficiently.

[0056] The amount of the water-soluble polymer dissolved in 100 g of water (at 25°C and normal pressure of 1013 hPa) is preferably 1 g or more from the viewpoint of affinity for the porous silica particles. For measuring the amount of dissolution, see, for example, Journal of the Chemical Society of Japan, 1985, No. 11, pp. 2116-2119 and Journal of the Chemical Society of Japan, 1982, No. 11, pp. 1830-1834.

[0057] From the viewpoint of affinity for the porous silica particles, the weight-average molecular weight of the water-soluble polymer is preferably 10,000 or more, more preferably 30,000 or more, even more preferably 50,000 or more, and is preferably 500,000 or less, more preferably 400,000 or less, even more preferably 300,000 or less. The weight-average molecular weight of the water-soluble polymer is measured by gel permeation chromatography (GPC) using liquid chromatography, specifically by the method described in the examples.

[0058] The water-soluble polymer is preferably one or more selected from synthetic polymers and natural polymers, with natural polymers being more preferred from the viewpoint of affinity with porous silica particles. Examples of synthetic polymers include salts such as sodium salts and potassium salts of polyacrylic acid, polymethacrylic acid, etc., and polyvinylpyrrolidone. Examples of natural polymers include water-soluble polysaccharides. Examples of water-soluble polysaccharides include sugars such as glucose, lactose, and sucrose, as well as polysaccharides and derivatives thereof that contain these sugars as structural units. Examples of derivatives include those that contain an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyalkylene oxide group such as a polyethylene oxide group or a polypropylene oxide group. Specific examples of water-soluble polysaccharides include mucopolysaccharides such as locust bean gum, guar gum, tamarind gum, quince seed-derived gum, gum arabic, tragacanth gum, karaya gum, carrageenan, pectin, hydroxypropyl guar gum, methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, tuberose polysaccharide, xanthan gum, gellan gum, dextran, pullulan, hyaluronic acid, chondroitin sulfate, dermatan sulfate, chitin, chitosan, etc. Among these, one or more selected from xanthan gum and pullulan are preferred, with pullulan being preferred.

[0059] In the present invention, the content of the water-soluble polymer per 100 parts by mass of porous silica particles is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, from the viewpoint of further improving the release of ceramides to oleic acid, the main component of sebum, due to its affinity with the porous silica particles, and from the viewpoint of obtaining granulated particles, and from the same viewpoint, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, and from these viewpoints, it is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, even more preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 15 parts by mass or less. The preferred content of the water-soluble polysaccharide per 100 parts by mass of porous silica particles is also in the same range as above.

[0060] In the present invention, the content of the water-soluble polymer in the composite silica particles is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, from the viewpoint of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to its affinity with the porous silica particles, and from the viewpoint of obtaining granulated particles, and is preferably 18% by mass or less, more preferably 14% by mass or less, and even more preferably 8% by mass or less, from the viewpoint of supporting ceramides.

[0061] In the present invention, the water content (water content) in the composite silica particles is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of supporting non-volatile components including ceramides in the pores, and may be preferably 0.01% by mass or more.

[0062] In the present invention, the average particle size of the composite silica particles is preferably 1.0 μm or more, more preferably 3.0 μm or more, and even more preferably 5.0 μm or more from the viewpoint of carrying nonvolatile components, and is preferably 50.0 μm or less, more preferably 30.0 μm or less, even more preferably 20.0 μm or less, and even more preferably 15.0 μm or less from the viewpoint of the feel when used in cosmetics and the like. The average particle size of the composite silica particles is determined by the median diameter D ５０ (Hereinafter, this is also referred to simply as "median diameter"), and is specifically measured by the method described in the Examples. The composite silica particles of the present invention are preferably in a powder form. The fact that they are in a powder form can be confirmed by the presence of each particle separately under an optical microscope.

[0063] <Method for producing composite silica particles> The method for producing composite silica particles of the present invention comprises the following steps 1 and 2 in this order: Step 1: mixing the porous silica particles with an emulsion or solution containing a non-volatile component including the above-mentioned ceramides to obtain a suspension; and Step 2: drying the suspension obtained in Step 1.

[0064] (Step 1) Step 1 is a step of mixing the above-mentioned porous silica particles with an emulsion or solution containing non-volatile components including the above-mentioned ceramides to obtain a suspension.

[0065] [Emulsion] An emulsion containing non-volatile components including ceramides can be obtained by mixing an oil phase containing ceramides with an aqueous phase containing a surfactant. That is, when an emulsion is used in Step 1, it is preferable to have the following Step A before Step 1. Step A: A step of mixing an oil phase containing ceramides with an aqueous phase containing a surfactant to obtain an emulsion containing non-volatile components including ceramides.

[0066] The solvent used in the oil phase is preferably an organic solvent having a boiling point (normal pressure: 1013 hPa) of 100°C or less, and is preferably one or more selected from ethanol, acetone, and methyl ethyl ketone, with ethanol being preferred. When the boiling point of the solvent used in the oil agent is 100°C or less, the solvent can be removed from the obtained composite silica particles by drying in step 2. In the method for producing composite silica particles of the present invention, when the above-mentioned alcohol, surfactant, and oil agent are used as non-volatile components in the composite silica particles, it is preferable to contain these components in the oil phase.

[0067] The solvent used in the aqueous phase is preferably water such as deionized water. In the method for producing composite silica particles of the present invention, from the viewpoint of efficiently obtaining an emulsion, it is preferable to add a surfactant to the aqueous phase, and it is more preferable to add an anionic surfactant.

[0068] In step 1, the content of ceramides in the emulsion 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 preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. In step 1, the content of oil in the emulsion is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. In step 1, from the viewpoint of emulsification, the content of surfactant in the emulsion 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 preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0069] [Solution] A solution containing a non-volatile component including ceramides can be obtained as an oil phase by mixing a solvent with a non-volatile component including ceramides.

[0070] The solvent used for the solution is preferably an organic solvent having a boiling point (normal pressure: 1013 hPa) of 100°C or less, and is preferably one or more selected from ethanol, acetone, and methyl ethyl ketone, with ethanol being preferred. When the boiling point of the solvent used for the oil solution is 100°C or less, the solvent can be removed from the obtained composite silica particles by drying in step 2.

[0071] In step 1, the emulsion or solution containing a non-volatile component including ceramides and the porous silica particles can be mixed by a known method, for example, mixing with a stirring blade. In step 1, the mixing mass ratio of the emulsion or solution to the porous silica particles (emulsion or solution / porous silica particles) is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, from the viewpoint of supporting the ceramides, and is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less, from the viewpoint of reducing the load of the drying step in step 2. In the method for producing composite silica particles of the present invention, if the obtained composite silica particles contain a water-soluble polymer, it is preferable that the water-soluble polymer is also mixed in step 1 when mixing the emulsion solution and the porous silica particles. That is, in the method for producing composite silica particles of the present invention, step 1 is preferably a step of mixing the emulsion or solution containing a non-volatile component including ceramides, the porous silica particles, and the water-soluble polymer to obtain a suspension.

[0072] In step 1, the content of ceramides in the emulsion or solution is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less.

[0073] (Step 2) Step 2 is a step of drying the suspension obtained in step 1. The composite silica particles of the present invention can be obtained by drying the suspension in step 2. As the drying method in step 2, a known method can be used, such as tray drying or spray drying.

[0074] When the drying in step 2 is shelf drying, the drying temperature is preferably 70 to 250°C, more preferably 75 to 220°C, and even more preferably 80 to 200°C. The drying time is preferably 8 to 72 hours, more preferably 10 to 24 hours, and even more preferably 12 to 18 hours. A commercially available electric dryer or the like can be used as the apparatus for shelf drying.

[0075] When the drying in step 2 is spray drying, examples of the spray drying method include known methods such as the rotating disk method, pressure nozzle method, two-fluid nozzle method, and four-fluid nozzle method. Among these, the two-fluid nozzle method is preferred for the spray drying in step 2. The inlet temperature of the hot air in spray drying is preferably 80°C to 250°C, more preferably 100°C to 220°C, and even more preferably 120°C to 200°C. The outlet temperature of the hot air in spray drying is preferably 50°C to 120°C, more preferably 60°C to 110°C, and even more preferably 70°C to 100°C. The outlet temperature can be adjusted by controlling the inlet temperature. A commercially available spray drying device can be used as the device used for spray drying.

[0076] [Granulated particles containing composite silica particles] The granulated particles of the present invention are granulated particles containing the composite silica particles described above. The granulated particles of the present invention are obtained by granulating the composite silica particles described above with a water-soluble polymer. That is, the granulated particles of the present invention preferably contain the composite silica particles described above and further contain a water-soluble polymer. As the water-soluble polymer, the same water-soluble polymer as in the composite silica particles described above can be preferably used, and from the viewpoint of granulation properties, a water-soluble polysaccharide is more preferable. As a granulation method, granulation can be performed by the manufacturing method of granulated particles containing composite silica particles described below. Since the granulated particles of the present invention contain the composite silica particles described above, they can easily release ceramides when they come into contact with oleic acid, a major component of sebum.

[0077] In the granulated particles of the present invention, the content of the water-soluble polymer relative to 100 parts by mass of the porous silica particles is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, from the viewpoint of further improving the release of ceramides to oleic acid, the main component of sebum, due to its affinity with the porous silica particles, and from the same viewpoint, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, and from these viewpoints, it is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, even more preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 15 parts by mass or less. The preferred content of the water-soluble polysaccharide relative to 100 parts by mass of the porous silica particles is also in the same range as above.

[0078] In the present invention, the moisture content (water content) in the granulated particles is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of supporting non-volatile components including ceramides in the pores, and may preferably be 0.01% by mass or more.

[0079] <Method for producing granulated particles containing composite silica particles> The method for producing granulated particles of the present invention comprises the following steps 1' and 2' in this order, and is a method for producing granulated particles containing composite silica particles, in which the pore volume ratio calculated by the following calculation formula (1) is 110% or less: (Pore volume ratio (%)) = (Total amount (mL) of non-volatile components supported on porous silica particles) / {(Amount (g) of porous silica particles) × (Pore volume of porous silica particles (mL / g))} × 100 (1) Step 1': mixing an emulsion or solution containing non-volatile components including the above-mentioned ceramides, the above-mentioned porous silica particles, and the above-mentioned water-soluble polymer to obtain a suspension. Step 2': spray-drying the suspension obtained in step 1'.

[0080] (Step 1') Step 1' is a step of mixing the emulsion or solution containing the non-volatile component including the ceramides, the porous silica particles, and the water-soluble polymer to obtain a suspension. The form of the emulsion or solution containing the non-volatile component including the ceramides in Step 1' is the same as that in Step 1 of the method for producing composite silica particles.

[0081] In step 1', the water-soluble polymer can be preferably the same as the water-soluble polymer in the composite silica particles described above, and from the viewpoint of efficiently obtaining granulated particles, it is more preferably a water-soluble polysaccharide. As the water-soluble polysaccharide, the same as the water-soluble polysaccharide in the composite silica particles described above is preferred.

[0082] (Step 2') Step 2' is a step of spray-drying the suspension obtained in step 1'. Since the water-soluble polymer contained in the emulsion or solution in step 1' acts as a so-called granulating agent, the granulated particles of the present invention can be obtained by spray-drying the suspension in step 2'. The spray-drying method in step 2' is preferably the same as the spray-drying method in step 2 of the above-mentioned method for producing composite silica particles.

[0083] The present invention further discloses the following [1] to

[37] . [1] Composite silica particles in which a non-volatile component including a ceramide is supported on a porous silica particle, the porous silica particles having a pore volume of 0.5 mL / g or more, the boiling point (1013 hPa) of the non-volatile component being 150°C or more, and the composite silica particles having a pore volume ratio of 110% or less calculated by the following calculation formula (1): (pore volume ratio (%)) = (total amount (mL) of non-volatile components supported on porous silica particles) / {(amount (g) of porous silica particles) × (pore volume of porous silica particles (mL / g))} × 100 (1). [2] The composite silica particles according to [1], in which the pore volume ratio calculated by the calculation formula (1) is 10% or more and 100% or less. [3] The composite silica particles according to [1] or [2], wherein the pore volume ratio calculated by the formula (1) is 25% or more and 80% or less. [4] The composite silica particles according to any one of [1] to [3], wherein the pore volume of the porous silica particles is 1.0 mL / g or more and 5.0 mL / g or less. [5] The composite silica particles according to any one of [1] to [4], wherein the pore volume of the porous silica particles is 1.2 mL / g or more and 3.0 mL / g or less. [6] The composite silica particles according to any one of [1] to [5], wherein the ceramides are in an amorphous state. [7] The composite silica particles according to any one of [1] to [6], wherein the content of the ceramides in the non-volatile component is 5% by mass or more and 100% by mass or less. [8] The composite silica particles according to any one of [1] to [7], wherein the content of the ceramides in the non-volatile component is 10% by mass or more and 80% by mass or less. [9] The composite silica particles according to any one of [1] to [8], wherein the content of the ceramides in the composite silica particles is 3% by mass or more and 80% by mass or less.

[10] The composite silica particles according to any one of [1] to [9], wherein the content of the ceramides in the composite silica particles is 4% by mass or more and 50% by mass or less.

[11] The composite silica particles according to claim 1 or 2, wherein the mass ratio of the nonvolatile component to the porous silica particles (nonvolatile component / porous silica particle) is 4 or less.

[12] The composite silica particles according to any one of [1] to

[11] , wherein the mass ratio of the nonvolatile component to the porous silica particles (nonvolatile component / porous silica particle) is 0.01 or more and 4 or less.

[13] The composite silica particles according to any one of [1] to

[12] , wherein the mass ratio of the nonvolatile component to the porous silica particles (nonvolatile component / porous silica particle) is 0.05 or more and 3 or less.

[14] The composite silica particles according to any one of [1] to

[13] , wherein the nonvolatile component contains an alcohol, and the solubility of the alcohol in 100 g of water (25°C, 1013 hPa) exceeds 1 g.

[15] The composite silica particles according to

[14] , wherein the mass ratio of the alcohol to the ceramides (alcohol / ceramides) is 0.1 or more and 20.0 or less.

[16] The composite silica particle according to

[14] or

[15] , wherein the mass ratio of the alcohol to the ceramides (alcohol / ceramides) is 1.0 or more and 10.0 or less.

[17] The composite silica particle according to any one of

[14] to

[16] , wherein the alcohol comprises a glycol-based solvent.

[18] The composite silica particle according to any one of

[14] to

[17] , wherein the alcohol comprises dipropylene glycol.

[19] The composite silica particle according to any one of [1] to

[17] , wherein the non-volatile component contains a surfactant.

[20] The composite silica particle according to

[19] , wherein the mass ratio of the surfactant to the ceramides (surfactant / ceramides) is 0.01 or more and 10.0 or less.

[21] The composite silica particle according to

[19] or

[20] , wherein the mass ratio of the surfactant to the ceramides (surfactant / ceramides) is 0.05 or more and 5.0 or less.

[22] The composite silica particles according to any one of [1] to

[21] , wherein the content of ceramides in the nonvolatile components is 5% by mass or more.

[23] The composite silica particles according to any one of [1] to

[22] , further comprising a water-soluble polymer.

[24] The composite silica particles according to

[23] , wherein the water-soluble polymer is a water-soluble polysaccharide.

[25] The composite silica particles according to

[23] or

[24] , wherein the content of the water-soluble polymer per 100 parts by mass of the porous silica particles is 0.5 parts by mass or more and 50 parts by mass or less.

[26] The composite silica particles according to any one of

[21] to

[23] , wherein the content of the water-soluble polymer relative to 100 parts by mass of the porous silica particles is 1 part by mass or more and 30 parts by mass or less.

[27] The composite silica particles according to any one of [1] to

[26] , wherein the water content in the composite silica particles is 10% by mass or less.

[28] The composite silica particles according to any one of [1] to

[27] , wherein the water content in the composite silica particles is 7% by mass or less.

[29] The composite silica particles according to any one of [1] to

[28] , wherein the composite silica particles are in powder form.

[30] Granulated particles comprising the composite silica particles according to any one of [1] to

[29] .

[31] The granulated particles according to

[30] , further comprising a water-soluble polymer.

[32] The granulated particles according to

[30] or

[31] , wherein the water content in the granulated particles is 10% by mass or less.

[33] Granulated particles according to any one of

[30] to

[32] , wherein the water content in the granulated particles is 7% by mass or less.

[34] Granulated particles according to any one of

[30] to

[33] , wherein the water content in the granulated particles is 5% by mass or less.

[35] A method for producing composite silica particles according to any one of [1] to

[29] , comprising the following steps 1 and 2 in this order: Step 1: mixing an emulsion or solution containing a non-volatile component including the ceramides with the porous silica particles to obtain a suspension; Step 2: drying the suspension obtained in step 1;

[36] A method for producing granulated particles containing the composite silica particles according to any one of

[30] to

[34] , comprising the following steps 1' and 2' in this order: Step 1': A step of mixing an emulsion or solution containing non-volatile components including ceramides with porous silica particles and a water-soluble polymer to obtain a suspension. Step 2': A step of spray-drying the suspension obtained in Step 1'.

[37] A method for producing granulated particles containing composite silica particles according to

[36] , wherein the water-soluble polymer is a water-soluble polysaccharide.

[0084] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Each property value was measured and evaluated by the following methods.

[0085] <Production of Composite Silica Particles> Examples 1 to 4 and Comparative Examples 2 to 5 (Preparation of Oil Phase) The oil phases (solutions) used in Examples 1 to 4 and Comparative Examples 2 to 5 were prepared by mixing the components according to the compositions shown in Table 1. Mixing was performed using a propeller blade (diameter 30 mm, width 5 mm) at a propeller blade rotation speed of 120 rpm, a mixing temperature of 60°C, and a mixing time of 10 minutes. (Preparation of Suspension) Porous silica particles or non-porous silica particles were mixed with the oil phase (solution) prepared according to the composition shown in Table 1 to obtain a suspension. The suspension was mixed using a stirring rod at a mixing temperature of 25°C and a mixing time of 5 minutes. (Production of Composite Silica Particles) 10 g of the suspension was placed in a crystallizing dish and shelf-dried using an electric dryer at a drying temperature of 90°C for 15 hours, and then allowed to cool to room temperature (25°C). The ethanol solvent for the oil phase was completely removed by the tray drying, and the ceramides were supported on the porous or non-porous silica particles to obtain composite silica particles. The composition, physical properties, and evaluation results of the obtained composite silica particles are shown in Table 2.

[0086] Examples 5 to 8 (Preparation of Oil Phase) The oil phase in Example 5 was prepared by melting ceramides at 80°C. The oil phases in Examples 6 to 8 were prepared by mixing components according to the compositions listed in Table 1. Mixing was performed using a propeller blade (diameter 30 mm, width 5 mm) at a propeller blade rotation speed of 120 rpm, a mixing temperature of 80°C, and a mixing time of 60 minutes. (Preparation of Aqueous Phase) The aqueous phases in Examples 5 to 8 were prepared by mixing components according to the compositions listed in Table 1. Mixing was performed using a propeller blade (diameter 30 mm, width 5 mm) at a propeller blade rotation speed of 120 rpm, a mixing temperature of 80°C, and a mixing time of 10 minutes. (Preparation of Emulsion) An oil phase prepared according to the composition listed in Table 1 was mixed with the aqueous phase prepared according to the composition listed in Table 1 to prepare an emulsion. The emulsion was mixed using a propeller blade (diameter 30 mm, width 5 mm) at a rotation speed of 120 rpm, a mixing temperature of 25°C, and a mixing time of 10 minutes. This emulsion was mixed with porous silica particles (Sunsphere H-52, manufactured by AGC Si-Tech Co., Ltd., pore volume 1.5 mL / g, BET specific surface area 700 m). ２10 g of the suspension was placed in a crystallizing dish and shelf-dried using an electric dryer at a drying temperature of 90°C for 15 hours, and then allowed to cool at room temperature. The shelf-drying completely removed the ethanol solvent for the oil phase and the deionized water solvent for the aqueous phase, allowing the ceramides to be supported on the porous silica particles, thereby obtaining composite silica particles. The resulting composite silica particles are shown in Table 2.

[0087] Example 9 (Preparation of Oil Phase) The oil phase used in Example 9 was a mixture of the composition shown in Table 1. Mixing was carried out using a propeller blade (diameter 30 mm, width 5 mm) at a propeller blade rotation speed of 120 rpm, a mixing temperature of 80°C, and a mixing time of 60 minutes. (Preparation of Aqueous Phase) The aqueous phase used in Example 9 was a mixture of the composition shown in Table 1. Mixing was carried out using a propeller blade (diameter 30 mm, width 5 mm) at a propeller blade rotation speed of 120 rpm, a mixing temperature of 80°C, and a mixing time of 10 minutes. (Preparation of Suspension) An oil phase prepared with the composition shown in Table 1 was mixed with the aqueous phase prepared with the composition shown in Table 1 to prepare an emulsion. This emulsion was mixed with pullulan (cosmetic pullulan, manufactured by Hayashibara Co., Ltd.) as a water-soluble polymer and porous silica particles (Sunsphere H-52, manufactured by AGC Si-Tech Co., Ltd., pore volume 1.5 mL / g, BET specific surface area 700 m ２ 10 g of the suspension was placed in a crystallizing dish and shelf-dried using an electric dryer at a temperature of 90°C for 15 hours, and then allowed to cool at room temperature. The shelf-drying completely removed the ethanol solvent for the oil phase and the deionized water solvent for the aqueous phase, allowing the ceramides to be supported on the porous silica particles, thereby obtaining composite silica particles. The resulting composite silica particles are shown in Table 2.

[0088] <Production of Granulated Particles> Example 10 (Preparation of Oil Phase) The oil phase used in Example 10 was a mixture of ingredients with the composition shown in Table 1. Mixing was carried out using a propeller blade (diameter 150 mm, width 10 mm) at a propeller blade rotation speed of 240 rpm, a mixing temperature of 80°C, and a mixing time of 60 minutes. (Preparation of Aqueous Phase) The aqueous phase used in Example 10 was a mixture of ingredients with the composition shown in Table 1. Mixing was carried out using a three-blade inclined propeller blade (diameter 320 mm, width 60 mm) at a propeller blade rotation speed of 120 rpm, a mixing temperature of 80°C, and a mixing time of 10 minutes. (Preparation of Suspension) An oil phase separately prepared with the composition shown in Table 1 was mixed with the aqueous phase prepared with the composition shown in Table 1 to prepare an emulsion. This emulsion was mixed with pullulan (cosmetic pullulan, manufactured by Hayashibara Co., Ltd.) as a water-soluble polymer and porous silica particles (Sunsphere H-52, manufactured by AGC Si-Tech Co., Ltd., pore volume 1.5 mL / g, BET specific surface area 700 m ２ / g, oil absorption 300 mL / 100 g, average particle size 5 μm) were mixed in the composition shown in Table 1 to obtain a suspension. The suspension was mixed using a three-blade inclined propeller blade (diameter 320 mm, width 60 mm) under conditions of a propeller blade rotation speed of 400 rpm, a mixing temperature of 25°C, and a mixing time of 60 minutes. (Production of Granulated Particles) The suspension was spray-dried at an air temperature of 180°C using a pilot-scale parallel-flow spray dryer (AD-0506 N / R type spray dryer, manufactured by Ashizawa Niro Atomizer Co., Ltd., tower length 8,650 mm, straight barrel 6,000 mm, tower diameter 3,200 mm). The dried product obtained by the spray drying was collected at two points, below the tower and below a cyclone, and then mixed at the collected mass ratio to obtain granulated particles containing composite silica particles. A two-fluid nozzle (CNP500 manufactured by Atmax Corporation) was used for spraying during spray drying, with the spray direction directed upward. Furthermore, the ethanol solvent for the oil phase and the deionized water solvent for the aqueous phase were removed by the spray drying. The composition, physical properties, and evaluation results of the resulting granulated particles are shown in Table 2.

[0089] <Ceramide Particles> Comparative Example 1 As the ceramide particles, a ceramide substance (SOFCARE CERAMIDE SL-E manufactured by Kao Corporation, average particle size 119 μm) was used in the state when received.

[0090] Details of each component listed in Tables 1 and 2 are as follows: [Silica particles] Porous silica particles: Sunsphere H-52: manufactured by AGC Si-Tech Co., Ltd., pore volume 1.5 mL / g, BET specific surface area 700 m ２ / g, oil absorption 300 mL / 100 g, average particle size 5 μm Non-porous silica particles: Sunsphere NP-200: manufactured by AGC Si-Tech Co., Ltd., pore volume 0.1 mL / g, BET specific surface area 100 m ２ / g, oil absorption 40mL / 100g, average particle size 20μm [Ceramides] N-(hexadecyloxyhydroxypropyl)-N-hydroxyethylhexadecanamide soft care ceramide: SL-E, manufactured by Kao Corporation, density 1.00g / mL [Alcohol] Dipropylene glycol: DPG-RF, manufactured by ADEKA Corporation, boiling point 232°C, density 1.03g / mL [Surfactants] Anionic surfactant: N-stearoyl-N-methyl taurate sodium: Nikkol SMT, manufactured by Nikko Chemical Co., Ltd., density 1.00g / mL Cationic surfactant: 1-(2-hydroxyethylamino)-3-isostearyloxy-2-propanol: HE-ISP, manufactured by Kao Corporation, density 0.91g / mL Nonionic surfactants: Polyoxyethylene hydrogenated castor oil: Emanone CH-60(K), manufactured by Kao Corporation, density 1.03 g / mL [Oil agents] Liquid oil: Dimethylpolysiloxane: KF-96A-6CS, manufactured by Shin-Etsu Chemical Co., Ltd., density 1.00 g / mL Solid oil: Cholesterol: Cholesterol JSQI, manufactured by Nippon Fine Chemical Co., Ltd., density 1.00 g / mL [Organic acids] L-glutamic acid: L-glutamic acid, manufactured by Ajinomoto Co., Inc. [Water-soluble polymers] Pullulan (water-soluble polysaccharide): Cosmetic pullulan, manufactured by Hayashibara Co., Ltd., weight-average molecular weight 200,000, density 1.00 g / mL [Oil phase solvent] Ethanol: Ethanol (99.5), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Aqueous phase solvent] Deionized water

[0091]

[0092] [Evaluation and Measurement Methods] <Calculation of Pore Volume Ratio> The pore volume ratio of the obtained composite silica particles or granulated particles was calculated using the composition and pore volume of the silica particles and the composition and density of the nonvolatile components listed in Table 2, according to the following calculation formula (1): (Pore volume ratio (%)) = (Total amount of nonvolatile components supported on porous silica particles (mL)) / {(Amount of porous silica particles (g)) × (Pore volume of porous silica particles (mL / g))} × 100 (1)

[0093] <Crystallization of Ceramides> The composite silica particles or granulated particles of the Examples and Comparative Examples were measured using a differential scanning calorimeter (DSC600, manufactured by Hitachi High-Tech Corporation) under the following measurement conditions. A particle having an endothermic peak of 1.0 J / g or more was considered to be crystalline, and a particle having no endothermic peak was considered to be non-crystalline (amorphous). (Measurement Conditions) Temperature range: 25 to 90°C Heating rate: 1°C / min

[0094] <Average particle size> The average particle size of the composite silica particles or granulated particles in the examples and comparative examples, and the porous silica particles used as raw materials, was measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) under the following measurement conditions: Measurement temperature: 25°C Relative refractive index: 1.07

[0095] <Concentration of ceramides released into oleic acid> 10 g of oleic acid (Lunac O-V, manufactured by Kao Corporation) was placed in a 50 mL glass bottle, and the composite silica particles or granulated particles of the Examples and Comparative Examples were mixed therein to a concentration of 7.2 g / L of ceramides. The glass bottle was placed in a 35°C water bath and stirred using a magnetic stirrer (stir bar (diameter 3.0 cm)) at 300 rpm for 10 minutes to obtain a dispersion. The dispersion was then filtered using a 0.8 μm pore size membrane filter (Dismic 25CS080AN, manufactured by Advantec Co., Ltd.) to remove solid residues, yielding a ceramide release solution as a measurement sample. The concentration of ceramide substances in the release solution was measured using high-performance liquid chromatography (Chromaster, manufactured by Hitachi High-Tech Corporation) under the following measurement conditions, and the release concentration of ceramides into oleic acid was determined. Oleic acid is one of the main components contained in sebum, and in this example, oleic acid was used as a model for sebum. In other words, the greater the concentration of ceramides released into oleic acid, the greater the amount of ceramides released into sebum, and ultimately into the skin. (Measurement Conditions) Detector: 5430 Diode Array Detector, Hitachi High-Tech Corporation Detection Method: Absorbance (212 nm) Column: CAPCELLPAK C18 MG, Osaka Soda Co., Ltd. Solvent: A mixture of 70% by volume of acetonitrile (for high-performance liquid chromatography, Fujifilm Wako Pure Chemical Industries, Ltd.) and 30% by volume of tetrahydrofuran (for high-performance liquid chromatography, Fujifilm Wako Pure Chemical Industries, Ltd.) Measurement Temperature: 40°C Flow Rate: 1.0 mL / min

[0096] <Weight-average molecular weight of water-soluble polymer> The weight-average molecular weight of the water-soluble polymer was measured by gel permeation chromatography (GPC) under the following conditions. <Measurement conditions> Column: TSKgel GMPWXL + TSKgel GMPWXL (manufactured by Tosoh Corporation) Eluent: 0.2 M phosphate buffer / CH ３CN=7 / 3 (volume ratio) Temperature: 40°C Flow rate: 1.0 mL / min Sample size: 2 mg / mL Detector: RI Standard substance: sodium polystyrene sulfonate (weight average molecular weight: 1,100, 3,610, 14,900, 152,000, manufactured by POLMER STANDARDS SERVICE)

[0097] <Moisture content> Measurement was performed using a Karl Fischer moisture analyzer (AQV-2200, manufactured by Hiranuma Sangyo Co., Ltd.) and an attached moisture vaporizer (EV-2000, manufactured by Hiranuma Sangyo Co., Ltd.) under the following measurement conditions: sample weight 0.1 g, nitrogen flow rate 0.2 L / min, and heating temperature 150°C.

[0098]

[0099] Table 2 shows that the composite silica particles of Examples 1 to 9 and the granulated particles of Example 10, which contain porous silica particles and a non-volatile component including ceramides, have a pore volume of 0.5 mL / g or more, a boiling point (1013 hPa) of the non-volatile component of 150°C or more, and a pore volume ratio of 110% or less, have a high release concentration of ceramides into oleic acid and can efficiently elute ceramides into sebum. As a result, when used in cosmetics, etc., the ceramides are efficiently applied to the skin. Furthermore, because the ceramides in the porous silica particles are amorphous, it is believed that the elution of ceramides into water, such as sweat, is also improved. On the other hand, Comparative Example 1, which does not contain porous silica particles, Comparative Examples 2, 3, and 5, which have a pore volume occupancy rate of more than 110%, and Comparative Example 4, which uses non-porous silica instead of porous silica, have a low release concentration of ceramides into oleic acid because the ceramides are crystalline.

[0100] According to the present invention, it is possible to provide composite silica particles and granulated particles containing composite silica particles and a water-soluble polymer, which can easily release ceramides upon contact with oleic acid, a major component of sebum, as well as methods for producing these.

Claims

1. Composite silica particles in which a non-volatile component containing ceramides is supported on porous silica particles, wherein the pore volume of the porous silica particles is 0.5 mL / g or more, the boiling point (normal pressure: 1013 hPa) of the non-volatile component is 150°C or more, and the pore volume ratio obtained by the following calculation formula (1) is 110% or less. (Pore volume ratio (%)) = (total amount of non-volatile component supported on porous silica particles (mL)) / {(amount of porous silica particles (g)) × (pore volume of porous silica particles (mL / g))} × 100 (1) 2. The composite silica particles according to claim 1, wherein the ceramides are in an amorphous state.

3. The composite silica particles according to claim 1 or 2, wherein the mass ratio of the non-volatile component to the porous silica particles (non-volatile component / porous silica particles) is 4 or less.

4. The composite silica particles according to any one of claims 1 to 3, wherein the non-volatile component contains alcohol, and the dissolution amount of the alcohol in 100 g of water (25°C, 1013 hPa) is more than 1 g.

5. The composite silica particles according to claim 4, wherein the alcohol contains a glycol-based solvent.

6. The composite silica particles according to claim 4 or 5, wherein the alcohol contains dipropylene glycol.

7. The composite silica particles according to any one of claims 1 to 6, wherein the non-volatile component contains a surfactant.

8. The composite silica particles according to any one of claims 1 to 7, wherein the content of ceramides in the non-volatile component is 5% by mass or more.

9. Granulated particles containing the composite silica particles according to any one of claims 1 to 8.

10. The granulated particles according to claim 9, further containing a water-soluble polymer.

11. The granulated particles according to claim 9 or 10, wherein the water content in the granulated particles is 10% by mass or less.

12. A method for producing the composite silica particles according to any one of claims 1 to 8, having the following steps 1 and 2 in this order. Step 1: A step of mixing an emulsion or solution containing a non-volatile component containing the ceramides with the porous silica particles to obtain a suspension. Step 2: A step of drying the suspension obtained in Step 1.

13. The method for producing granulated particles according to claim 10 or 11, having the following steps 1' and 2' in this order. Step 1': A step of mixing an emulsion or solution containing a non-volatile component containing ceramides, porous silica particles, and a water-soluble polymer to obtain a suspension. Step 2': A step of spray-drying the suspension obtained in step 1'.

14. The method for producing granulated particles according to claim 13, wherein the water-soluble polymer is a water-soluble polysaccharide.

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