WO2018221406A1 - 中空粒子及び化粧料 - Google Patents
中空粒子及び化粧料 Download PDFInfo
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- WO2018221406A1 WO2018221406A1 PCT/JP2018/020149 JP2018020149W WO2018221406A1 WO 2018221406 A1 WO2018221406 A1 WO 2018221406A1 JP 2018020149 W JP2018020149 W JP 2018020149W WO 2018221406 A1 WO2018221406 A1 WO 2018221406A1
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- particles
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- silica
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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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- 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
- 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
- A61K8/025—Explicitly spheroidal or spherical shape
-
- 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
- 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
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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
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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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- 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
-
- 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
Definitions
- the present invention relates to hollow particles having soft touch characteristics unique to plastic beads, and cosmetics including the same.
- plastics are used in various industries and support modern and convenient lives. Many synthetic polymers have been developed for long-term stability. Therefore, it is not decomposed in the natural environment and causes various environmental problems. For example, plastic products that have spilled into the water environment have accumulated for a long period of time, causing the problem of serious damage to the marine and lake ecosystems. In recent years, a fine plastic having a length of 5 mm or less to a nano level, called a micro plastic, has become a big problem. Examples of micro plastics include fine particles contained in cosmetics, small lumps of plastic resin before processing, and products that have become finer as large products float in the sea.
- plastic particles for example, polyethylene particles
- plastic particles have a low true specific gravity and are difficult to remove at sewage treatment plants, and flow into rivers, oceans, ponds and marshes. Since plastic particles are easy to adsorb chemical substances such as insecticides, there is a possibility that the human body is affected by bioconcentration. This is pointed out in the United Nations Environment Program, etc., and various countries and various industry groups are considering regulations.
- inorganic oxide particles that do not use organic substances have been proposed.
- porous or non-porous spherical particles obtained by coating an aggregate of inorganic oxide fine particles with a silica layer are used as a filler for cosmetics, a cosmetic that is very light, soft, and has good elongation can be obtained. It is known (see, for example, WO 2004/006873).
- porous particles having an average particle diameter in the range of 0.5 to 30 ⁇ m and excellent in surface smoothness for example, JP-A 2009-2009). No. 137806).
- an inorganic oxide particle having a touch property that is highly adherent to the skin and low in sharpness it has cavities (porosity of 20 to 95% by weight) inside the nonporous outer shell. Hollow particles having a negative pressure are known (for example, see JP 2011-256098 A).
- inorganic oxide particles that do not use organic substances are not satisfactory as a substitute for plastic beads because it is difficult to develop soft touch characteristics during coating.
- an object of the present invention is to realize inorganic oxide particles having soft touch characteristics such as plastic beads.
- the inventors of the present invention indicate that the true specific gravity of the particles is a factor that gives a soft feeling during coating, and that the adhesive force is reduced by forming fine convex portions on the particle surface, and appropriate fluidity is imparted. I found out. As a result, inorganic oxide particles with soft feel like plastic beads were realized.
- the inorganic oxide particles of the present invention are hollow particles having cavities inside the outer shell, have convex portions of 3 to 100 nm on the outer shell surface, and the true specific gravity of the particles is 0.3 to 3. 0 g / cm 3 .
- the average particle diameter of the hollow particles is 1 to 20 ⁇ m, and the specific surface area per unit volume determined by the BET method is 0.5 or more and less than 60 m 2 / cm 3 . According to such particles, it is possible to obtain a soft touch characteristic and an effect of easily extending and spreading uniformly on the skin (that is, high fluidity).
- the convex portions on the particle surface are preferably provided at a ratio of 5 or more per 1 ⁇ m 2 , and a spherical crown shape is preferable.
- the outer shell of the hollow particles is preferably nonporous. Therefore, the true specific gravity is preferably 2.2 g / cm 3 or more.
- the cosmetic of the present invention contains any of the hollow particles described above.
- the hollow particles of the present invention have a balloon structure having a cavity inside the outer shell. Projections of 3 to 100 nm are provided on the surface of the particles.
- the true specific gravity of the particles is 0.3 to 3.0 g / cm 3 and the specific surface area (m 2 / cm 3 ) per unit volume determined by the BET method is 0.5 or more and less than 60.
- the average particle diameter (d 1 ) determined by the laser diffraction method is in the range of 1 to 20 ⁇ m. According to such particles, soft feel characteristics and appropriate fluidity can be obtained.
- the average particle diameter (d 1 ) is less than 1 ⁇ m, the adhesion becomes high, and it becomes difficult to uniformly spread on the skin (that is, the fluidity is low).
- the particle diameter exceeds 20 ⁇ m it feels rough when the particle powder is touched, and the soft feeling is reduced.
- the average particle size is preferably 2 to 8 ⁇ m.
- the hollow particles are inorganic oxide particles containing silica. That is, the outer shell of the hollow particles is formed of a composite oxide such as silica-alumina, silica-zirconia, and silica-titania, and silica. In consideration of blending into cosmetics, amorphous silica particles are suitable for the hollow particles.
- the preferable range of the true specific gravity varies depending on the composition of the particles. For example, if 99% or more of the composition is silica, the true specific gravity of the particles is preferably 0.3 to 2.1 g / cm 3 . Since the specific gravity of silica is 2.2 g / cm 3 , it can be considered that there is a cavity inside if it is 2.1 g / cm 3 or less. Hollow particles having a true specific gravity of 0.3 g / cm 3 or less have a thin outer shell and a low strength. Therefore, there is a possibility that particles are destroyed due to mechanical share when blended in cosmetics. On the other hand, when the true specific gravity exceeds 2.1 g / cm 3 , sufficient cavities do not exist. Therefore, it is difficult to obtain soft touch characteristics.
- the true specific gravity of the particles is more preferably 0.5 to 2.0 g / cm 3 , further preferably 0.7 to 1.8 g / cm 3 .
- the calculated specific gravity is 2.5 g / cm 3 .
- the true specific gravity is preferably 0.4 to 2.4 g / cm 3 .
- the composition ratio (silica / alumina) is 35/65, the calculated specific gravity is 3.1 g / cm 3 , so the true specific gravity of the particles is 0.5 to 3.0 g / cm 3. preferable.
- the specific gravity of the particles is lower than the theoretical specific gravity calculated from the composition, it can be said that there is a cavity inside.
- porosity (1 ⁇ true specific gravity / (theoretical specific gravity calculated from the composition of particles)) ⁇ 100”
- porosity 1 ⁇ true specific gravity / (theoretical specific gravity calculated from the composition of particles)
- the specific surface area of the hollow particles obtained by the BET method is 60 m 2 / cm 3 or more, the definition of the nanomaterial is satisfied, and there is a possibility that the hollow particles cannot be used with peace of mind in the same applications as conventional plastic beads.
- the size of the convex portion on the particle surface is less than 3 nm, the adhesiveness is high, and the fluidity is significantly lowered. On the other hand, when it exceeds 100 nm, the adhesion is too low, and the rolling property of the particles is increased, and as a result, it becomes difficult to obtain a desired soft feeling.
- the height of the convex portion is preferably 5 to 60 nm, and more preferably 7 to 20 nm. Further, it is preferable that 5 or more convex portions having a size of 3 nm or more exist per 1 ⁇ m 2 . If there are five or more, uniform frictional resistance can be imparted. Furthermore, it is preferable that the convex portion has a spherical crown shape. The spherical crown shape makes it easy to uniformly control the frictional resistance.
- the outer shell is preferably nonporous. That is, when 99% or more of the composition of the particles is silica, the true specific gravity of the outer shell is preferably 2.2 g / cm 3 . When the true specific gravity of the outer shell is less than 2.2 g / cm 3 , the mechanical strength of the outer shell is lowered, and the particles may be broken due to the mechanical share when blended in the cosmetic.
- the preferable true specific gravity value increases as the proportion of alumina increases. That is, a true specific gravity of 2.2 g / cm 3 or less is not preferable for a nonporous outer shell.
- the haze when the haze is measured by putting hollow particles in a dispersion having a refractive index of 1.46, it is suitable that the haze is 50% or more. Since the refractive index of sebum secreted from the skin is around 1.46, even when the hollow particles are applied to the skin and then wet with sebum, the appropriate light diffusivity is not impaired.
- the maximum absorbance (I 1) in the 3730 ⁇ 3750cm -1, the ratio of the maximum absorbance (I 2) in the 1160 ⁇ 1260cm -1 (I 1 / I 2) is 0.05 or less is suitable.
- the silanol group (Si—OH) on the particle surface decreases, the infrared absorbance at 3730-3750 cm ⁇ 1 decreases.
- the infrared absorbance at 1160 to 1260 cm ⁇ 1 belonging to Si—O—Si increases. Since silanol groups bind to water, the less silanol groups, the lower the hydrophilicity.
- the surface may be hydrophobized by surface treatment with a silane compound or the like, or crushing silanol groups by high-temperature baking or the like.
- a sol in which spherical inorganic oxide fine particles are dispersed in water is prepared.
- the sol preferably contains 1 to 30% by weight of inorganic oxide fine particles in terms of solid content.
- the inorganic oxide fine particles are fine particles containing silica as a component, and examples thereof include fine particles of composite oxides such as silica-alumina, silica-zirconia, silica-titania, and silica fine particles.
- amorphous silica fine particles are preferable. Note that it is not necessary to change the production conditions depending on the difference in the composition of the fine particles.
- a slurry is prepared by adding a silicic acid solution having a silica concentration of 1 to 50% by weight to this inorganic oxide sol.
- the inorganic oxide sol and the silicic acid so that the solid weight ratio (I / II) of the inorganic oxide component (I) of the sol and the silica component (II) of the silicic acid solution is in the range of 0.05 to 1. Mix the liquid.
- Silicate salts include alkali metal silicates such as sodium silicate (water glass) and potassium silicate, and silicates of organic bases such as quaternary ammonium silicate.
- granulation is performed by a conventionally known spray drying method.
- a spray liquid slurry
- a spray liquid sprayed into a hot air stream at a rate of 1 to 3 liters / hour.
- the temperature of the hot air is preferably in the range of 70 to 600 ° C. at the inlet temperature and 40 to 300 ° C. at the outlet temperature.
- the inlet temperature is less than 70 ° C.
- the solid content is insufficiently dried.
- it exceeds 600 degreeC there exists a possibility that a particle shape may be distorted.
- the outlet temperature is less than 40 ° C., the degree of drying of the solid content is poor, and the particles tend to adhere to the inside of the apparatus. If necessary, the obtained particles may be washed, dried, and fired.
- particles having a balloon structure in which cavities are formed inside the outer shell are obtained.
- this hollow particle has a convex part of 3 to 100 nm on the surface, and the true specific gravity of the hollow particle is 0.3 to 3.0 g / cm 3 .
- the outer shell is composed of a silicic acid component contained in the slurry, and the convex portion formed in the outer shell is composed of inorganic oxide fine particles. Therefore, the average particle diameter (d 2 ) of the inorganic oxide fine particles is preferably 6 nm to 200 nm. When the average particle diameter exceeds 200 nm, the convex portions on the particle surface are too large, and desired touch characteristics cannot be obtained.
- inorganic oxide fine particles having an average particle diameter of less than 6 nm have low stability and are not preferable from an industrial viewpoint.
- the average particle size is more preferably from 10 to 120 nm, particularly preferably from 14 to 90 nm.
- the particle size variation coefficient (CV) of the inorganic oxide fine particles is preferably within 10%.
- the inorganic oxide fine particles fine particles having the above composition may be used, and a metal component such as alumina, zirconia, or titania may be included in the silicic acid solution. That is, hollow particles having various compositions can be obtained by adjusting the composition of the inorganic oxide sol and the composition of the silicic acid solution. For example, particles having outer shells and convex portions made of silica, particles having outer shells and convex portions made of silica-alumina, and particles made of silica-based materials having different outer shells and convex portions are easily obtained. be able to.
- generated from the raw material derived from a plant it is preferable from a viewpoint of realization of a sustainable society to comprise a hollow particle using the silica component produced
- ISO16128-1 (Guidelines on technical definitions and criteria for natural And organic cosmetic ingredients and products Part1: Definitions for ingredients)
- the raw materials are defined.
- Silica sand, which is frequently used as a silica source, is classified as a mineral component, but if it is a plant-derived silica component, it is classified as a naturally-derived component, so that it can meet the needs.
- Plant-derived silica components are abundant in gramineous plants and can be extracted from rice husks and their ears. For example, it is known that high-purity silica can be obtained by a firing method disclosed in JP-A-7-196312, a pressurized hot water method disclosed in JP-A-2002-265257, or the like. The plant-derived silica component thus obtained is dissolved in sodium hydroxide to prepare sodium silicate, and then silica-based particles can be prepared according to a conventional method.
- Example 1 The sol (commercial product: manufactured by JGC Catalysts &Chemicals; Cataloid SI-30, silica concentration of 30% by weight) in which silica fine particles having an average particle diameter of 11 nm are dispersed in water is subjected to cation exchange to adjust the pH to 2.0. did. Thereby, a silica sol having a solid concentration of 30% by weight was obtained as an inorganic oxide sol.
- This silica sol contains silica fine particles as inorganic oxide fine particles.
- the dispersion slurry is spray-dried by using 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 200 ° C. and an outlet temperature of 50 to 55 ° C., gas is supplied from one of the two-fluid nozzles at a flow rate of 2 L / hour and from the other nozzle at a pressure of 0.15 MPa. Spray dried to obtain a dry powder.
- a spray dryer NIRO-ATMIZER, manufactured by NIRO
- the dried powder was baked at 600 ° C. for 4 hours. Thereafter, dry sieving was performed to obtain a powder of hollow particles.
- Table 2 shows the physical properties of this powder.
- Table 1 shows the particle preparation conditions. Each measured value in the table was measured by the following method.
- Average particle size (d 1 ), (d 2 ), and particle size variation coefficient (CV) The particle size distribution of each particle was measured by a laser diffraction method. The average particle diameter of the hollow particles based on the particle size distribution (d 1), to obtain an average particle size of the inorganic oxide fine particles (d 2) and the particle diameter coefficient of variation (CV). At this time, the median value obtained from the particle size distribution was defined as the average particle size.
- the particle size distribution was measured using a laser diffraction / scattering particle size distribution measuring apparatus LA-950v2 (manufactured by Horiba, Ltd.).
- Pore Volume After taking 10 g of hollow particle powder in a crucible and drying at 105 ° C. for 1 hour, it was placed in a desiccator and cooled to room temperature. Next, 1.0 g of a sample was placed in a well-cleaned cell, nitrogen was adsorbed using a nitrogen adsorption device, and the pore volume was calculated from the following equation.
- Pore volume (ml / g) (0.001567 ⁇ (V ⁇ Vc) / W)
- V is the adsorption amount (ml) in the standard state at a pressure of 735 mmHg
- Vc is the cell blank capacity (ml) at a pressure of 735 mmHg
- W is the mass (g) of the sample.
- the ratio of the density of nitrogen gas and liquid nitrogen is 0.001567.
- Shape and number of convex portions of hollow particles SEM photographs taken using a scanning electron microscope were observed to evaluate the number of convex portions of the hollow particles. An SEM image of 100 to 200 randomly selected particles was analyzed to confirm whether the shape of the convex portion was a spherical crown. Moreover, the convex part of a magnitude
- Haze in dispersion (refractive index 1.46) 9.0 g of distilled water and 91.0 g of glycerin (special grade, manufactured by Kanto Chemical Co., Ltd.) were mixed to prepare an aqueous glycerin solution having a refractive index of 1.46. To 7.0 g of this glycerin aqueous solution, 3.0 g of hollow particle powder was added and dispersed by irradiating ultrasonic waves for 30 minutes (US-2KS manufactured by SND Co., Ltd.). The Haze of the obtained dispersion was measured using a color / turbidity simultaneous measuring device (300A manufactured by Nippon Denshoku Co., Ltd.) to obtain a Haze of hollow particles.
- a color / turbidity simultaneous measuring device 300A manufactured by Nippon Denshoku Co., Ltd.
- Example 2 In Example 1, instead of silica sol (SI-30), SS-160 (manufactured by JGC Catalysts & Chemicals Co., Ltd., average particle size 160 nm) was used to prepare an inorganic oxide sol having a solid content concentration of 16% by weight. . This sol and the silicic acid solution of Example 1 were added so as to have a solid content weight ratio shown in Table 1 to obtain a dispersed slurry. Using this dispersion slurry, a hollow particle powder was prepared and measured in the same manner as in Example 1.
- Example 3 In this example, the gas supply pressure of the two-fluid nozzle was set to 0.3 MPa. Except for this, a hollow particle powder was prepared and measured in the same manner as in Example 1.
- Example 4 In this example, the gas supply pressure of the two-fluid nozzle was set to 0.6 MPa. Except for this, a hollow particle powder was prepared and measured in the same manner as in Example 1.
- Example 5 JIS No. 3 water glass was used as a silicate solution (II) without cation exchange, and the inlet temperature during spray drying was 380 ° C. Except for this, a dry powder was prepared in the same manner as in Example 1. 100 g of the obtained dry powder was suspended in a sulfuric acid aqueous solution (25%) and neutralized. The slurry obtained by neutralization was filtered through a quantitative filter paper (No. 2 manufactured by Advantech Toyo Co., Ltd.) using a Buchner funnel (3.2 L manufactured by Sekiya Rika Glass Instruments Co., Ltd.). Thereafter, it was repeatedly washed with pure water to obtain a cake-like substance.
- a quantitative filter paper No. 2 manufactured by Advantech Toyo Co., Ltd.
- This cake-like substance was dried (120 ° C., 16 hours) to obtain a dry powder ⁇ . Then, it baked at 1000 degreeC for 3 hours, the dry-type sieve process was performed, and the powder was obtained. This powder was measured in the same manner as in Example 1.
- Example 6 the solid content weight ratio (I / II) of the silica component (I) of the inorganic oxide sol and the silica component (II) of the silicic acid solution in the dispersion slurry was changed to 50/50. Except for this, a hollow particle powder was prepared and measured in the same manner as in Example 1.
- Example 7 In Example 1, an inorganic oxide sol was prepared using SI-80P (manufactured by JGC Catalysts & Chemicals, Inc., average particle size of 80 nm) instead of silica sol (SI-30). This sol and the silicic acid solution of Example 1 were added so as to have a solid content weight ratio shown in Table 1. Using the resulting dispersion slurry, a hollow particle powder was prepared and measured in the same manner as in Example 1.
- SI-80P manufactured by JGC Catalysts & Chemicals, Inc., average particle size of 80 nm
- SI-30 silica sol
- Example 8 In this example, the firing conditions were 1000 ° C. and 3 hours. Except for this, a hollow particle powder was prepared and measured in the same manner as in Example 1.
- Example 1 In Example 1, instead of silica sol (SI-30), SI-550 (manufactured by JGC Catalysts & Chemicals Co., Ltd., average particle size 5 nm) was used to prepare an inorganic oxide sol having a solid content concentration of 10% by weight. . This sol and the silicic acid solution of Example 1 were added so as to have a solid content weight ratio shown in Table 1. Using the resulting dispersion slurry, a particle powder was prepared and measured in the same manner as in Example 1.
- SI-550 manufactured by JGC Catalysts & Chemicals Co., Ltd., average particle size 5 nm
- Comparative Example 5 In this comparative example, a dispersion slurry was prepared only with silicic acid solution without using silica sol. Except for this, a powder of particles was prepared and measured in the same manner as in Example 1.
- the particle powder obtained in each example and comparative example was subjected to a sensory test by 20 professional panelists, and it was smooth, moist, rolling, uniform spreadability, adhesion to the skin, and rolling.
- Interviews were conducted on seven evaluation items (feel characteristics) of the sustainability and soft feeling. The results were evaluated based on the following evaluation point criteria (a). Furthermore, the evaluation points given by each person were totaled, and the feel of the particles was evaluated based on the following evaluation criteria (b).
- Evaluation point criteria (a) 5 points: Very good 4 points: Excellent 3 points: Normal 2 points: Inferior 1 point: Very inferior evaluation criteria (b) ⁇ : 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
- Table 3 As can be seen from the table, the powder of each example is extremely excellent as a feel-improving material for cosmetics, but the powder of the comparative example is not suitable as a feel-improving material.
- the cosmetics A to C according to Examples 1, 2, and 5 were found to be very excellent in use feeling both during and after application. However, it was found that the cosmetics a to c of Comparative Examples 1, 2, and 4 were not good in use feeling.
- hollow particles obtained in each of the above-described examples are used by blending with various cosmetic ingredients exemplified below.
- Oils such as olive oil, rapeseed oil, and beef tallow.
- Jojoba oil carnauba wax, candelilla wax, beeswax as waxes.
- hydrocarbons paraffin, squalane, synthetic and vegetable squalane, ⁇ -olefin oligomer, microcrystalline wax, pentane, hexane.
- fatty acids stearic acid, myristic acid, oleic acid, ⁇ -hydroxy acid.
- alcohols examples include isostearyl alcohol, octyldodecanol, lauryl alcohol, ethanol, isopropanol, butyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, and behenyl alcohol.
- Esters include alkyl glyceryl ethers, isopropyl myristate, isopropyl palmitate, ethyl stearate, ethyl oleate, cetyl laurate, decyl oleate.
- polyhydric alcohols ethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, glycerin, diglycerin.
- Silicone oils include methylpolysiloxane, methylhydrogenpolysiloxane, methylphenyl silicone oil, various modified silicone oils, and cyclic dimethylsilicone oil. Silicone gel cross-linked with silicone and / or other organic compounds. Nonionic, cationic and anionic surfactants. Fluorine oil such as perfluoropolyether. Various polymers such as gum arabic, carrageenan, agar, xanthan gum, gelatin, alginic acid, guar gum, albumin, pullulan, carboxyvinyl polymer, cellulose and its derivatives, polyacrylamide, sodium polyacrylate, polyvinyl alcohol and the like.
- UV protection agents such as cinnamic acid such as octyl paramethoxycinnamate, salicylic acid, benzoic acid ester, urocanic acid and benzophenone.
- Disinfectant / preservative Antioxidant. Modified or unmodified clay mineral. Solvents such as butyl acetate, acetone, and toluene. Various organic facial dyes. water. Perfume.
- the surface of the inorganic compound such as titanium oxide or zinc oxide may be subjected to silicone treatment, fluorine treatment, metal soap treatment, or the like in advance.
- resin particles such as polymethyl acrylate, nylon, silicone resin, silicone rubber, polyethylene, polyester, and polyurethane may be included.
- resin particles such as polymethyl acrylate, nylon, silicone resin, silicone rubber, polyethylene, polyester, and polyurethane may be included.
- a component having a whitening effect arbutin, kojic acid, vitamin C, sodium ascorbate, magnesium ascorbate phosphate, ascorbyl di-palmitate, glucoside ascorbate, other ascorbic acid derivatives, placenta extract, sulfur, oil Plant extracts such as soluble licorice extract and mulberry extract, linoleic acid, linolenic acid, lactic acid, tranexamic acid and the like may be included.
- Anti-aging effects such as vitamin C, carotenoids, flavonoids, tannins, caffeic acid 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.
- cosmetics for cleaning (soaps, cleansing foams, makeup-removing creams, etc.), skin care cosmetics (moisturizing, preventing rough skin, acne, keratin care, massage, wrinkle / sagging, dullness / bearing, UV care , Whitening, antioxidant care, etc.), base makeup cosmetics (powder foundation, liquid foundation, cream foundation, mousse foundation, pressed powder, makeup base), point makeup cosmetics (eye shadow, eyebrow, Eyeliner, mascara, lipstick), hair care cosmetics (for hair growth, anti-dandruff, itching prevention, cleaning, conditioning / hair styling, permanent wave, hair color / hair bleach cosmetic), body care cosmetics (for cleaning) , Sunburn prevention, rough hand prevention, For rimming, blood circulation improvement, itching suppression, body odor prevention, antiperspirant, hair care, repellant,
Abstract
Description
ここで、組成の99%以上がシリカであれば、粒子の空隙率は5~86%である。
次に、本発明の中空粒子の製造方法について説明する。
はじめに、球状の無機酸化物微粒子が水に分散されたゾルを用意する。ゾルには、無機酸化物微粒子が固形分換算で1~30重量%含まれることが望ましい。ここで、無機酸化物微粒子は、成分にシリカを含有する微粒子であり、シリカ-アルミナ、シリカ-ジルコニア、シリカ-チタニアなどの複合酸化物の微粒子、およびシリカ微粒子が例示できる。化粧料に配合することを考慮すると、非晶質のシリカ微粒子が好適である。なお、微粒子の組成の違いによって製造条件を変更する必要はない。
工程Aで得られたスラリーを用いて、従来公知の噴霧乾燥方法で造粒する。例えば、スプレードライヤーによる噴霧乾燥法では、噴霧液(スラリー)を熱風気流中に1~3リットル/時の速度で噴霧する。これによって中空粒子が得られる。このとき、熱風の温度は、入口温度で70~600℃、出口温度で40~300℃の範囲が好ましい。入口温度が70℃未満だと、固形分の乾燥が不充分となる。また600℃を超えると、粒子形状が歪むおそれがある。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、粒子が装置内に付着しやすい。必要に応じて、得られた粒子を、洗浄、乾燥、焼成してもよい。
本発明の中空粒子を化粧料に用いると、従来のシリカ粒子等の無機粒子と異なり、転がり感、転がり感の持続性、及び均一な延び広がり性だけでなく、プラスチックビーズ特有のソフト感としっとり感という、化粧料の感触改良材に求められる代表的な感触特性が得られる。
平均粒子径11nmのシリカ微粒子が水に分散されたゾル(市販品:日揮触媒化成(株)製;Cataloid SI-30、シリカ濃度30重量%)を陽イオン交換し、pHを2.0に調整した。これにより、固形分濃度30重量%のシリカゾルが無機酸化物ゾルとして得られた。このシリカゾルにはシリカ微粒子が無機酸化物微粒子として含まれている。
それぞれの粒子の粒度分布をレーザー回折法により測定した。この粒度分布に基づいて中空粒子の平均粒子径(d1)、無機酸化物微粒子の平均粒子径(d2)と粒子径変動係数(CV)を求めた。このとき、粒度分布から得られたメジアン値を平均粒子径とした。なお、レーザー回折/散乱式粒子径分布測定装置LA-950v2(株式会社堀場製作所製)を用いて粒度分布を測定した。
中空粒子の粉体を磁性ルツボ(B-2型)に約30ml採取し、300℃で1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た。
中空粒子の粉体をメノウ乳鉢に入れ、乳棒を用いて粉砕し、得られた粉砕物の真比重を測定した。粉砕により、中空粒子が崩壊して、内部の空洞がなくなっている。そのため、粉砕物の真比重を外殻の真比重とした。
中空粒子の粉体を磁性ルツボ(B-2型)に約30ml採取し、300℃で1時間乾燥させた後、デシケーターに入れて室温まで冷却した。次に、試料を1.0g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、BET法で比表面積(m2/g)を測定した。そして、シリカの比重を2.2g/cm3として単位体積当たりの比表面積に換算した。
中空粒子の粉体10gをルツボに取り、105℃で1時間乾燥させた後、デシケーターに入れて室温まで冷却した。次いで、よく洗浄したセルに試料1.0gを入れ、窒素吸着装置を用いて窒素を吸着させ、以下の式から細孔容積を算出した。
上式で、Vは圧力735mmHgにおける標準状態の吸着量(ml)、Vcは圧力735mmHgにおけるセルブランクの容量(ml)、Wは試料の質量(g)を表す。また、窒素ガスと液体窒素の密度の比は0.001567とする。
中空粒子の粉体0.1gをエポキシ樹脂約1g(BUEHLHER製EPO-KWICK)に均一に混合して常温で硬化させた後、FIB加工装置(日立製作所製、FB-2100)を用いて、20μmエリアの断面加工を行い、厚み100~200nmの切片の試料を作製した。次いで、透過型電子顕微鏡(日立製作所製、HF-2200)を用いて、この試料を加速電圧200kVの条件下で、倍率100000倍のTEM写真を撮影した。さらに、任意のTEM写真10枚について、粒子表面の外接円と内接円の差を計測し、その平均値を中空粒子表面の凸部の大きさとした。
走査型電子顕微鏡を用いて撮影したSEM写真を観察し、中空粒子の凸部の数を評価した。無作為に選択した粒子100~200個のSEM画像を解析して凸部の形状が球冠状かどうかを確認した。また、5nm以上の大きさの凸部をカウントし、1μm2の投影部に5個以上形成されているかどうかを確認した。
蒸留水9.0gとグリセリン(関東化学(株)製、特級)91.0gを混合し、屈折率1.46のグリセリン水溶液を調製した。このグリセリン水溶液7.0gに中空粒子の粉体3.0gを加え、超音波を30分間照射((株)エスエヌディ製US-2KS)して分散した。得られた分散液のHazeを色彩・濁度同時測定器(日本電色(株)製300A)を用いて測定し、中空粒子のHazeとした。
中空粒子の粉体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した。冷却後、水約50mlを加えて加温溶解した。冷却後、水200mlに希釈しこれを試験溶液とした。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、中空粒子の組成率を求めた。
中空粒子の赤外吸収スペクトルを、FT-IR6300(日本分光社製)を用いて測定し、波数(cm-1)とクベルカムンク式で計算した吸光度との関係を示すグラフを作成した。得られたグラフから、3730~3750cm-1における最大吸光度(I1)と1160~1260cm-1における最大吸光度(I2)を読み取り、吸光度比(I1/ I2)を算出した。
実施例1で、シリカゾル(SI-30)の代わりに、SS-160(日揮触媒化成(株)製、平均粒子径160nm)を使用し、固形分濃度16重量%の無機酸化物ゾルを調製した。このゾルと実施例1の珪酸液を表1に示した固形分重量比になるように加え、分散スラリーを得た。この分散スラリーを用いて、実施例1と同様に中空粒子の粉体を調製し、測定した。
本実施例では、2流体ノズルの気体供給圧力を0.3MPaとした。これ以外は実施例1と同様に、中空粒子の粉体を調製し、測定した。
本実施例では、2流体ノズルの気体供給圧力を0.6MPaとした。これ以外は実施例1と同様に、中空粒子の粉体を調製し、測定した。
本実施例では、JIS3号水硝子を陽イオン交換せずに珪酸液(II)として使用し、噴霧乾燥時の入口温度を380℃とした。これ以外は実施例1と同様に乾燥粉体を調製した。得られた乾燥粉体100gを、硫酸水溶液(25%)中に懸濁し、中和した。中和して得られたスラリーをブフナー漏斗(関谷理化硝子器械(株)製3.2L)を用いて定量濾紙(アドバンテック東洋(株)製No.2)で濾過した。その後、純水で繰り返し洗浄し、ケーキ状物質を得た。このケーキ状物質を乾燥(120℃、16時間)させ、乾燥粉体αを得た。その後、1000℃で3時間焼成し、乾式篩処理を行って粉体を得た。この粉体を実施例1と同様に測定した。
本実施例では、分散スラリー内の無機酸化物ゾルのシリカ成分(I)と珪酸液のシリカ成分(II)の固形分重量比(I/II)を50/50に変更した。これ以外は実施例1と同様に、中空粒子の粉体を調製し、測定した。
実施例1で、シリカゾル(SI-30)の代わりに、SI-80P(日揮触媒化成(株)製、平均粒子径80nm)を使用して無機酸化物ゾルを調製した。このゾルと実施例1の珪酸液を表1に示した固形分重量比になるように加えた。これにより得られた分散スラリーを用いて、実施例1と同様に中空粒子の粉体を調製し、測定した。
本実施例では、焼成条件を1000℃、3時間とした。これ以外は実施例1と同様に、中空粒子の粉体を調製し、測定した。
実施例1で、シリカゾル(SI-30)の代わりに、USBB-120(日揮触媒化成(株)製、平均粒子径5nm、組成:シリカ/アルミナ=70/30)を使用し、固形分濃度23重量%の無機酸化物ゾルを調製した。このゾルと実施例1の珪酸液を表1に示した固形分重量比になるように加えた。これにより得られた分散スラリーを用いて、実施例1と同様に中空粒子の粉体を調製し、測定した。
実施例1で、シリカゾル(SI-30)の代わりに、SI-550(日揮触媒化成(株)製、平均粒子径5nm)を使用し、固形分濃度10重量%の無機酸化物ゾルを調製した。このゾルと実施例1の珪酸液を表1に示した固形分重量比になるように加えた。これにより得られた分散スラリーを用いて、実施例1と同様に粒子の粉体を調製し、測定した。
分散スラリー内の無機酸化物ゾルのシリカ成分(I)と珪酸液のシリカ成分(II)の固形分重量比(I/II)が95/5になるように混合した。これ以外は実施例1と同様に、粒子の粉体を調製し、測定した。
本比較例では、分散スラリー内の無機酸化物ゾルのシリカ成分(I)と珪酸液のシリカ成分(II)の固形分重量比(I/II)が50/50になるように混合した。さらに、2流体ノズルの気体供給圧力を0.05MPa、噴霧速度を4L/時とした。これ以外は実施例1と同様に、粒子の粉体を調製し、測定した。
本比較例では、分散スラリー内の無機酸化物ゾルのシリカ成分(I)と珪酸液のシリカ成分(II)の固形分重量比(I/II)が1/99になるように混合した。これ以外は実施例1と同様に、粒子の粉体を調製し、測定した。
本比較例では、シリカゾルを用いずに珪酸液だけで分散スラリーを調製した。これ以外は実施例1と同様に、粒子の粉体を調製し、測定した。
各実施例と比較例により得られた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、およびソフト感の7つの評価項目(感触特性)に関して聞き取り調査を行った。その結果を以下の評価点基準(a)に基づき評価した。さらに、各人がつけた評価点を合計し、以下の評価基準(b)に基づき粒子の感触を評価した。
評価点基準(a)
5点:非常に優れている
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
その結果を表3に示す。表から解るように、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。
表4に示す配合比率(重量%)で、各実施例(または比較例)の粒子の粉体と、他の成分(2)~(9)を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、さらに均一に混合させた。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、(i)肌への塗布中の均一な延び、しっとり感、滑らかさ、および(ii)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った。その結果を前述の評価点基準(a)に基づき評価する。また、各人がつけた評価点を合計し、前述の評価基準(b)に基づきファンデーションの使用感を評価した。結果を表5に示す。
Claims (7)
- 平均粒子径(d1)が1~20μmの範囲にあり、外殻の内部に空洞を有するバルーン構造の中空粒子であって、該粒子の真比重が0.3~3.0g/cm3、BET法で求めた単位体積あたりの比表面積が0.5m2/cm3以上60m2/cm3未満であり、粒子表面に3~100nmの凸部を有することを特徴とする中空粒子。
- 前記凸部が、1μm2当たり5個以上存在することを特徴とする請求項1に記載の中空粒子。
- 前記凸部が球冠状であることを特徴とする請求項1または2に記載の中空粒子。
- 前記外殻が成分としてシリカを含むことを特徴とする請求項1~3のいずれか一項に記載の中空粒子。
- 前記外殻の真比重は2.2g/cm3以上であることを特徴とする請求項1~4のいずれか一項に記載の中空粒子。
- 屈折率1.46の分散液中における該中空粒子のHazeが50%以上で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中空粒子。
- 請求項1~6のいずれか一項に記載の中空粒子が配合された化粧料。
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Also Published As
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EP3632849B1 (en) | 2022-07-06 |
BR112019024941A2 (pt) | 2020-06-23 |
BR112019024941B1 (pt) | 2022-04-26 |
EP3632849A4 (en) | 2020-05-06 |
CN110603223A (zh) | 2019-12-20 |
US11020326B2 (en) | 2021-06-01 |
CN110603223B (zh) | 2023-05-09 |
JPWO2018221406A1 (ja) | 2020-05-21 |
JP7170633B2 (ja) | 2022-11-14 |
KR20200014744A (ko) | 2020-02-11 |
CA3063038A1 (en) | 2019-12-03 |
US20200179244A1 (en) | 2020-06-11 |
EP3632849A1 (en) | 2020-04-08 |
KR102575425B1 (ko) | 2023-09-07 |
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