Composite silica particles

Abstract

To provide composite silica particles and granulated particles of the composite silica particles, and methods for producing them, which can easily release ceramides by coming into contact with oleic acid, which is a main component of sebum.SOLUTION: [1] Composite silica particles in which a non-volatile component including ceramides is supported on porous silica particles, wherein a pore volume of the porous silica particles is 0.5 mL / g or more, and a ratio to pore volume (a volume ratio of a content of the non-volatile component to a volume of pore portions of the porous silica particles) is 110% or less. [2] Granulated particles comprising the composite silica particles [1]. [3] A method for producing the composite silica particles [1], the method comprising, in the following order, a step 1 for obtaining a suspension and a step 2 for drying. [4] A method for producing the granulated particles [2], the method comprising, in the following order, a step 1' for obtaining a suspension and a step 2' for spray drying.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Ceramides exist as components of the intercellular lipids of the stratum corneum cells that cover the outermost layer of the skin, and play an important role in maintaining the function of the natural barrier membrane between the living body and the outside world of the skin. When such ceramides are formulated into external preparations or cosmetics and applied to the skin, it is widely known that they are effective in improving the moisturizing effect and enhancing care effects such as preventing or improving rough skin.

[0003] As a method of using ceramides as cosmetics or the like, for example, Patent Document 1 discloses a solid powder cosmetic containing (A) 60 to 75% by weight of a powder component containing 0.1 to 20% by weight of porous inorganic powder in the total composition and (B) 25 to 40% by weight of an oil component containing 0.1 to 15% by weight of a moisturizing component in the total composition, and ceramides are disclosed as the moisturizing component.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, although the solid powder cosmetic of Cited Document 1 has both a moist feeling and a smooth feeling when using the cosmetic, no study has been made on the amount of release of the moisturizing component (especially ceramides) into sebum, and there are cases where 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 by contacting with oleic acid, which is a main component of sebum, and methods for producing the same.

Means for Solving the Problems

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

Advantages of the Invention

[0007] According to the present invention, there can be provided composite silica particles capable of easily releasing ceramides by contacting with oleic acid which is a main component of sebum, granulated particles containing the composite silica particles and a water-soluble polymer, and methods for producing them.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] [Composite silica particles] The composite silica particles of the present invention are composite silica particles in which a porous silica particle supports a nonvolatile component containing ceramides, the pore volume of the porous silica particle is 0.5 mL / g or more, the boiling point (normal pressure: 1013 hPa) of the nonvolatile component is 150°C or more, and the relative pore volume ratio obtained by the following calculation formula (1) is 110% or less. (Relative pore volume ratio (%)) = (total amount (mL) of nonvolatile components supported on the porous silica particles) / {(amount (g) of the porous silica particles) × (pore volume (mL / g) of the porous silica particles)} × 100 (1)

[0009] The composite silica particles of the present invention can easily release ceramides contained in the pore portions of the porous silica particles by contacting with oleic acid which is a main component of sebum. The reason is not clear, but it is considered as follows. The composite silica particles of the present invention are those in which a nonvolatile component containing ceramides is supported on the pore portions of the porous silica particles, and thereby it is considered that the ceramides can be maintained in an amorphous state. Since the ceramides are in an amorphous state, it is considered that the time until the ceramides dissolve in oleic acid is shorter than when the ceramides are in a crystalline state. Therefore, it is considered that the composite silica particles of the present invention increase the release amount of ceramides when contacting with oleic acid present on the skin. In addition, in the composite silica particles of the present invention, since the pore volume of the porous silica particles is 0.5 mL / g or more, a sufficient amount of a nonvolatile component containing ceramides can be supported in the pores. In addition, in the composite silica particles of the present invention, by setting the relative pore volume ratio (the volume ratio of the content of the non-volatile component to the volume of the pore portion of the porous silica particles) to 110% or less, the amount of ceramides crystallizing outside the pores of the porous silica particles can be suppressed, and it means that blocking the entrance of the pore portion can be suppressed. As a result, it is considered that a decrease in the release amount of ceramides when contacting oleic acid, which is a main component of sebum, can be suppressed. Note that a relative pore volume ratio of 110% indicates that at least 10% of the non-volatile component adheres to and exists on the surface outside the pores of the porous silica particles in addition to 100% inside the pores of the porous silica particles.

[0010] In this specification, the relative pore volume ratio obtained by the above calculation formula (1) represents the volume ratio of the content of the non-volatile component to the volume of the pore portion of the porous silica particles. In the composite silica particles of the present invention, from the viewpoint of suppressing a decrease in the release amount of ceramides to oleic acid, which is a main component of sebum, the relative pore volume ratio obtained by the above calculation formula (1) is 110% or less, preferably 100% or less, more preferably 80% or less, still more preferably 70% or less, even more preferably 60% or less, and from the viewpoint of increasing the loading amount of ceramides and further improving the release amount of ceramides to oleic acid, which is a main component of sebum, it is preferably 5% or more, more preferably 10% or more, still more preferably 25% or more, 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, still more preferably 25% or more and 80% or less, even more preferably 35% or more and 70% or less, even more preferably 35% or more and 60% or less.

[0011] <Porous silica particles> In the present invention, from the viewpoint of supporting a non-volatile component containing ceramides in the pores, the pore volume of the porous silica particles is 0.5 mL / g or more. The pore volume of the porous silica particles is 0.5 mL / g or more, preferably 1.0 mL / g or more, more preferably 1.2 mL / g or more, still more preferably 1.4 mL / g or more, from the viewpoint of retaining ceramides in an amorphous state in the pores. And from the viewpoint of ensuring the strength of the particles, it is preferably 8.0 mL / g or less, more preferably 5.0 mL / g or less, still more preferably 3.0 mL / g or less, and even more preferably 2.0 mL / g or less. From these viewpoints, it is 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, more preferably 1.2 mL / g or more and 3.0 mL / g or less, and 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 under a vacuum of 1 kPa or less at a temperature of 200 °C for 3 hours or more, and then obtaining an adsorption isotherm only on the adsorption side of nitrogen at the liquid nitrogen temperature and analyzing it 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 the "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 pore volume in this range is the pore volume in the present invention.

[0013] The specific surface area (BET specific surface area) of the porous silica particles by the BET method is preferably 200 m 2 / g or more, more preferably 300 m 2 / g or more, still more preferably 500 m 2 / g or more from the viewpoint of supporting non-volatile components and retaining ceramides in an amorphous state. And from the viewpoint of ensuring the strength of the particles, it is preferably 1500 m 2 / g or less, more preferably 1000 m 2 / g or less, still more preferably 850 m 2 / g or less. From these viewpoints, it is preferably 200 m 2 / g or more and 1500 m 2 / g or less, more preferably 300 m 2 / g or more and 1000 m2 500 m / g or less, more preferably 500 m / g or less 2 850 m / g or more and 500 m / g or less 2 / g or less. The specific surface area by the BET method is a value obtained by drying the sample to be measured under a vacuum of 1 kPa or less at a temperature of 200 °C for 3 hours or more, and then obtaining an adsorption isotherm only on the adsorption side of nitrogen at the liquid nitrogen temperature and analyzing it by the BET method.

[0014] From the viewpoint of the feel when used in cosmetics or the like, the average particle diameter of the porous silica particles is preferably 1.0 μm or more, more preferably 2.0 μm or more, still more preferably 3.0 μm or more, and even more preferably 5.0 μm or more. Similarly, from the viewpoint of the feel when used in cosmetics or the like, it is preferably 50.0 μm or less, more preferably 30.0 μm or less, still more preferably 20.0 μm or less, and even more preferably 15.0 μm or less. 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, still 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 diameter of the porous silica particles is the median diameter D 50 (hereinafter, also simply referred to as "median diameter"). Specifically, it is measured by the method described in the examples.

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

[0016] The shape of the porous silica particles is not particularly limited, but from the perspective of the feel when used in cosmetics or the like, it is preferably spherical. The shape of the porous silica particles is not particularly limited, and may be amorphous, spherical, elliptical, polyhedral, prismatic, etc., and is usually spherical or elliptical. Also, two or more kinds having different shapes may be used. The shape of the porous silica particles is not particularly limited, but from the perspective of the usability when used in cosmetics or the like, a spherical shape is preferred.

[0017] <Non-volatile component> The composite silica particles of the present invention contain a non-volatile component containing ceramides. In the present invention, the non-volatile component refers to those 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 from the perspective of suppressing volatilization from the composite silica particles, preferably 180°C or higher, more preferably 200°C or higher. 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 non-volatile component is preferably 80 or higher, more preferably 100 or higher, from the perspective of raising the boiling point, and preferably 6000 or lower, more preferably 3000 or lower, further preferably 2000 or lower, even more preferably 1500 or lower, even more preferably 1000 or lower, from the perspective of being supported in the pores of the porous silica particles. From these perspectives, it is preferably 80 or higher and 6000 or lower, more preferably 100 or higher and 3000 or lower, further preferably 100 or higher and 2000 or lower, even more preferably 100 or higher and 1500 or lower, even more preferably 100 or higher and 1000 or lower.

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

[0019] As the natural ceramides, natural ceramides such as glycosphingolipid, ceramide EOS, ceramide EOP, ceramide NS, ceramide NG, ceramide NP, ceramide EOH, ceramide AS, ceramide AG, and ceramide AP are preferably exemplified. Examples of commercially available natural ceramides include Ceramide I, Ceramide III, Ceramide IIIB, Ceramide VI (manufactured by Evonik Industries AG), Ceramide TIC-001 (manufactured by Takasago International Corporation), CERAMIDE II (manufactured by Croda Inc.), DS-Ceramide VI, C6-Phytoceramide, DS-ceramide Y3S (manufactured by Doosan Corporation), and CERAMIDE2 (manufactured by Croda Inc.).

[0020] As the pseudo-ceramide, a pseudo-ceramide represented by the following general formula (1) is preferred.

[0021]

Chemical formula

[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 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-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 is preferably nonyl, tridecyl, pentadecyl, undecyl group ester-bonded with linoleic acid at the ω-position, pentadecyl group ester-bonded with linoleic acid at the ω-position, pentadecyl group ester-bonded with 12-hydroxystearic acid at the ω-position, or undecyl group amide-bonded with methyl-branched isostearic acid at the ω-position.

[0024] R 1 When R is a hydrogen atom, R 3 is an alkyl group having 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 When 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 preferably represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a hydroxyl group, a hydroxyalkoxy group, an alkoxy group or an acetoxy group. As the hydroxyalkoxy group or alkoxy group of R 3 those having 1 to 7 carbon atoms are preferred.

[0025] As the pseudo-ceramide represented by the general formula (1), 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 are preferred, and N-(hexadecyloxyhydroxypropyl)-N-hydroxyethyldecanamide is more preferred.

[0026] In the present invention, since the ceramides are supported in the pores of the porous silica particles, they 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. Since the ceramides are in an amorphous state, they are more easily dissolved in oleic acid and the like as compared with the case of being in a crystalline state. Therefore, when the composite silica particles of the present invention come into contact with oleic acid which is a main component of sebum, the ceramides can be easily released. In the present invention, the crystalline state of 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 the conditions of a temperature range of 25 to 90°C and a heating rate of 1°C / min. When an endothermic peak of 1.0 J / g or more is present, it is determined that the ceramides are crystalline. On the other hand, when 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 confirmation of the crystallinity of the ceramides is specifically determined by the method of the examples.

[0027] In the present invention, the content of ceramides in the non-volatile component is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 12% by mass or more, and even more preferably 15% by mass or more from the viewpoint of increasing the loading amount of ceramides and further improving the release amount of ceramides to oleic acid, which is the main component of sebum. And from the viewpoint of suppressing the crystallization of ceramides due to excessive loading of ceramides, it is preferably 100% by mass or less, more preferably 80% by mass or less, still 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, still 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, still more preferably 5% by mass or more, and even more preferably 6% by mass or more from the viewpoint of increasing the loading amount of ceramides and further improving the release amount of ceramides to oleic acid, which is the main component of sebum. And, from the viewpoint of suppressing the crystallization of ceramides due to excessive loading of ceramides, it is preferably 80% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and even more preferably 10% by mass or less. From these viewpoints, it 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, still 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) In the composite silica particles of the present invention, the non-volatile component preferably contains alcohol. The dissolution amount of alcohol in 100 g of water (25 °C, normal pressure: 1013 hPa) is preferably more than 1 g. For the measurement of the dissolution amount, reference can be made to, for example, Journal of the Chemical Society of Japan, 1985, No. 11, p2116 - 2119 and Journal of the Chemical Society of Japan, 1982, No. 11, p1830 - 1834, etc. Since alcohol has an affinity for ceramides, when the composite silica particles of the present invention contain alcohol, the release amount of ceramides to oleic acid, which is the main component of sebum, can be further improved.

[0030] Alcohol may have substituents and functional groups. Examples of the substituent include an alkoxy group having 1 to 3 carbon atoms and an acetyl group. Examples of the functional group include an ether group and 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 still 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, 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] From the viewpoint of suppressing volatilization from the composite silica particles, the boiling point of the alcohol (normal pressure: 1013 hPa) is preferably 150 °C or higher, more preferably 180 °C or higher, and still more preferably 200 °C or higher. 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 still more preferably 400 °C or lower. Also, from the viewpoint of the affinity for porous silica, the melting point of the alcohol (normal pressure: 1013 hPa) is preferably less than 25 °C, more preferably 20 °C or lower.

[0032] As the alcohol, one or more selected from glycol solvents and glycerin solvents are preferred, and from the viewpoint of improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to the affinity with ceramides, glycol solvents are more preferred.

[0033] From the viewpoint of the affinity with ceramides, the number of carbon atoms of the glycol solvent is preferably 2 or more and 12 or less, more preferably 3 or more and 8 or less, and still more preferably 4 or more and 7 or less. Also, the glycol solvent may be alkoxylated with a hydrocarbon having 1 to 3 carbon atoms or may be acetylated.

[0034] Examples of the glycol-based solvents as described above 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), 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), polypropylene glycol (boiling point 287 °C). The glycol-based solvent may be alkoxylated with a hydrocarbon having 1 to 3 carbon atoms and may be further acetylated. Examples thereof 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). Among these, as the glycol-based solvent, one or more selected from monoalkyl glycols and polyalkyl glycols are preferable, polyalkyl glycols are more preferable, and dipropylene glycol (boiling point 232 °C) is still more preferable.

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

[0036] In the present invention, the content of alcohol in the nonvolatile component is preferably 10% by mass or more, more preferably 20% by mass or more, still 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 the affinity with ceramides; and preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, from the viewpoint of supporting ceramides. From these viewpoints, it 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, still more preferably 40% by mass or more and 80% by mass or less. In the present invention, the preferred content of the glycol-based solvent in the non-volatile component and dipropylene glycol in the non-volatile component is also in the same range as described 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, still 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 the affinity with ceramides; and from the viewpoint of carrying ceramides, it is preferably 20.0 or less, more preferably 10.0 or less, still more preferably 6.0 or less. From these viewpoints, it is preferably from 0.1 to 20.0, more preferably from 1.0 to 10.0, still more preferably from 2.0 to 6.0. In the present invention, the preferred mass ratio of the glycol-based solvent to ceramides and dipropylene glycol to ceramides is also in the same range as described 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, still 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 the affinity with ceramides; and from the viewpoint of carrying ceramides, it is preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less. From these viewpoints, it is preferably from 5% by mass to 40% by mass, more preferably from 10% by mass to 35% by mass, still more preferably from 20% by mass to 30% by mass. In the present invention, the preferred content of the glycol-based solvent in the composite silica particles is also in the same range as described above.

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

[0040] Examples of the anionic surfactant include fatty acid salts such as sodium laurate, potassium laurate, and potassium palmitate; polyoxyethylene alkyl ether carboxylates such as sodium polyoxyethylene tridecyl ether 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 sodium polyoxyethylene oleyl ether phosphate and sodium polyoxyethylene stearyl ether phosphate; alkyl sulfate esters such as sodium lauryl sulfate and potassium lauryl sulfate; polyoxyethylene alkyl ether sulfate esters such as potassium polyoxyethylene lauryl sulfate, sodium polyoxyethylene lauryl sulfate, and triethanolamine polyoxyethylene lauryl sulfate; acylated amino acid salts such as sodium lauroyl sarcosine, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, triethanolamine N-lauroyl glycine, potassium N-coconut oil fatty acid acyl glycine, triethanolamine N-lauroyl-β-alanine, and triethanolamine N-stearoyl-β-alanine; fatty acid amide sulfonates such as sodium N-myristoyl-N-methyl taurate and sodium N-stearoyl-N-methyl taurate; and sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate, etc. Among these, as the anionic surfactant, fatty acid amide sulfonates are preferred, and sodium N-stearoyl-N-methyl taurate is more preferred.

[0041] Examples of cationic surfactants include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salts. As the primary amine compound, secondary amine compound, and tertiary amine compound, those formed into salts with organic acids and / or inorganic acids can be used. Examples of the primary amine compound include long-chain alkylamines such as laurylamine, myristylamine, and palmitylamine. Examples of the secondary amine compound include dialkylamines having a long-chain alkyl group and a short-chain alkyl group such as long-chain alkylmethylamine, long-chain alkylethylamine, and long-chain alkylpropylamine, sphingosines such as 4D-hydroxysphinganine, and 1-(2-hydroxyethylamino)-3-isostearyloxy-2-propanol. Examples of the tertiary amine compound include trialkylamines having a long-chain alkyl group and a short-chain alkyl group such as long-chain alkyldimethylamine, long-chain alkyldiethylamine, and long-chain alkyldipropylamine, long-chain fatty acid dialkylaminoethylamides and long-chain fatty acid dialkylaminopropylamides such as dimethylaminopropylamide stearate and diethylaminoethylamide stearate, acyloxyethyl dialkylamines and acyloxypropyl dialkylamines such as hexadecyloxypropyl dimethylamine, stearoxypropyl dimethylamine, stearoxyethyl dimethylamine, octadecyloxypropyl dimethylamine (N,N-dimethyl-3-octadecyloxypropylamine), arachiloxypropyl dimethylamine, and behenyloxypropyl dimethylamine. Examples of the quaternary ammonium salt 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, as the cationic surfactant, a secondary amine compound is preferable, sphingosines are more preferable, and 1-(2-hydroxyethylamino)-3-isostearyloxy-2-propanol is still more preferable.

[0042] When using the primary amine compound, secondary amine compound, and tertiary amine compound as salts, examples of the inorganic acids include phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, carbonic acid, and the like. Examples of the 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 the nonionic surfactants include sorbitan fatty acid esters such as sorbitan monostearate; polyglycerin fatty acid esters such as glycerin fatty acid ester and polyglyceryl monoisostearate; polyoxyethylene fatty acid esters such as propylene glycol fatty acid ester 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 sorbitan; 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; polyoxyalkylene-modified silicones such as polyoxyethylene·methylpolysiloxane copolymer, and the like. Among these, as the nonionic surfactant, polyoxyethylene hydrogenated castor oil is preferred.

[0044] Examples of the amphoteric surfactants include betaine-based amphoteric surfactants such as lauryldimethylaminoacetic acid betaine, lauroylamidobetaine, and laurylsulfobetaine.

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

[0046] In the present invention, the mass ratio of the surfactant to ceramides (surfactant / ceramides) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, even more preferably 0.3 or more, from the viewpoint of further improving the release amount of ceramides into oleic acid, which is the main component of sebum, due to the affinity with ceramides. And from the viewpoint of supporting ceramides, it is preferably 10.0 or less, more preferably 5.0 or less, still more preferably 3.0 or less, 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, still more preferably 0.1 or more and 3.0 or less, 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, still more preferably 2% by mass or more, from the viewpoint of further improving the release amount of ceramides into oleic acid, which is the main component of sebum, due to the affinity with ceramides. And from the viewpoint of supporting ceramides, it is preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 6% by mass or less. From these viewpoints, it 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, still more preferably 2% by mass or more and 6% by mass or less.

[0048] (Oil agent) In the composite silica particles of the present invention, the nonvolatile component preferably contains an oil agent. Since the oil agent has an affinity for ceramides, the inclusion of the oil agent in the composite silica particles of the present invention can further improve the release amount of ceramides to oleic acid, which is the main component of sebum. The oil agent is preferably a compound that is hardly soluble in water from the viewpoint of its affinity for ceramides. Therefore, the amount of the oil agent dissolved 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 still more preferably 0.001 g or less. For the measurement of the dissolution amount, reference can be made to, for example, Journal of the Chemical Society of Japan, 1985, No. 11, p2116-2119 and Journal of the Chemical Society of Japan, 1982, No. 11, p1830-1834. Examples of the oil agent include liquid oils and solid oils, and one or more selected from liquid oils and solid oils are preferred, and solid oils are preferred. In the present invention, the oil agent does not include the alcohol having a dissolution amount in 100 g of water (25 °C, normal pressure: 1013 hPa) exceeding 1 g.

[0049] 〔Liquid oil〕 Examples of the liquid oil include hydrocarbon oils, ether oils, ester oils, other alcohols excluding the alcohol having a dissolution amount in 100 g of water (25 °C, normal pressure: 1013 hPa) exceeding 1 g, silicone oils, fluorine oils, etc., having a melting point (normal pressure: 1013 hPa) of less than 25 °C. Specific examples of the liquid oil 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 perfluoroalkyl ethyl phosphate, perfluoroalkyl polyoxyethylene 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 the solid oil include higher alcohols (including sterols) excluding the above-mentioned alcohols, higher fatty acids, and hydrocarbon oils such as petrolatum. Among these, sterols are preferable from the viewpoint of improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to their affinity with ceramides. Examples of the sterols include animal-derived sterols and plant-derived sterols. Examples of the animal-derived sterols include cholesterol, dihydrocholesterol, and cholesteryl succinate. Examples of the plant-derived sterols include sitosterol, stigmasterol, and campesterol. Among these, animal-derived sterols are preferable as the sterols, and cholesterol is more preferable.

[0051] In the present invention, 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, the content of the oil agent in the non-volatile component is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and even more preferably 5% by mass or more. From the viewpoint of supporting ceramides, it is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and even more preferably 10% by mass or less. From these viewpoints, it is preferably from 0.5% by mass to 50% by mass, more preferably from 1% by mass to 30% by mass, still more preferably from 3% by mass to 20% by mass, and even more preferably from 5% by mass to 10% by mass.

[0052] In the present invention, 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, the mass ratio of the oil agent to ceramides (oil agent / ceramides) is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.1 or more. From the viewpoint of supporting ceramides, it is preferably 10.0 or less, more preferably 5.0 or less, and still more preferably 1.0 or less. From these viewpoints, it is preferably from 0.01 to 10.0, more preferably from 0.05 to 5.0, and still more preferably from 0.1 to 1.0.

[0053] In the present invention, 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, the content of the oil agent in the composite silica particles is preferably 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably 2% by mass or more. From the viewpoint of supporting ceramides, it is preferably 15% by mass or less, more preferably 12% by mass or less, and still more preferably 6% by mass or less. From these viewpoints, it is preferably from 1% by mass to 15% by mass, more preferably from 1.5% by mass to 12% by mass, and still more preferably from 2% by mass to 6% by mass.

[0054] In the present invention, the mass ratio of the non-volatile component to the porous silica particles (non-volatile component / porous silica particles) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and even more preferably 0.15 or more from the viewpoint of supporting the non-volatile component containing ceramides. And from the viewpoint of containing the non-volatile component containing ceramides in the pores, it is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and even more preferably 1.5 or less. From these viewpoints, it is preferably 0.01 or more and 4 or less, more preferably 0.05 or more and 3 or less, still 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 the porous silica particles. Therefore, the surface of the composite silica particles of the present invention can be modified, so that when the composite silica particles are used in cosmetics or the like, the compatibility with the skin becomes better and the feel is further improved. In addition, since the surface of the porous silica particles is modified by the water-soluble polymer, ceramides are more likely to elute from the composite silica particles, and the release amount of ceramides to oleic acid, which is the main component of sebum, can be further improved. In addition, when producing granulated particles containing the composite silica particles described below, since the water-soluble polymer exhibits the effect of a granulating agent, the granulated particles can be obtained more efficiently.

[0056] The amount of the water-soluble polymer dissolved in 100 g of water (25 °C, normal pressure: 1013 hPa) is preferably 1 g or more from the viewpoint of the affinity for the porous silica particles. For the measurement of the dissolution amount, reference can be made to, for example, Journal of the Chemical Society of Japan, 1985, No. 11, p2116 - 2119 and Journal of the Chemical Society of Japan, 1982, No. 11, p1830 - 1834, etc.

[0057] The weight average molecular weight of the water-soluble polymer is preferably 10,000 or more, more preferably 30,000 or more, still more preferably 50,000 or more, and preferably 500,000 or less, more preferably 400,000 or less, still more preferably 300,000 or less, from the viewpoint of the affinity for the porous silica particles. 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] As the water-soluble polymer, one or more selected from synthetic polymers and natural polymers are preferable, and natural polymers are more preferable from the viewpoint of the affinity for the porous silica particles. Examples of the synthetic polymer include salts such as sodium salts and potassium salts of polyacrylic acid and polymethacrylic acid, and polyvinylpyrrolidone. As the natural polymer, water-soluble polysaccharides are preferable. Examples of the water-soluble polysaccharides include saccharides such as glucose, lactose, and sucrose, polysaccharides having these saccharides as constituent units, and derivatives thereof. The derivatives have 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 the water-soluble polysaccharides include locust bean gum, guar gum, tamarind gum, quince seed-derived gum, gum arabic, tragacanth gum, karaya gum, carrageenan, pectin, hydroxypropyl guar gum, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, tuberose polysaccharide, xanthan gum, gellan gum, dextran, pullulan, hyaluronic acid, chondroitin sulfate, dermatan sulfate, mucopolysaccharides such as chitin and chitosan. Among these, one or more selected from xanthan gum and pullulan are preferable, and pullulan is preferable.

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

[0060] In the present invention, from the viewpoints of further improving the release amount of ceramides to oleic acid, which is the main component of sebum, due to the affinity with porous silica particles, and obtaining granulated particles, 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 still more preferably 3% by mass or more. And from the viewpoint of supporting ceramides, it is preferably 18% by mass or less, more preferably 14% by mass or less, and still more preferably 8% by mass or less.

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

[0062] In the present invention, from the viewpoint of supporting non-volatile components, the average particle diameter of the composite silica particles is preferably 1.0 μm or more, more preferably 3.0 μm or more, and still more preferably 5.0 μm or more. And from the viewpoint of the feel when used in cosmetics or the like, it is preferably 50.0 μm or less, more preferably 30.0 μm or less, still more preferably 20.0 μm or less, and even more preferably 15.0 μm or less. The average particle diameter of the composite silica particles is the median diameter D in the particle size distribution of volume frequency by laser diffraction measurement 50 (hereinafter, also simply referred to as "median diameter"), and specifically, it is measured by the method described in the examples. Moreover, it is preferable that the composite silica particles of the present invention are in powder form. The fact that it is in powder form can be confirmed by the fact that each particle exists separately under an optical microscope.

[0063] <Method for producing composite silica particles> The method for producing the composite silica particles of the present invention has 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 above-mentioned ceramides with the above-mentioned porous silica particles to obtain a suspension Step 2: A step of drying the suspension obtained in Step 1.

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

[0065] 〔Emulsion〕 An emulsion containing a non-volatile component containing ceramides can be obtained by mixing an oil phase containing ceramides and an aqueous phase containing a surfactant. That is, when using an emulsion 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 and an aqueous phase containing a surfactant to obtain an emulsion containing a non-volatile component containing ceramides

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

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

[0068] In Step 1, the content of ceramides in the above emulsion is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less. In Step 1, the content of the oil agent in the above emulsion is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less. In Step 1, the content of the surfactant in the above emulsion is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more from the viewpoint of emulsification, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

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

[0070] As the solvent used for the solution, an organic solvent having a boiling point (normal pressure: 1013 hPa) of 100°C or lower is preferable, one or more selected from ethanol, acetone, and methyl ethyl ketone are preferable, and ethanol is preferable. Since the boiling point of the solvent used for the oil agent is 100°C or lower, the solvent can be removed from the obtained composite silica particles by drying in Step 2.

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

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

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

[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, still more preferably 80 to 200°C. Also, the drying time is preferably 8 to 72 hours, more preferably 10 to 24 hours, still more preferably 12 to 18 hours. As the apparatus used for shelf drying, a commercially available electric dryer or the like can be used.

[0075] When the drying in Step 2 is spray drying, examples of the spray drying method include known methods such as the rotary disk method, pressure nozzle, two-fluid nozzle method, four-fluid nozzle method, etc. Among these, the two-fluid nozzle method is preferred as 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, still 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, still more preferably 70°C to 100°C. The outlet temperature can be adjusted by controlling the inlet temperature. As the apparatus used for spray drying, a commercially available spray drying apparatus can be used.

[0076] [Granular particles containing composite silica particles] The granular particles of the present invention are granular particles containing the above-mentioned composite silica particles. The granular particles of the present invention are obtained by granulating the above-mentioned composite silica particles with a water-soluble polymer. That is, the granular particles of the present invention preferably contain the above-mentioned composite silica particles and further contain a water-soluble polymer. As the water-soluble polymer, the same ones as the water-soluble polymer in the above-mentioned composite silica particles can be preferably used, and from the viewpoint of granulation properties, it is more preferably a water-soluble polysaccharide. The granulation can be carried out by the method for producing granular particles containing the composite silica particles described below. Since the granular particles of the present invention contain the above-mentioned composite silica particles, they can easily release ceramides by contacting with oleic acid, which is a main component of sebum.

[0077] In the granulated particles of the present invention, the content of the water-soluble polymer with respect to 100 parts by mass of the porous silica particles is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, still 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 amount of ceramides to oleic acid, which is the main component of sebum, due to the affinity with the porous silica particles. From the same viewpoint, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. From these viewpoints, it is preferably 0.5 part 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, still 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 preferable content of the water-soluble polysaccharide with respect to 100 parts by mass of the porous silica particles is also in the same range as above.

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

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

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

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

[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' functions as a so-called granulating agent, the granulated particles of the present invention can be obtained by spray-drying the suspension in Step 2'. As the method of spray-drying in Step 2', the same method as the spray-drying method in Step 2 of the method for producing the above-mentioned composite silica particles is preferable.

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

[37] . [1] Composite silica particles in which a non-volatile component including 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 (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 (mL) of non-volatile components supported on porous silica particles) / {(amount (g) of porous silica particles) × (pore volume (mL / g) of porous silica particles)} × 100 (1) [2] The composite silica particles according to [1], wherein the pore volume ratio obtained 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 obtained 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 non-volatile component to the porous silica particles (non-volatile component / porous silica particles) is 4 or less. 〔12〕The composite silica particles according to any one of 〔1〕 to 〔11〕, wherein the mass ratio of the non-volatile component to the porous silica particles (non-volatile component / porous silica particles) 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 non-volatile component to the porous silica particles (non-volatile component / porous silica particles) is 0.05 or more and 3 or less. 〔14〕The composite silica particles according to any one of 〔1〕 to 〔13〕, 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. 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. The composite silica particles 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. The composite silica particles according to any one of

[14] to

[16] , wherein the alcohol contains a glycol-based solvent. The composite silica particles according to any one of

[14] to

[17] , wherein the alcohol contains dipropylene glycol. The composite silica particles according to any one of [1] to

[17] , wherein the non-volatile component contains a surfactant. The composite silica particles 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. The composite silica particles 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. The composite silica particles according to any one of [1] to

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

[22] , further comprising a water-soluble polymer. The composite silica particles according to

[23] , wherein the water-soluble polymer is a water-soluble polysaccharide. The composite silica particles according to

[23] or

[24] , wherein the content of the water-soluble polymer with respect to 100 parts by mass of the porous silica particles is 0.5 part by mass or more and 50 parts by mass or less. The composite silica particles according to any one of

[21] to

[23] , wherein the content of the water-soluble polymer with respect to 100 parts by mass of the porous silica particles is 1 part by mass or more and 30 parts by mass or less. 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. 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. The composite silica particles according to any one of [1] to

[28] , which are in powder form. Granulated particles containing the composite silica particles according to any one of [1] to

[29] . The granulated particles according to

[30] , further containing a water-soluble polymer. The granulated particles according to

[30] or

[31] , wherein the water content in the granulated particles is 10% by mass or less. The granulated particles according to any one of

[30] to

[32] , wherein the water content in the granulated particles is 7% by mass or less. The granulated particles according to any one of

[30] to

[33] , wherein the water content in the granulated particles is 5% by mass or less. A method for producing the composite silica particles according to any one of [1] to

[29] , comprising 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. 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 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'. The method for producing granulated particles containing the composite silica particles according to

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

Examples

[0084] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples in any way. Each property value was measured and evaluated by the following method.

[0085] <Production of Composite Silica Particles> Examples 1 to 4 and Comparative Examples 2 to 5 (Preparation of oil phase) For the oil phases (solutions) of Examples 1 to 4 and Comparative Examples 2 to 5, those mixed with the compositions described in Table 1 were used. The mixing was carried out using a propeller blade (diameter 30 mm, width 5 mm) under the conditions of a propeller blade rotation speed of 120 rpm, a mixing temperature of 60°C, and a mixing time of 10 minutes. (Preparation of suspension) The oil phase (solution) prepared with the composition described in Table 1 was mixed with porous silica particles or non-porous silica particles with the compositions shown in Table 1 to obtain a suspension. The mixing of the suspension was carried out using a stirring rod under the conditions of a mixing temperature of 25°C and a mixing time of 5 minutes. (Production of composite silica particles) 10 g of the suspension was put into a crystallizing dish and shelf-dried using an electric dryer under the conditions of a drying temperature of 90°C and a drying time of 15 hours, and then allowed to cool at room temperature (25°C). By the shelf drying, ethanol, which is the solvent of the oil phase, was completely removed, and ceramides were supported on the porous silica particles or non-porous silica particles to obtain composite silica particles. The compositions, 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) For the oil phase of Example 5, that obtained by melting ceramides at 80°C was used. For the oil phases of Examples 6 to 8, those mixed with the compositions described in Table 1 were used. The 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) For the aqueous phases of Examples 5 to 8, those mixed with the compositions described in Table 1 were used. The mixing was carried out using a propeller blade (diameter 30 mm, width 5 mm) under the conditions of a propeller blade rotation speed of 120 rpm, a mixing temperature of 80°C, and a mixing time of 10 minutes. (Preparation of emulsion) The oil phase prepared with the composition described in Table 1 was mixed with the aqueous phase prepared with the composition described in Table 1 to prepare an emulsion. The mixing of the emulsion was carried out using a propeller blade (diameter 30 mm, width 5 mm) under the conditions of a propeller blade rotation speed of 120 rpm, a mixing temperature of 25°C, and a mixing time of 10 minutes. To this emulsion, 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 diameter 5 μm) were mixed in the composition shown in Table 1 to obtain a suspension. The mixing of the suspension was carried out using a propeller blade (diameter 30 mm, width 5 mm) under the conditions of a propeller blade rotation speed of 200 rpm, a mixing temperature of 25°C, and a mixing time of 60 minutes. (Production of composite silica particles) 10 g of the suspension was put into a crystallization dish and shelf-dried using an electric dryer under the conditions of a drying temperature of 90°C and a drying time of 15 hours, and then allowed to cool at room temperature. By the shelf-drying, ethanol as the solvent of the oil phase and deionized water as the solvent of the aqueous phase were completely removed, and ceramides were supported on the porous silica particles to obtain composite silica particles. The obtained composite silica particles are shown in Table 2.

[0087] Example 9 (Preparation of oil phase) The oil phase of Example 9 was the one mixed in the composition described in Table 1. The mixing was carried out using a propeller blade (diameter 30 mm, width 5 mm) under the conditions of 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 of Example 9 was the one mixed in the composition described in Table 1. The mixing was carried out using a propeller blade (diameter 30 mm, width 5 mm) under the conditions of a propeller blade rotation speed of 120 rpm, a mixing temperature of 80°C, and a mixing time of 10 minutes. (Preparation of suspension) The oil phase prepared in the composition described in Table 1 was mixed with the aqueous phase prepared in the composition described in Table 1 to prepare an emulsion. To this emulsion, pullulan (pullulan for cosmetics, 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 of 300 mL / 100 g, and an average particle size of 7.7 μm) were mixed in the composition shown in Table 1 to obtain a suspension. The mixing of the suspension was carried out using a propeller blade (diameter 30 mm, width 5 mm) under the conditions of a propeller blade rotation speed of 200 rpm, a mixing temperature of 25 °C, and a mixing time of 60 minutes. (Production of composite silica particles) 10 g of the suspension was placed in a crystallizing dish and shelf-dried using an electric dryer under the conditions of a drying temperature of 90 °C and a drying time of 15 hours, and then allowed to cool to room temperature. By the shelf drying, ethanol, which is the solvent of the oil phase, and deionized water, which is the solvent of the aqueous phase, were completely removed, and ceramides were supported on porous silica particles to obtain composite silica particles. The obtained composite silica particles are shown in Table 2.

[0088] (Production of granulated particles) Example 10 (Preparation of oil phase) The oil phase of Example 10 was the one mixed in the composition described in Table 1. The mixing was carried out using a propeller blade (diameter 150 mm, width 10 mm) under the conditions of 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 of Example 10 was the one mixed in the composition described in Table 1. The mixing was carried out using three inclined propeller blades (diameter 320 mm, width 60 mm) under the conditions of a propeller blade rotation speed of 120 rpm, a mixing temperature of 80 °C, and a mixing time of 10 minutes. (Preparation of suspension) The oil phase separately prepared in the composition described in Table 1 was mixed with the aqueous phase prepared in the composition described in Table 1 to prepare an emulsion. To this emulsion, pullulan (pullulan for cosmetics, 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 of 300 mL / 100 g, and an average particle size of 5 μm) were mixed in the composition shown in Table 1 to obtain a suspension. The mixing of the suspension was carried out using three inclined propeller blades (diameter 320 mm, width 60 mm) under the 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 supply temperature of 180°C using a pilot-scale co-current type spray dryer (AD-0506 N / R type spray dryer, manufactured by Asizawa Niro Atomizer Co., Ltd., tower length 8,650 mm, straight cylinder 6,000 mm, tower diameter 3,200 mm). The dried product obtained by the spray drying was collected at two points, under the tower and under the cyclone, and then mixed in the recovered mass ratio to obtain granulated particles containing composite silica particles. For the spraying during the spray drying, a two-fluid nozzle (CNP500 manufactured by Atmax Co., Ltd.) was used, and the spraying direction was upward. Also, by the spray drying, ethanol which is a solvent of the oil phase and deionized water which is a solvent of the aqueous phase were removed. The composition, physical properties, and evaluation results of the obtained granulated particles are shown in Table 2.

[0089] <Ceramide particles> Comparative Example 1 As the ceramide particles, a ceramide substance (Soft Care Ceramide SL-E, manufactured by Kao Corporation, average particle diameter 119 μm) was used in the as-received state.

[0090] Details of each component described 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 diameter 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 40 mL / 100 g, average particle diameter 20 μm 〔Ceramides〕 · N-(Hexadecyloxyhydroxypropyl)-N-hydroxyethylhexadecanamide Soft Care Ceramide: SL-E, manufactured by Kao Corporation, density 1.00 g / mL 〔Alcohol〕 · Dipropylene glycol: DPG-RF, manufactured by ADEKA Corporation, boiling point 232 °C, density 1.03 g / mL 〔Surfactant〕 · Anionic surfactant: Sodium N-stearoyl-N-methyltaurine: Nikkol SMT, manufactured by Nikko Chemicals Co., Ltd., density 1.00 g / mL · Cationic surfactant: 1-(2-Hydroxyethylamino)-3-isostearyloxy-2-propanol: HE-ISP, manufactured by Kao Corporation, density 0.91 g / mL · Nonionic surfactant: Polyoxyethylene hydrogenated castor oil: Emalex CH-60(K), manufactured by Kao Corporation, density 1.03 g / mL 〔Oil agent〕 · 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 Seika Co., Ltd., density 1.00 g / mL 〔Organic acid〕 · L-Glutamic acid: L-Glutamic acid, manufactured by Ajinomoto Co., Inc. 〔Water-soluble polymer〕 · Pullulan (water-soluble polysaccharide): Pullulan for cosmetics, manufactured by Hayashibara Co., Ltd., weight average molecular weight 200,000, density 1.00 g / mL 〔Solvent for oil phase〕 · Ethanol: Ethanol (99.5), manufactured by FUJIFILM Wako Pure Chemical Corporation 〔Solvent for aqueous phase〕 · Deionized water

[0091]

Table 1

[0092] [Evaluation and measurement methods] <Calculation of relative pore volume ratio> Regarding the relative pore volume ratio of the obtained composite silica particles or granulated particles, it was determined from the composition and pore volume of the silica particles described in Table 2, as well as the composition and density of the non-volatile components, using the following calculation formula (1). (Porosity ratio (%)) = (Total amount of non-volatile components supported on porous silica particles (mL)) / {(Amount of porous silica particles (g)) × (Pore volume of porous silica particles (mL / g))} × 100 (1)

[0093] <Crystallinity of ceramides> For the composite silica particles or granulated particles of the examples and comparative examples, measurement was carried out using a differential scanning calorimeter (manufactured by Hitachi High-Tech Corporation, DSC600) under the following measurement conditions. When there is an endothermic peak of 1.0 J / g or more, it is considered crystalline, and when there is no such endothermic peak, it is considered non-crystalline (amorphous). (Measurement conditions) · Temperature range: 25 to 90 °C · Heating rate: 1 °C / min

[0094] <Average particle diameter> The average particle diameters of the composite silica particles or granulated particles of the examples and comparative examples, and the porous silica particles used as raw materials were measured using a laser diffraction / scattering particle size distribution measuring device LA-920 (manufactured by Horiba, Ltd.). Under the following measurement conditions, the D50 (median diameter) measured after dispersing in ethanol was taken as the average particle diameter. (Measurement conditions) · Measurement temperature: 25 °C · Relative refractive index: 1.07

[0095] <Release concentration of ceramides into oleic acid> 10 g of oleic acid (Lunac O-V, manufactured by Kao Corporation) was added to a glass bottle with a capacity of 50 mL, and the composite silica particles or granulated particles of the examples and comparative examples were mixed therein so that the ceramides would be 7.2 g / L. The above glass bottle was placed in a water bath at 35°C, and using a magnetic stirrer (a stir bar (diameter 3.0 cm)), it was stirred under the conditions of 300 rpm for 10 minutes to obtain a dispersion. Thereafter, the dispersion was filtered through a membrane filter with a pore size of 0.8 μm (DISMIC 25CS080AN, manufactured by Advantec) to remove solid residues, and a release solution of ceramides, which is a sample for measurement, was obtained. 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. Note that oleic acid is one of the main components contained in sebum, and in this example, oleic acid was used as a model of sebum. That is, the larger the release concentration of ceramides into oleic acid, the larger the release amount of ceramides into sebum and thus into the skin. (Measurement conditions) · Detector: 5430 Diode Array Detector, manufactured by Hitachi High-Tech Corporation · Detection method: Absorbance (212 nm) · Column: CAPCELLPAK C18 MG, manufactured by Osaka Soda Co., Ltd. · Solvent: A mixture of 70 volume percent of acetonitrile (for high performance liquid chromatography, manufactured by Fujifilm Wako Pure Chemical Corporation) and 30 volume percent of tetrahydrofuran (for high performance liquid chromatography, manufactured by Fujifilm Wako Pure Chemical Corporation) · 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) method under the following conditions. <Measurement conditions> Column: TSKgel GMPWXL + TSKgel GMPWXL (manufactured by Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN = 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 weights: 1,100, 3,610, 14,900, 152,000, manufactured by POLMER STANDARDS SERVICE)

[0097] <Water content> Measurement was carried out using a Karl Fischer moisture meter (AQV-2200 manufactured by Hiranuma Sangyo Co., Ltd.) and an attached moisture vaporizer (EV-2000 manufactured by Hiranuma Sangyo Co., Ltd.). The measurement conditions were a sample amount of 0.1 g, a nitrogen flow rate of 0.2 L / min, and a heating temperature of 150 °C.

[0098]

Table 2

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

Industrial applicability

[0100] According to the present invention, composite silica particles capable of easily releasing ceramides by contacting with oleic acid which is a main component of sebum, granulated particles containing the composite silica particles and a water-soluble polymer, and methods for producing these can be provided.

Claims

1. Composite silica particles in which a porous silica particle supports 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 (atmospheric pressure: 1013 hPa) of the non-volatile component is 150°C or higher, and the ratio to pore volume calculated by the following formula (1) is 110% or less. Composite silica particles. (Ratio to pore volume (%)) = (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, 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 non-volatile component contains alcohol, and the amount of the alcohol dissolved in 100 g of water (25°C, 1013 hPa) is more than 1 g. The composite silica particles according to claim 1.

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, wherein the alcohol contains dipropylene glycol.

7. The composite silica particles according to claim 1, wherein the non-volatile component contains a surfactant.

8. The composite silica particles according to claim 1, 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. Furthermore, the granulated particles according to claim 9, which contain a water-soluble polymer.

11. The granulated particles according to claim 9, 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 claim 1, 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. A method for producing the granulated particles according to claim 10, 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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