WO2016002797A1 - 多孔質シリカ系粒子、その製造方法及びそれを配合した化粧料 - Google Patents
多孔質シリカ系粒子、その製造方法及びそれを配合した化粧料 Download PDFInfo
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- WO2016002797A1 WO2016002797A1 PCT/JP2015/068872 JP2015068872W WO2016002797A1 WO 2016002797 A1 WO2016002797 A1 WO 2016002797A1 JP 2015068872 W JP2015068872 W JP 2015068872W WO 2016002797 A1 WO2016002797 A1 WO 2016002797A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0279—Porous; Hollow
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/12—Face or body powders for grooming, adorning or absorbing
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Definitions
- the present invention relates to porous silica-based particles having a small specific surface area and a large pore volume, a method for producing the same, and a cosmetic containing the same.
- Patent Document 1 Japanese Patent Application Laid-Open No. 61-1741073 discloses that a colloidal solution containing primary particles (silica fine particles) having an average particle diameter of 2500 mm or less is spray-dried using a spray dryer to obtain average particles.
- a method for preparing porous silica-based particles having a diameter of 1 to 20 ⁇ m is disclosed.
- Patent Document 2 Japanese Patent Laid-Open No. 2002-160907 discloses an aggregate of inorganic silica fine particles having an average particle diameter of 1 to 100 ⁇ m in which inorganic silica fine particles having an average particle diameter of 2 to 250 nm are collected by spray drying a colloidal liquid. It is disclosed that a spherical porous particle is prepared by coating the aggregate with an oxide layer.
- Patent Document 3 Japanese Patent Laid-Open No. 2010-138021 discloses a porous material having an average particle diameter of 0.5 to 50 ⁇ m and a specific surface area of 30 to 250 m 2 / g by spray-drying a silica-based fine particle dispersion of 10 to 50 nm. The production of silica-based particles is disclosed, and in Patent Document 4 (Japanese Patent Laid-Open No. 2010-138822), a silica-based fine particle dispersion of 50 to 300 nm is spray-dried to obtain an average particle size of 0.5 to 50 ⁇ m, Production of porous silica-based particles having a specific surface area of 10 to 100 m 2 / g is disclosed.
- Patent Document 5 Japanese Patent Application Laid-Open No. 2005-298739
- a porous silica is prepared by spray drying a slurry containing a ceramic powder and a chemical reaction generated at a temperature of 40 ° C. to 250 ° C. or a substance that disappears due to a state change. Making system particles is disclosed.
- Patent Document 6 Japanese Patent Application Laid-Open No. 2009-137806 discloses a smooth feeling as a typical touch characteristic required for a cosmetic feel improving material by blending porous silica-based particles in a cosmetic.
- a method of obtaining a powdered solid cosmetic having a moist feeling, a rolling feeling, a uniform spread and spreadability, adhesion to the skin, and a persistent rolling feeling has been disclosed.
- porous silica-based particles described above fall under the definition of nanomaterials shown below. According to the recommendation from the European Commission dated 18 October 2011, (1) the particle size distribution in the range of 1 to 100 nm exceeds 50% by number, (2) the specific surface area (SA) per unit volume is 60 m 2 / Those exceeding cm 3 were defined as nanomaterials. Each of the porous silica-based particles described above has nano-sized pores and a high specific surface area, and the specific surface area per unit weight converted to a silica density of 2.2 g / cm 3 is 27 m 2 / g. Over. Although particles that belong to nanomaterials have not been immediately confirmed to cause serious environmental, health and safety problems, users and consumers are requested to avoid using particles that fall under nanomaterials. Will be done.
- an object of the present invention is to realize porous silica-based particles having a small specific surface area and a large pore volume.
- Such porous silica-based particles have good feel characteristics, but the definition of nanomaterial is not applied. Therefore, it can be used for the same use as conventional porous silica-based particles with peace of mind.
- grains of such a characteristic as a touch improvement material can be provided.
- the porous silica particles of the present invention are composed of silica particles, the average particle diameter of the porous silica particles is 0.5 to 25 ⁇ m, the specific surface area determined by the BET method is 5 to 60 m 2 / cm 3 , The pore volume is 0.35 to 2.0 ml / g.
- the mode pore diameter (D m ) in the pore diameter distribution (X axis: pore diameter, Y axis: value obtained by differentiating the pore volume with the pore diameter) of the porous silica-based particles is greater than 100 nm and less than 4000 nm. .
- the minimum pore size (D 0 ) is 25 to 500 nm
- the maximum pore size (D 100 ) is 300 to 8000 nm
- Ratio (D 100 / D 0 ) was in the range of 4 to 320.
- porous silica-based particles may contain inorganic oxide fine particles containing at least one of titanium oxide, iron oxide and zinc oxide in a range of 10 to 50% by weight.
- organic fine particles may be included.
- the average particle size of the silica-based fine particles is preferably in the range of 0.01 to 0.30 with respect to the average particle size of the porous silica-based particles.
- the method for producing porous silica-based particles according to the present invention comprises (A) silica sol having an average particle diameter of more than 100 to 1000 nm and a solid content of 10 to 30% by weight, and a silicate binder having a solid content of 1 to 40% by weight. Dispersing to obtain a slurry, and (B) spraying a spray liquid containing the slurry into an air stream to obtain porous silica-based particles.
- the cosmetic of the present invention contains any of the porous silica-based particles described above.
- the porous silica-based particles according to the present invention have a large pore volume despite a small specific surface area. Therefore, the definition of nanomaterials does not apply. Therefore, it can be used for the same use as conventional porous silica-based particles with peace of mind. In particular, unlike conventional porous silica-based particles, it is possible to impart touch characteristics having a high slide feeling without feeling a crispness when blended in cosmetics.
- FIG. 3 is a chart showing the pore size distribution (X axis: pore size, Y axis: value obtained by differentiating pore volume with pore size) of the porous silica-based particles of Example 1.
- 2 is an SEM photograph (magnification 10,000 times) of the appearance of the porous silica-based particles of Example 1 taken with a scanning electron microscope.
- 2 is a SEM photograph (magnification 10,000 times) of a cross section of the porous silica-based particles of Example 1 taken with a scanning electron microscope. It is a model figure explaining the number of contacts.
- silica, silica-alumina, silica-zirconia, silica-titania and the like can be used as the silica-based fine particles constituting the porous silica-based particles. There is no need to change the production conditions of the porous silica particles depending on the difference in the composition of the silica particles. In consideration of blending in cosmetics, amorphous silica is suitable as the silica-based fine particles.
- the sphericity of the silica-based fine particles is preferably 0.85 to 1.00.
- the sphericity is the ratio of the maximum diameter (DL) to the short diameter (DS) perpendicular to each of any 50 particles in a photographic projection obtained by photographing with a transmission electron microscope. It means the average value of (DS / DL).
- a sphericity of less than 0.85 is not preferable because it greatly affects the strength of the porous silica-based particles.
- Silica-based fine particles preferably have an average particle size (d 2 ) of more than 100 nm and 1000 nm or less, and a particle size variation coefficient (CV value) of 5 to 15%. Porous silica-based particles obtained with silica-based fine particles in this average particle size range do not conform to the definition of nanomaterials and can be used for the same purposes as conventional porous silica-based particles with peace of mind. it can.
- the average particle diameter (d 2 ) is preferably in the range of 110 to 600 nm, and particularly preferably in the range of 120 to 550 nm.
- the porous silica-based particles of the present invention are composed of silica-based fine particles.
- the average particle diameter (d 1 ) of the porous silica-based particles is 0.5 to 25 ⁇ m, the specific surface area determined by the BET method is 5 to 60 m 2 / cm 3 , and the pore volume is 0.35 to 2.0 ml / g. is there.
- the average particle diameter is determined by a laser diffraction method. If the average particle size of the porous silica-based particles is less than 0.5 ⁇ m, when the particle powder is touched, not only the rolling feeling as a spherical powder is felt, but also the feeling of spreading and spreading is felt. Become. On the other hand, when the particle diameter exceeds 25 ⁇ m, when the particle powder is touched, a feeling of roughness or sharpness is felt.
- the average particle diameter (d 1 ) of the porous silica-based particles is more preferably in the range of 2 to 10 ⁇ m.
- the pore volume of the porous silica-based particles is less than 0.35 ml / g, the porosity of the particles themselves is lowered, so that the oil absorbency in the pores inside the particles is lowered.
- the feeling of touching the particle powder is reduced, such as a smooth feeling, a rolling feeling, a uniform spreadability, and a rolling feeling.
- the pore volume exceeds 2.0 ml / g, the particle strength is lowered due to the high porosity of the particles themselves, so that the particles are liable to collapse when applied on the skin. As a result, the durability of the rolling feeling is significantly reduced.
- the mode of pore diameter distribution (D m ) in the pore size distribution (X axis: pore diameter, Y axis: value obtained by differentiating the pore volume by the pore diameter) of the porous silica-based particles is greater than 100 nm and less than 4000 nm. (100 ⁇ D m ⁇ 4000 [nm]).
- D m the most frequent pore diameter
- a desired pore volume “0.35 ml / g or more” and a desired specific surface area “60 m 2 / cm 3 or less” in the case of silica, 27 m 2 / g
- a mode pore diameter (D m ) of 4000 nm or more is not preferable because the strength of the particles tends to decrease.
- the most frequent pore diameter (D m ) is preferably in the range of more than 150 to less than 3000 nm (150 ⁇ D m ⁇ 3000), and more preferably in the range of more than 200 to less than 2000 nm (200 ⁇ D m ⁇ 2000).
- FIG. 1 shows the pore size distribution of porous silica particles produced in Example 1 described later.
- the X-axis is the pore diameter (Pore Diameter)
- the Y-axis is the value ( ⁇ V) obtained by differentiating the pore volume with the pore diameter.
- Two distribution curves are lined up with a pore diameter value (represented by a broken line in the figure) having an X axis. That is, in FIG. 1, ⁇ V is 0 between the first distribution curve due to the pores present inside the porous silica-based particles and the second distribution curve due to the voids between the particles of the porous silica-based particles. % Pore size is present.
- the smallest pore diameter D 0 in which ⁇ V is measured is the minimum pore diameter
- the pore diameter D m corresponding to the first peak is the most frequent pore diameter.
- the rightmost pore diameter D 100 (the largest measured ⁇ V) is the maximum pore diameter.
- the most frequent pore diameter (D m ) is 834 nm
- the minimum pore diameter (D 0 ) is 150 nm
- the maximum pore diameter (D 100 ) is 1211 nm
- the vertex of the second distribution curve is 2445 nm.
- the porous silica-based particles have a sparse packing structure of silica-based fine particles (primary particles made of silica sol). Therefore, the minimum pore size (D 0 ) in the pore size distribution of the porous silica-based particles is in the range of 25 to 500 nm, the maximum pore size (D 100 ) is in the range of 300 to 8000 nm, and the maximum pore size (D 100 ) is The ratio (D 100 / D 0 ) to the minimum pore diameter (D 0 ) is in the range of 4 to 320.
- the minimum pore diameter (D 0 ) is less than 25 nm, it is practically difficult to achieve both a desired pore volume (0.35 ml / g or more) and a desired specific surface area (60 m 2 / cm 3 or less).
- the thickness exceeds 500 nm, the strength of the particles tends to decrease, which is not preferable.
- the maximum pore diameter (D 100 ) is less than 300 nm, it is practically difficult to achieve both desired pore volume and specific surface area. When it exceeds 8000 nm, the strength of the particles tends to decrease, which is not preferable.
- D 100 / D 0 is less than 4, or more than 320, the desired pore volume and specific surface area should be compatible. Is practically difficult.
- the minimum pore diameter (D 0 ) is particularly preferably in the range of 50 to 400 nm, and the maximum pore diameter (D 100 ) is particularly preferably in the range of 500 to 4000 nm.
- the pore diameter ratio (D 100 / D 0 ) is preferably in the range of 4 to 80, and particularly preferably in the range of 4 to 20.
- Patent Document 4 discloses particles having a packing structure in which silica-based fine particles are dense. In this case, it is known that the particle size is 70% or more of the total pore volume.
- the porous silica-based particles of the present invention have a sparse packing structure.
- This structure will be described using a photograph (SEM photograph) taken with an electron microscope.
- FIG. 2 is an SEM photograph (magnification 10,000 times) of the porous silica particles produced in Example 1 described later. A plurality of silica-based fine particles are joined while forming many voids to form a sparse packing structure and an uneven structure on the particle surface.
- FIG. 3 is an SEM photograph (magnification 10,000 times) of a cross section of the particles obtained by curing the porous silica-based particles in a liquid resin.
- FIG. 4 is a model diagram for explaining the number of contacts between one particle at the most central portion of the porous silica-based particle and another adjacent particle.
- the number of contacts 6 indicates a dense packing structure that is a close-packed structure.
- the particle size distribution of the silica-based fine particles is wide, and the number of contacts may exceed 6 when many fine small particles and coarse large particles are mixed in comparison with the silica-based fine particles of the average particle size. obtain.
- the porous silica-based particles have a sparse packing structure with 4 or less contacts.
- the smaller the number of contacts the larger the pore volume even if the specific surface area is the same.
- the number of contacts is preferably 3 or less, and more preferably 2 or less. Further, when the number of contacts exceeds 4, that is, when having a dense packing structure (for example, the number of contacts is 6), particles having a large pore volume cannot be obtained.
- the porous silica-based particles have a structure in which the number of contacts of the silica-based fine particles on the surface (outer periphery) portion is larger than the number of contacts of the silica-based fine particles in the central portion. For this reason, the range of the ratio (D 100 / D 0 ) of the maximum pore diameter (D 100 ) to the minimum pore diameter (D 0 ) becomes large (4 ⁇ (D 100 / D 0 ) 320). I can explain. Furthermore, with such a structure, it is considered that the compressive strength of the porous silica-based particles exhibits 10 MPa or more as described later.
- the average particle diameter (d 2 ) of the silica-based fine particles is in the range of 0.01 to 0.30, preferably 0.02 to 0, with respect to the average particle diameter (d 1 ) of the porous silica-based particles. .20 range. If it is this range, the optimal unevenness
- the compressive strength of the porous silica-based particles is preferably 10 MPa or more, particularly 30 MPa or more. If the compressive strength is less than 10 MPa, the particles may collapse during the step of blending into the cosmetic, and the desired feel characteristics may not be obtained.
- the upper limit of the compressive strength is not particularly limited, but may be, for example, about 200 MPa.
- the porous silica-based particles may contain inorganic oxide fine particles containing at least one of titanium oxide, iron oxide, and zinc oxide within a range of 50% by weight or less. Within this range, the inorganic oxide fine particles can be uniformly contained inside the porous silica-based particles.
- iron oxide is preferably ferric oxide, ⁇ -iron oxyhydroxide, or triiron tetroxide.
- the average particle diameter of the inorganic oxide fine particles is preferably at the same level as the silica-based fine particles. Therefore, the range of 100 to 1000 nm is suitable.
- the porous silica-based particles may contain organic fine particles.
- the organic fine particles will be described later.
- the porous silica-based particles may contain a binder.
- the binder is a silica-based binder.
- (B) A spray drying step of preparing porous silica-based particles by spraying a spray liquid containing the dispersed slurry in an air stream.
- the concentration of the silica sol is in the range of 10 to 30% by weight in terms of solid content.
- the silicic acid binder is in the range of 1 to 40% by weight in terms of solid content.
- the gelation of the binder component inside the particles occurs at the initial stage of drying during spray drying, and the primary structure composed of silica sol (silica fine particles) has a sparse packing structure (aggregation structure). None, porous silica-based particles with a large pore volume can be prepared for a small specific surface area.
- the silicic acid binder since the silicic acid binder has an effect of adhering primary particles composed of silica sol (silica-based fine particles), porous silica-based particles having high mechanical strength can be prepared.
- the solid content concentration (in terms of silicon dioxide) of the silicate binder in the slurry is preferably 1.5 to 10.0% by weight.
- the range of 2.0 to 5.0% by weight is particularly suitable.
- the silica-based fine particles tend to have a dense packing structure. Therefore, it becomes difficult to prepare porous silica-based particles having a large pore volume.
- it exceeds 10.0% by weight the stability of the silicic acid binder is lowered, so that fine gel or particulate silica is formed over time. Therefore, the specific surface area increases, which is not preferable.
- Spray drying can be performed by a conventionally known method using a commercially available spray dryer (disc rotation type, nozzle type, etc.). For example, it is performed by spraying the spray liquid at a rate of 1 to 3 liters / minute in a hot air stream.
- the temperature of the hot air is preferably in the range of 70 to 400 ° C. at the inlet temperature and 40 to 60 ° C. at the outlet temperature.
- the inlet temperature is less than 70 ° C.
- the solid content contained in the dispersion is insufficiently dried.
- it exceeds 400 degreeC the shape of particle
- the outlet temperature is less than 40 ° C., the degree of drying of the solid content is poor and adheres to the inside of the apparatus.
- a more preferable inlet temperature is in the range of 100 to 300 ° C.
- Dry powder of porous silica-based particles is formed by spray drying.
- a powder mainly composed of calcined porous silica-based particles (simply referred to as porous silica-based particles) can be obtained. That is, a powder of porous silica-based particles can be produced by firing the dry powder at a temperature of 200 to 800 ° C. for 1 to 24 hours. The compressive strength of the powder is increased by firing.
- the calcination temperature is less than 200 ° C., the siloxane bond between the primary particles constituting the porous silica-based particles is not sufficient, so that improvement in compressive strength cannot be expected.
- the firing temperature exceeds 800 ° C.
- the pores in the particles disappear due to the sintering of the particles, and the desired porosity cannot be obtained.
- crystalline silica may produce
- the firing time is less than 1 hour, the siloxane bond between the primary particles is not sufficient, so improvement in compressive strength cannot be expected, and even if the firing time exceeds 24 hours, no particular effect can be obtained. Not economical.
- silicate binder a silicate aqueous solution such as an alkali metal silicate or an organic base silicate treated with a cation exchange resin and dealkalized (removal of Na ions, etc.) can be used.
- the silicate include alkali metal silicates such as sodium silicate (water glass) and potassium silicate, and silicates of organic bases such as quaternary ammonium silicate.
- inorganic oxide fine particles may be included in the spray liquid as a metal oxide other than silica. It is desirable that the average particle diameter of the inorganic oxide fine particles is substantially the same as that of the silica-based fine particles. That is, the average particle diameter of the inorganic oxide fine particles is 100 to 1000 nm.
- the inorganic oxide fine particles have optical properties such as concealment and UV shielding properties when applied to the skin, so that when applied to the skin, the touch has a high slide feeling without feeling a crispness. It can produce characteristics and optical characteristics.
- organic fine particles may be included in the spray liquid.
- examples thereof include polymer latex particles such as natural rubber, styrene-butadiene copolymer, acrylate latex, and polybutadiene.
- the average particle size of the organic fine particles is preferably in the range of 25 to 1000 nm, particularly preferably in the range of 100 to 1000 nm.
- the organic fine particles may be removed by heat-treating the porous silica-based particles containing the organic fine particles at 400 to 1200 ° C. under atmospheric pressure or reduced pressure. Thereby, it is possible to prepare porous silica-based particles having a larger pore volume.
- Cosmetics obtained by blending the porous silica-based particles and various cosmetic ingredients will be specifically described. The present invention is not necessarily limited to these cosmetics.
- oils such as olive oil, rapeseed oil, beef tallow, wax such as jojoba oil, carnauba wax, candelilla wax, beeswax, paraffin, squalane, synthetic and vegetable squalane, ⁇ -olefin oligomer, Microcrystalline wax, hydrocarbons such as pentane, hexane, fatty acids such as stearic acid, myristic acid, oleic acid, ⁇ -hydroxy acid, isostearyl alcohol, octyldodecanol, lauryl alcohol, ethanol, isopropanol, butyl alcohol, myristyl Alcohols such as alcohol, cetanol, stearyl alcohol, and behenyl alcohol, alkyl glyceryl ethers, isopropyl myristate, isopropyl palmitate, ethyl stearate, ethyl oleate , Esters such as
- resin particles such as polymethyl acrylate, nylon, silicone resin, silicone rubber, polyethylene, polyester, and polyurethane may be included.
- arbutin as an active ingredient having a whitening effect, arbutin, kojic acid, vitamin C, sodium ascorbate, magnesium ascorbate phosphate, ascorbyl dipartate, ascorbyl glucoside, other ascorbic acid derivatives, placenta extract, sulfur, Plant extracts such as oil-soluble licorice extract and mulberry extract, linoleic acid, linolenic acid, lactic acid, tranexamic acid and the like can be included.
- Anti-aging effects such as vitamin C, carotenoids, flavonoids, tannins, caffeine derivatives, lignans, saponins, retinoic acid and retinoic acid structural analogs, N-acetylglucosamine, ⁇ -hydroxy acids, etc.
- Such cosmetics can be produced by a conventionally known general method.
- Cosmetics are used in various forms such as powder, cake, pencil, stick, cream, gel, mousse, liquid, and cream.
- soaps, cleansing foams makeup cosmetics such as creams for removing makeup, moisturizing and rough skin prevention, acne, keratin care, massage, wrinkle / sagging, dullness / bearing, UV care, whitening, antioxidant
- Skin care cosmetics for care powder foundation, liquid foundation, cream foundation, mousse foundation, pressed powder, base makeup cosmetics such as makeup base, eye shadow, eyebrow, eyeliner, mascara, lipstick, etc.
- a silicic acid solution (silica sol concentration of 10.0% by weight). 889 g of this silicic acid solution is added to 2000 g of silica sol (I) to obtain a dispersion slurry having a silica sol concentration of 27.7 wt%, a water glass-derived silicic acid concentration of 3.1 wt%, and a solid content concentration of 30.8 wt%.
- the obtained slurry is spray-dried with a spray dryer (NIRO-ATMIZER, manufactured by NIRO) as a spray solution. That is, in a dry air flow set at an inlet temperature of 220 ° C. and an outlet temperature of 50 to 55 ° C., slurry is supplied from one of the two-fluid nozzles at a flow rate of 2 L / hr and gas from the other nozzle at a pressure of 0.4 MPa. And dried by spraying to obtain a dry powder composed of porous silica-based particles.
- the conditions for preparing the dry powder are shown in Table 1 for each example.
- This dry powder is fired at 500 ° C. for 4 hours, and then subjected to dry sieving to obtain a powder composed of fired porous silica particles.
- the pore distribution of the porous silica particles is shown in FIG. From FIG. 1, it can be seen that the porous silica particles of this example have a modest pore size (D m ) of 834 nm, a minimum pore size (D 0 ) of 150 nm, and a maximum pore size (D 100 ) of 1211 nm. .
- FIG. 2 shows an SEM photograph (magnification 10,000 times) showing the appearance of the porous silica particles.
- FIG. 3 is an SEM photograph (magnification 10,000 times) of the cross section of the porous silica particles.
- the physical properties of the porous silica particle powder were measured by the following method. The results are shown in Table 2.
- Measuring method of pore volume and pore diameter of porous silica-based particles Take 10 g of porous silica-based particle powder in a crucible, dry at 300 ° C. for 1 hour, place in a desiccator, cool to room temperature, and automatically It measured by the mercury intrusion method using the porosimeter (PoreMasterPM33GT by Counterchrome Instruments). Mercury was injected at 1.5 kPa to 231 MPa, and the pore size distribution was determined from the relationship between pressure and pore size.
- the small diameter pores present inside the porous silica-based particles and the large diameter between the particles of the porous silica-based particles. are measured (approximately 1/5 to 1/2 of the average particle diameter of the porous silica-based particles). Based on the measurement results of the small-diameter pores excluding the large-diameter, the pore volume, mode pore diameter (D m ), minimum pore diameter (D 0 ), and maximum pore diameter (D 100 ) are calculated. At this time, peak separation software (attached to an automatic porosimeter) is used as necessary.
- FIG. 3 is an SEM photograph (magnification 10,000 times) of the cross section of the porous silica-based particle, showing one porous silica-based particle according to this example. Fine particles closest to the intersection indicating the approximate center of the porous silica-based particles are particles marked with ⁇ in the lower right of the intersection. It can be seen that the number of contacts between the most central particle and other adjacent particles (marked with ⁇ ) is two.
- a powder foundation was prepared using a porous silica-based powder so as to have a blending ratio (% by weight) shown in Table 4. That is, the powder (component (1)) and components (2) to (9) of Example 1 were placed in a mixer and stirred to mix uniformly. Next, the cosmetic ingredients (10) to (12) were put into this mixer and stirred, and further mixed uniformly. Next, after crushing the obtained cake-like substance, about 12 g was taken out from it, put into a square metal pan of 46 mm ⁇ 54 mm ⁇ 4 mm, and press molded. The powder foundation thus obtained was subjected to a sensory test by 20 professional panelists.
- ⁇ Total score is 80 or more ⁇ : Total score is 60 or more and less than 80 ⁇ : Total score is 40 or more and less than 60 ⁇ : Total score is 20 or more and less than 40 ⁇ : Total score is less than 20
- Example 2 153 g of JIS No. 3 water glass (silica concentration 29 wt%) is added to 2000 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SS-300, average particle size 300 nm, silica concentration 20 wt%).
- silica sol manufactured by JGC Catalysts & Chemicals Co., Ltd .: SS-300, average particle size 300 nm, silica concentration 20 wt%.
- 40 g of cation exchange resin manufactured by Mitsubishi Kasei Co., Ltd., SK-1B
- SK-1B cation exchange resin
- Example 1 The obtained slurry is spray-dried in the same manner as in Example 1 under the conditions shown in Table 1 to obtain a dry powder of porous silica-based particles.
- This dry powder is fired at 500 ° C. for 4 hours to obtain a powder composed of porous silica-based particles.
- the physical properties of this powder were measured in the same manner as in Example 1. The results are shown in Table 2.
- Examples 3 to 12, Comparative Examples 1 to 4 A dry powder is produced in the same manner as in Example 1 using the preparation conditions shown in Table 1 instead of the silica sol and silicate binder used in Example 1.
- the dried powder is fired in the same manner as in Example 1 to produce porous silica-based particle powder.
- a slurry having a silicic acid concentration derived from a silicic acid solution of 1.2 wt% and a solid content concentration of 5.0 wt% is prepared. The obtained slurry is spray-dried with a spray dryer as a spray solution. At this time, in a dry air flow set at an inlet temperature of 240 ° C.
- Example 5 shows the results. It was found that the cosmetics A to C according to the examples were very excellent in use feeling both during and after application. However, it was found that the cosmetics a to c of the comparative examples were not good in use feeling.
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Abstract
Description
本発明では、多孔質シリカ系粒子を構成するシリカ系微粒子として、シリカ、シリカ-アルミナ、シリカ-ジルコニア、シリカ-チタニアなどを用いることができる。シリカ系微粒子の組成の違いによって多孔質シリカ系粒子の製造条件を変更する必要はない。化粧料に配合することを考慮すると、シリカ系微粒子として非晶質シリカが好適である。
<多孔質シリカ系粒子>
本発明の多孔質シリカ系粒子は、シリカ系微粒子で構成されている。多孔質シリカ系粒子の平均粒子径(d1)は0.5~25μm、BET法で求めた比表面積は5~60m2/cm3、細孔容積は0.35~2.0ml/gである。平均粒子径はレーザー回折法で求められる。多孔質シリカ系粒子の平均粒子径が0.5μm未満であると、粒子粉体に触ったとき、球状粉体としての転がり感が感じられないばかりでなく、延び広がり感の悪さを感じるようになる。一方、25μmを超えると、粒子粉体に触ったとき、ざらつき感やシャリシャリ感を感じるようになる。多孔質シリカ系粒子の平均粒子径(d1)は2~10μmの範囲がより好ましい。
<多孔質シリカ系粒子の製造方法>
本発明の多孔質シリカ系粒子の製造方法は、以下の工程(A)と工程(B)を含んでいる。
<工程(A)>
シリカゾルの濃度は、固形分換算で10~30重量%の範囲にある。さらに、珪酸バインダーについては、固形分換算で1~40重量%の範囲にある。この範囲のシリカゾルと珪酸バインダーを用いると、噴霧乾燥時に、粒子内部のバインダー成分のゲル化が乾燥初期に起こり、シリカゾルからなる構成一次粒子(シリカ系微粒子)が疎なパッキング構造(凝集構造)をなし、比表面積が小さい割には細孔容積が大きい多孔質シリカ系粒子を調製できる。また、珪酸バインダーにはシリカゾルからなる構成一次粒子(シリカ系微粒子)を接着する効果があることから、機械的強度が強い多孔質シリカ系粒子を調製できる。
<工程(B)>
噴霧乾燥は、市販のスプレイドライヤー(ディスク回転式やノズル式等がある)を用いた従来公知の方法で行うことができる。例えば、熱風気流中に1~3リットル/分の速度で噴霧液を噴霧することによって行われる。この際、熱風の温度は、入口温度で70~400℃、出口温度で40~60℃の範囲にあることが好ましい。ここで、入口温度が70℃未満であると、分散液中に含まれる固形分の乾燥が不充分となる。また400℃を超えると、噴霧乾燥時に粒子の形状が歪んでしまう。また、出口温度が40℃未満であると、固形分の乾燥度合いが悪くて装置内に付着してしまう。より好ましい入口温度は、100~300℃の範囲である。
<化粧料>
以下に、多孔質シリカ系粒子と各種化粧料成分とを配合して得られる化粧料について具体的に説明する。本発明は、これらの化粧料に必ずしも限定されるものではない。
[実施例1]
シリカゾル(日揮触媒化成(株)製:SS-550、平均粒子径550nm、シリカ濃度20重量%)4000gを限外ろ過膜(旭化成社製、SIP-1013)を用いて濃縮し、シリカ濃度40重量%のシリカゾル2000gを調製する。これを陽イオン交換し、pH=2.0に調整してシリカゾル(I)を得る。このとき、後述する方法によりシリカ系微粒子の変動係数(CV値)と真球度を測定する。実施例で用いたシリカゾル(I)の特性を表1に示す。
レーザー回折法を用いて多孔質シリカ系粒子の粒度分布を測定し、この粒度分布からメジアン径で表わされる平均粒子径(d1)を求めた。レーザー回折法による粒度分布の測定は、レーザー回折/散乱式粒子径分布測定装置LA-950(株式会社堀場製作所製)を用いた。
レーザーパーティクルアナライザー(大塚電子製、LP-510)を用いてシリカ系微粒子の粒度分布を測定し、この粒度分布からメジアン径で表わされる平均粒子径(d2)を求めた。
走査型電子顕微鏡(日本電子社製JSM-7600F)により、倍率2万倍から25万倍で写真(SEM写真)を撮影する。この画像の250個の粒子について、画像解析装置(旭化成社製、IP-1000)を用いて、平均粒子径を測定し、粒子径分布に関する変動係数(CV値)を算出した。
透過型電子顕微鏡(日立製作所製、H-8000)により、倍率2万倍から25万倍の倍率で写真撮影して得られる写真投影図から、任意の50個の粒子を選び、それぞれその最大径(DL)と、これに直交する短径(DS)との比(DS/DL)を測定し、それらの平均値を真球度とした。
多孔質シリカ系粒子の粉体を磁性ルツボ(B-2型)に約30ml採取し、105℃の温度で2時間乾燥後、デシケーターに入れて室温まで冷却する。次に、サンプルを1g取り、全自動表面積測定装置(湯浅アイオニクス社製、マルチソーブ12型)を用いて、比表面積(m2/g)をBET法にて測定し、シリカの比重2.2g/cm3で換算した単位重量当たりの比表面積とした。
多孔質シリカ系粒子の粉体10gをルツボに取り、300℃で1時間乾燥後、デシケーターに入れて室温まで冷却し、自動ポロシメーター(カウンタークローム・インスツルメンツ社製PoreMasterPM33GT)を使用して水銀圧入法により測定した。水銀を1.5kPa~231MPaで圧入し、圧力と細孔径の関係から細孔径分布を求めた。この方法によれば、約7nmから約1000μm迄の細孔に水銀が圧入されるため、多孔質シリカ系粒子の内部に存在する小径の細孔と、多孔質シリカ系粒子の粒子間の大径の空隙(おおむね多孔質シリカ系粒子の平均粒子径に対して1/5~1/2のサイズに計測される)の両方が計測される。大径を除く、小径の細孔の計測結果をもとに、細孔容積、最頻細孔径(Dm)、最小細孔径(D0)、および最大細孔径(D100)を算出する。このとき、必要に応じてピーク分離ソフト(自動ポロシメーターに付属)が用いられる。
多孔質シリカ系粒子の粉体0.2gを白金皿で精秤し、硫酸10mlと弗化水素酸10mlを加えて、砂浴上で硫酸の白煙が出るまで加熱する。冷却後、水約50mlを加えて加温溶解する。冷却後、水200mlに希釈しこれを試験溶液とする。この試験溶液について誘導結合プラズマ発光分光分析装置(島津製作所(株)製、ICPS-8100、解析ソフトウェアICPS-8000)を使用し、多孔質シリカ系粒子の組成を求める。
多孔質シリカ系粒子を磁性ルツボ(B-2型)に約30ml採取し、105℃で2時間乾燥後、デシケーターに入れて室温まで冷却する。次に、サンプルを15ml採取し、全自動ピクノメーター(QUANTACHROME社製:Ultrapyc1200e)を用いて真比重を測定し、粒子の密度とする。
多孔質シリカ系粒子0.1gをエポキシ樹脂(日新EM社製、Quetol651)100gに混合し、60℃の温度で24時間硬化する。次いで、硬化したブロックをアルゴンイオンビーム(日本電子社、クロスセクションポリッシャ、加速電圧6.2kV)で切断する。作製された断面試料を走査電子顕微鏡(日本電子社製JSM-7600F)により、倍率1,000倍から50,000倍の倍率で写真(SEM写真)を撮影する。この写真10枚について、球の最中心部の一微粒子について、隣接する他の微粒子との接点数を計測する。それらの平均値を四捨五入した整数値を平均接点数とする。
多孔質シリカ系粒子の粉体から、平均粒子径±0.5μmの範囲にある粒子1個を試料として取り、微小圧縮試験機(島津製作所製、MCTM-200)を用いて、この試料に一定の負荷速度で荷重を負荷し、粒子が破壊した時点の加重値を圧縮強度(Mpa)とする。さらに、この操作を4回繰り返し、5個の試料について圧縮強度を測定し、その平均値を粒子圧縮強度とする。
多孔質シリカ系粒子の粉体について、20名の専門パネラーによる官能テストを行い、さらさら感、しっとり感、転がり感、均一な延び広がり性、肌への付着性、転がり感の持続性、およびシリカ系粒子独特のシャリシャリ感の低さの7つの評価項目に関して聞き取り調査を行う。その結果を以下の評価点基準(a)に基づき評価する。さらに、各人がつけた評価点を合計し、以下の評価基準(b)に基づき多孔質シリカ系粒子の感触に関する評価を行った。結果を表3に示す。
多孔質シリカ系粒子の粉体を用いて表4に示す配合比率(重量%)となるようにパウダーファンデーションを作製した。すなわち、実施例1の粉体(成分(1))と成分(2)~(9)をミキサーに入れて撹拌し、均一に混合した。次に、化粧料成分(10)~(12)をこのミキサーに入れて撹拌し、さらに均一に混合した。次いで、得られたケーキ状物質を解砕処理した後、その中から約12gを取り出し、46mm×54mm×4mmの角金皿に入れてプレス成型した。この様にして得られたパウダーファンデーションについて、20名の専門パネラーによる官能テストを行い、(1)肌への塗布中の均一な延び、しっとり感、滑らかさ、および(2)肌に塗布後の化粧膜の均一性、しっとり感、やわらかさの6つの評価項目に関して聞き取り調査を行う。その結果を以下の評価点基準(a)に基づき評価する。また、各人がつけた評価点を合計し、以下の評価基準(b)に基づきファンデーションの使用感に関する評価を行った。結果を表5に示す。
評価点基準(a)
4点:優れている。
3点:普通。
2点:劣る。
1点:非常に劣る。
評価基準(b)
◎:合計点が80点以上
○:合計点が60点以上80点未満
△:合計点が40点以上60点未満
▲:合計点が20点以上40点未満
×:合計点が20点未満
シリカゾル(日揮触媒化成(株)製:SS-300、平均粒子径300nm、シリカ濃度20重量%)2000gにJIS3号水硝子153g(シリカ濃度29重量%)を加える。これに、陽イオン交換樹脂(三菱化成社製、SK-1B)40gを一気に加えてpHを2.5とした後、陽イオン交換樹脂を分離する。このようにして、シリカゾル濃度18.6重量%、水硝子由来の珪酸濃度2.1重量%、全固形分濃度20.6重量%の分散スラリーが得られる。
[実施例3~12、比較例1~4]
実施例1で使用したシリカゾルや珪酸バインダーの代わりに、表1に示す調製条件を用いて、実施例1と同様に乾燥粉体を作製する。乾燥粉体を実施例1と同様に焼成して、多孔質シリカ系粒子の粉体を作製する。このようにして得られた実施例3~12の粉体、比較例1~4の粉体の物性を実施例1と同様に測定した。その結果を表2に示す。
[比較例5]
シリカゾル(日揮触媒化成(株)製:SS-160、平均粒子径160nm、シリカ濃度20重量%)の水希釈品(シリカ濃度15重量%)2000gを陽イオン交換し、pHを2.0に調整する。これに[シリカゾル中のシリカ]/[珪酸液中のシリカ]=9/1の比率になるように珪酸液(シリカ濃度4.8重量%)694.4gを加え、シリカゾル濃度11.1重量%、珪酸液由来の珪酸濃度1.2重量%、固形分濃度5.0重量%のスラリーを調製する。得られたスラリーを噴霧液として、スプレイドライヤーにより噴霧乾燥する。このとき、入口温度240℃、出口温度50~55℃に設定した乾燥気流中に、2流体ノズルの一方からスラリーを2L/hrの流量で、他方のノズルから0.75MPaの圧力で気体を供給して噴霧乾燥する。このようにして得られた乾燥粉体を500℃で4時間焼成後、乾式篩処理を行って多孔質シリカ系粒子の粉体を作製した。この粉体の物性を実施例1と同様に測定した。その結果を表2に示す。
各実施例と比較例により得られた粉体を用いて、実施例1と同様に感触特性を評価した。その結果を表3に示す。その結果、各実施例の粉体は、化粧料の感触改良材として極めて優れているが、比較例の粉体は、感触改良材として適していないことが分かった。
表4に示す配合比率(重量%)となるように、各実施例と比較例の粉体(成分(1))を、他の成分(2)~(9)とともにミキサーに入れて撹拌し、均一に混合させた。次に、化粧料成分(10)~(12)をこのミキサーに入れて撹拌し、均一に混合させた。得られたケーキ状物質を用いて実施例1と同様に化粧料を得た。
Claims (11)
- シリカ系微粒子で構成された多孔質シリカ系粒子において、平均粒子径(d1)が0.5~25μm、BET法で求めた比表面積が5~60m2/cm3、細孔容積が0.35~2.0ml/gであることを特徴とする多孔質シリカ系粒子。
- 前記多孔質シリカ系粒子の細孔径分布(X軸:細孔径、Y軸:細孔容積を細孔径で微分した値)における最頻細孔径(Dm)が、100<Dm<4000[nm]であることを特徴とする請求項1に記載の多孔質シリカ系粒子。
- 前記多孔質シリカ系粒子の細孔径分布(X軸:細孔径、Y軸:細孔容積を細孔径で微分した値)における最小細孔径(D0)が25~500nmの範囲にあり、最大細孔径(D100)が300~8000nmの範囲にあり、最大細孔径(D100)と最小細孔径(D0)の比(D100/D0)が4~320の範囲にあることを特徴とする請求項1または2に記載の多孔質シリカ系粒子。
- 前記多孔質シリカ系粒子は、酸化チタン、酸化鉄および酸化亜鉛の少なくとも1つを含む無機酸化物微粒子を10~50重量%の範囲で含有することを特徴とする請求項1~3のいずれか一項に記載の多孔質シリカ系粒子。
- 前記多孔質シリカ系粒子は、有機系微粒子を含むことを特徴とする請求項1~4のいずれか一項に記載の多孔質シリカ系粒子。
- 前記シリカ系微粒子の真球度が、0.85~1.00の範囲にあることを特徴とする請求項1~5のいずれか一項に記載の多孔質シリカ系粒子。
- 前記シリカ系微粒子の平均粒子径(d2)は、前記多孔質シリカ系粒子の平均粒子径(d1)に対して、0.01~0.30の範囲にあることを特徴とする請求項1~6のいずれか一項に記載の多孔質シリカ系粒子。
- 平均粒子径100超~1000nm、固形分濃度10~30重量%のシリカゾルに、固形分濃度1~40重量%の珪酸バインダーを分散させ、スラリーを得る工程と、
前記スラリーを含む噴霧液を気流中に噴霧して、多孔質シリカ系粒子を得る工程と、を備える多孔質シリカ系粒子の製造方法。 - 前記珪酸バインダーは、珪酸液、アルカリ金属珪酸塩、有機塩基の珪酸塩および有機珪素化合物の部分加水分解物の少なくとも1つを含み、前記珪酸バインダーのスラリー中の固形分濃度が、1.5~10.0重量%であることを特徴とする請求項8に記載の多孔質シリカ系粒子の製造方法。
- 請求項1~7のいずれか一項に記載の多孔質シリカ系粒子、または、請求項8または9に記載の製造方法で作製された多孔質シリカ系粒子が配合された化粧料。
- 前記化粧料が、メークアップ化粧料、スキンケア化粧料またはサンスクーン化粧料であることを特徴とする請求項10に記載の化粧料。
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