Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
  • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
• • 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
  • A61K8/0245—Specific shapes or structures not provided for by any of the groups of A61K8/0241
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
  • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
  • C01B21/0645—Preparation by carboreductive nitridation
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
  • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
  • C01B21/0648—After-treatment, e.g. grinding, purification
• • 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
• • 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
  • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/51—Particles with a specific particle size distribution
• • 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

Definitions

• the present invention relates to hexagonal boron nitride powder (hereinafter sometimes abbreviated as boron nitride powder or h-BN powder). More particularly, it relates to a hexagonal boron nitride powder suitable for use in cosmetics and a method for producing the same.
• boron nitride powder hereinafter sometimes abbreviated as boron nitride powder or h-BN powder.
• Inorganic materials such as talc, mica and kaolin, and resin materials such as nylon powder and polyethylene powder have been used as cosmetics.
• their usability and stability were not always satisfactory.
• inorganic materials such as talc, mica, and kaolin are said to cause deterioration of fragrances and oils and cause offensive odors due to their catalytic activity.
• Resin materials such as nylon powder and polyethylene powder are chemically stable, but have the problem of poor moldability. Therefore, hexagonal boron nitride, which has a flat shape and is superior in lubricity as compared with other materials, has been used as a pigment for cosmetics.
• Cosmetics are bases for dispersing color pigments, and have a great influence on the feeling of use, such as spreadability (property of being applied smoothly on the skin surface) and stickiness (property of maintaining the applied state on the skin).
• Patent Document 1 boric acid, urea, and boron carbide are reacted at a predetermined ratio of oxygen to carbon, and plate-like aggregates in which primary particles having a predetermined average length and thickness and having a flat shape are laminated are prepared.
• a boron nitride powder consisting of aggregates is described.
• Patent Document 2 discloses a hexagonal boron nitride powder that has a predetermined average particle size, maximum particle size, specific surface area, and a predetermined graphitization index as a hexagonal boron nitride powder that can improve slipperiness and reduce roughness. , average coefficient of friction, and hexagonal boron nitride powders with varying values of average coefficient of friction are described.
• Patent Literature 2 describes a method for producing hexagonal boron nitride powder by defining first firing conditions and second firing conditions.
• “mochi” which is the property of maintaining the state of being applied to the skin, is closely related to the oil absorption of the constituent powder of the cosmetic, and has a predetermined water penetration rate and oil absorption.
• Boron nitride powder has been proposed.
• the boron nitride powder described in Patent Document 3 is produced by subjecting boric acid, urea, and boron carbide to two-stage heat treatment.
• Patent Document 4 describes a boron nitride powder that is suitable for cosmetics, has excellent tactile sensations such as "moist” and “slimy” while maintaining moderate lubricity, and has an amount of eluted boron, an average particle size, and specific particles.
• a boron nitride powder has been proposed in which the content of particles with a diameter is less than or equal to a predetermined value.
• Patent Document 4 describes the average friction coefficient of this boron nitride powder and the fluctuation value of the average friction coefficient. Further, Patent Document 4 describes a method for producing boron nitride powder by two-step firing, pulverization and washing.
• Patent Document 5 discloses a hexagonal boron nitride powder capable of realizing a resin sheet with high thermal conductivity and high dielectric strength, which has a predetermined specific surface area, major diameter of primary particles, and an aspect ratio. is proposed. Patent Document 5 describes a method for producing hexagonal boron nitride powder by heating boron oxide, nitrogen-containing organic compound, and lithium carbonate in a predetermined weight ratio.
• Patent Document 6 a raw material powder containing hexagonal boron nitride particles having an aspect ratio within a predetermined range and hexagonal boron nitride particles having an aspect ratio exceeding a predetermined value is prepared by a means that does not substantially involve pulverization of primary particles. A method for producing a low aspect ratio hexagonal boron nitride powder that is crushed at is described.
• the present inventors found that when producing hexagonal boron nitride powder by a reduction nitriding method in which a raw material mixture is heated in a nitrogen atmosphere, if BN seed crystals produced by a melamine method are present as seed crystals, the particle size A uniform boron nitride powder can be produced, and such a boron nitride powder having a uniform particle size has good slipperiness, good moist feeling (skin familiarity), and less roughness. completed.
• the present invention includes the following inventions. 1.
• the particle size of D95 is 70 ⁇ m or less and the dynamic friction coefficient (MIU) is 0.50 or less.
• the D95 is the cumulative 95% value in the cumulative distribution (a) of the volume-based particle diameter in the particle size distribution curve
• the average particle size (D50) is 3 to 15 ⁇ m
• (D90 ⁇ D10)/D50 is 1.30 or less
• the content of coarse particles exceeding 3 times D50 is 2.0% by volume or less
• the D10, the D50 and the D90 are each the volume-based particle diameter in the particle size distribution curve
• a method for producing hexagonal boron nitride powder which includes a reductive nitriding step of heating a raw material mixture in a nitrogen atmosphere,
• the raw material mixture contains an oxygen-containing boron compound, an oxygen-containing alkaline earth metal compound, a carbon source compound and a seed crystal (S), and the seed crystal (S) is a BN seed crystal produced by a melamine method.
• a method for producing the hexagonal boron nitride powder is a BN seed crystal produced by a melamine method.
• the atomic ratio (B/C ratio) of the boron atom (B) of the oxygen-containing boron compound and the carbon atom (C) of the carbon source compound is 0.70 to 2.00
• the molar ratio (MO/B 2 O 3 ) between the oxygen-containing alkaline earth metal compound (MO; M is an alkaline earth metal) and the oxygen-containing boron compound in terms of oxide is 0.01 to 1.0.
• the atomic ratio (B S /C ratio) of the boron atom (B s ) of the BN seed crystal of the seed crystal (S) and the carbon atom (C) of the carbon source compound is 0.01 to 13 Method of manufacture as described. 6.
• the melamine method includes a step of heating a raw material mixture containing an oxygen-containing boron compound and a nitrogen-containing organic compound at 500 to 1200 ° C. under a nitrogen atmosphere.
• the hexagonal boron nitride powder of the present invention has a sharp particle size distribution and a uniform particle size, and can be suitably used in cosmetics. Furthermore, the cosmetic containing the hexagonal boron nitride powder of the present invention has good slipperiness, good moist feeling (compatibility with the skin), and less roughness. According to the method for producing a boron nitride powder of the present invention, a hexagonal boron nitride powder having a sharp particle size distribution and a uniform particle size can be produced.
• the boron nitride powder of the present invention has a particle size of D95 in the cumulative distribution (a) of the volume-based particle size measured by the laser diffraction/scattering method without ultrasonic treatment, preferably 70 ⁇ m or less, preferably 65 ⁇ m or less. More preferably, it is 60 ⁇ m or less.
• D95 is the value for unsonicated boron nitride powder. If the D95 exceeds the above value, properties required for cosmetics such as slipperiness, moist feeling, and roughness are deteriorated.
• D95 when ultrasonic treatment is not performed means the cumulative 95% value in cumulative distribution (a) of volume-based particle diameters in the particle size distribution curve.
• MIU dynamic friction coefficient
• MMD variation value of dynamic friction coefficient
• MIU indicates that the smaller the value, the smaller the roughness of the cosmetic.
• the dynamic friction coefficient (MIU) of the boron nitride powder of the present invention is 0.50 or less, preferably 0.46 or less, more preferably 0.43 or less.
• the dynamic friction coefficient variation (MMD) of the boron nitride powder of the present invention is 0.005 or less, preferably 0.004 or less, more preferably 0.003 or less.
• MIU coefficient of dynamic friction
• MMD variation value of coefficient of dynamic friction
• the measurement conditions of the friction tester are sensitivity: H, test table moving speed: 1 mm/sec, and static load: 25 gf. Measurement is performed once. Sample preparation (spreading boron nitride powder onto artificial leather) and measurement with a friction tester are repeated five times, and the average value of the five measurement results obtained is taken as the MIU and MMD of the boron nitride powder.
• the hexagonal boron nitride powder of the present invention contains primary particles and secondary particles in which the primary particles are agglomerated. Therefore, in order to measure the particle size of the primary particles, it is necessary to perform ultrasonic treatment under specific conditions so that the secondary particles are almost completely destroyed, leaving only the primary particles.
• particles that have been subjected to ultrasonic treatment under specific conditions may be referred to as primary particles.
• the ultrasonic treatment is performed by dispersing 1 g of the hexagonal boron nitride powder of the present invention in 20 g of ethanol and using an ultrasonic homogenizer.
• the particle size distribution of primary particles is the volume-based cumulative distribution (b) of particle sizes measured by a laser diffraction/scattering method.
• the average particle size (D50) of the primary particles is 3-15 ⁇ m, preferably 4-12 ⁇ m.
• the average particle diameter (D50) is a cumulative 50% value based on volume. If the D50 of the primary particles of the boron nitride powder is less than 3 ⁇ m, the lubricity is insufficient. When the D50 average particle size of the primary particles exceeds 15 ⁇ m, the lubricity is too high, and the tactile sensation such as “moist” and “slimy” of the cosmetic is impaired, and the appearance of the boron nitride powder becomes more glittery. , it becomes unfavorable as a cosmetic raw material.
• (D90-D10)/D50 of the primary particles is 1.30 or less, preferably 1.20 or less, more preferably 1.10 or less. It can be said that the smaller the value of (D90-D10)/D50, the sharper the particle size distribution and the more uniform the particle size.
• the lower limit is not particularly limited, it is generally 0.60 or more for boron nitride powder.
• the content of coarse particles exceeding 3 times D50 is 2.0% by volume or less, preferably 1.8% by volume or less, more preferably 1.3% by volume or less. The smaller the content of coarse particles is, the more “moist” the feel is obtained and the more the roughness can be suppressed.
• the D10, D50 and D90 of the primary particles are respectively the cumulative 10% value (D10), cumulative 50% value (D50), cumulative It means the 90% value (D90).
• the particle size distribution curve is calculated from the results of the volume-based particle size distribution measured with a laser diffraction/scattering particle size distribution analyzer after dispersing the measurement powder in ethanol and subjecting it to ultrasonic treatment.
• Ultrasonic treatment is performed by adding 20 g of ethanol as a dispersion medium to a 50 mL screw tube bottle, dispersing 1 g of the powder to be measured in ethanol, and then using an ultrasonic homogenizer (manufactured by Branson, trade name: SFX250). The tip (1/4 inch) is placed 1 to 5 mm from the bottom of the screw tube, and subjected to ultrasonic treatment with an amplitude of 40% for 20 minutes.
• the hexagonal boron nitride powder can be used in cosmetics.
• the present invention includes cosmetics containing the hexagonal boron nitride powder.
• cosmetics include foundation (powder foundation, liquid foundation, cream foundation), face powder, point makeup, eyeshadow, eyeliner, nail polish, lipstick, blush, and mascara.
• foundation porosity foundation
• face powder point makeup, eyeshadow, eyeliner, nail polish, lipstick, blush, and mascara.
• the cosmetics of the present disclosure are particularly well suited for powder foundations and face powders among the cosmetics described above.
• the content of the boron nitride powder in the cosmetic is, for example, preferably 0.1 to 70% by mass, more preferably 1 to 30% by mass, based on the total amount of the cosmetic.
• Other ingredients include red iron oxide, yellow iron oxide, black iron oxide, titanium oxide, silica, aluminum hydroxide, pigments such as mica, esters such as diisostearyl malate and glyceryl tri-2-ethylhexanoate, and oils such as petrolatum. types are mentioned.
• Talc, silicone powder, urethane powder, methylparaben, sodium dehydroacetate and the like are also included.
• the production method of the present invention is a method for producing boron nitride powder, which includes a reductive nitriding step of heating a raw material mixture in a nitrogen atmosphere in the presence of a seed crystal (S).
• the seed crystal (S) is a hexagonal boron nitride powder (hereinafter also referred to as BN seed crystal) produced by the melamine method.
• the melamine method is a method of producing BN seed crystals by nitriding an oxygen-containing boron compound using a nitrogen-containing organic compound described later as a nitrogen source, and is obtained by using a nitrogen-containing organic compound other than melamine.
• BN seed crystals obtained from the above can also be preferably used.
• a seed crystal (S) having a specific surface area of 5 m 2 /g or more as measured by the nitrogen adsorption BET single-point method can be suitably used.
• the larger the primary particles, the smaller the specific surface area, and those with a specific surface area of less than 5 m 2 /g may be particles as large as or larger than the target BN seed crystal primary particles.
• the particle size distribution may not be accurately measured by the laser diffraction/scattering method. do.
• the specific surface area of the seed crystal (S) is preferably 5 m 2 /g or more, more preferably 8 m 2 /g or more, still more preferably 10 m 2 /g or more.
• the upper limit is not particularly limited, it is preferably 200 m 2 /g or less, particularly preferably 100 m 2 /g or less, because handling becomes difficult if it is too large.
• the seed crystal (S) can be produced by heating a raw material mixture containing an oxygen-containing boron compound and a nitrogen-containing organic compound in a nitrogen atmosphere.
• oxygen-containing boron compounds include boric acid, boric anhydride (boron oxide), metaboric acid, perboric acid, hypoboric acid, sodium tetraborate, sodium perborate and the like.
• Nitrogen-containing organic compounds include melamine, ammeline, cyandiamide, urea, and the like.
• the raw material mixture may contain an oxygen-containing alkaline earth metal compound.
• Magnesium carbonate (MgCO 3 ), calcium carbonate (CaCO 3 ), calcium oxide (CaO) and the like can be used as oxygen-containing alkaline earth metal compounds. Moreover, you may use together 2 or more types of these.
• the heating temperature is preferably 500 to 1200°C, more preferably 600 to 1100°C, still more preferably 650 to 1000°C. The lower the heating temperature, the easier it is for the obtained seed crystals (S) to have a uniform primary particle size.
• the heating time is preferably 5-20 hours, more preferably 6-15 hours. The longer the heating time, the easier it is for the obtained seed crystals (S) to have a uniform primary particle size.
• the boron/nitrogen element ratio (B/N) is preferably 0.2 to 1, more preferably 0.25 to 0.5.
• the produced seed crystals (S) may be used as they are, but for the purpose of facilitating uniform mixing with other raw materials used in the reduction-nitriding step, they are crushed by a jet mill, stone mill crusher, or the like. It is preferable to use from Furthermore, it may be used after purification by acid washing, filtration, water washing and drying.
• the seed crystals (S) are BN seed crystals having a uniform particle diameter by being produced by the melamine method.
• the reaction temperature boron nitride formation temperature
• the reaction temperature is as high as 1400° C. or higher
• the formation of boron nitride and the crystal growth proceed at the same time, making it difficult to obtain BN seed crystals with a uniform particle size.
• grain growth occurs with the seed crystals (S) serving as nuclei. Therefore, if the seed crystals (S) have a uniform particle size, the boron nitride powder tends to have a uniform primary particle size.
• the reductive nitriding step is a step of heating the raw material mixture in a nitrogen atmosphere.
• the raw material mixture contains an oxygen-containing boron compound, an oxygen-containing alkaline earth metal compound, a carbon source compound and a boron nitride powder produced by the melamine method as a seed crystal (S).
• oxygen-containing boron compounds examples include diboron trioxide (boron oxide), diboron dioxide, tetraboron trioxide, tetraboron pentoxide, borax, anhydrous borax, and the like. 3 ) is preferred.
• diboron trioxide as a boron compound is industrially beneficial because it uses inexpensive raw materials.
• oxygen-containing alkaline earth metal compounds include oxides or carbonates of alkaline earth metals such as calcium and magnesium.
• alkaline earth metals such as calcium and magnesium.
• magnesium oxide, calcium oxide, magnesium carbonate, calcium carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate, magnesium hydroxide, calcium hydroxide, magnesium nitrate, calcium nitrate, magnesium sulfate, calcium sulfate, magnesium phosphate, calcium phosphate , magnesium oxalate, calcium oxalate and the like can be used.
• oxygen-containing alkaline earth metal compound By using a carbonate such as magnesium carbonate or calcium carbonate as the oxygen-containing alkaline earth metal compound, carbon dioxide gas is generated in the heating step, causing pores inside the mixed raw material layer, and nitrogen gas is generated inside the mixed raw material layer. It becomes easy to permeate, and the reduction nitriding reaction progresses efficiently. Two or more of these oxygen-containing alkaline earth metal compounds may be used in combination.
• Carbon source compounds include amorphous carbon such as carbon black, activated carbon, and carbon fiber, crystalline carbon such as diamond, graphite, and nanocarbon, and pyrolytic carbon obtained by thermally decomposing a monomer or polymer. can be done.
• amorphous carbon such as carbon black, activated carbon, and carbon fiber
• crystalline carbon such as diamond, graphite, and nanocarbon
• pyrolytic carbon obtained by thermally decomposing a monomer or polymer. can be done.
• carbon black is used as the carbon source compound, a hexagonal boron nitride powder having a particularly uniform particle size can be obtained.
• the carbon source compound By using the carbon source compound, a reductive nitriding reaction occurs in the subsequent heating step, and the newly generated boron nitride contributes to the growth of the seed crystal (S).
• the seed crystal (S) dissolves in the oxygen-containing boron compound, and the dissolved seed crystal (S) contributes to the growth of another seed crystal (S).
• the particle size becomes large, the primary particle size of the obtained hexagonal boron nitride powder is not sufficiently uniform.
• the atomic ratio (B/C ratio) of the boron atom (B) of the oxygen-containing boron compound and the carbon atom (C) of the carbon source compound in the raw material mixture in the reduction nitriding step is preferably 0.70 to 2.00, and more It is preferably 0.71 to 1.70, more preferably 0.72 to 1.30.
• the content of the oxygen-containing alkaline earth metal compound in the raw material mixture is determined by the molar ratio of the oxygen-containing alkaline earth metal compound (MO; M is an alkaline earth metal) in terms of oxide to the oxygen-containing boron compound ( MO/B 2 O 3 ) is preferably 0.01 to 1.0, more preferably 0.03 to 0.8, still more preferably 0.05 to 0.6, particularly preferably 0.08 to 0.4. is.
• the oxygen- containing alkaline earth metal compound acts as a grain growth aid for boron nitride particles. It is possible to obtain a boron nitride powder having a desired primary particle size, good lubricity, and less roughness.
• the atomic ratio (B S /C ratio) of the boron atom (B S ) of the boron nitride powder (BN seed crystal) of the seed crystal ( S ) and the carbon atom (C) of the carbon source compound is preferably 0.01 to 13, more preferably 0.1-10, more preferably 0.2-8.
• the reductive nitriding step is a step of heating the raw material mixture under a nitrogen stream. Nitriding using boron oxide (B 2 O 3 ) or an oxygen-containing boron compound that is thermally decomposed into boron oxide (B 2 O 3 ) and carbon (C) or pyrolytic carbon that is thermally decomposed into carbon (C)
• the reaction for producing boron powder (BN) is as follows. B2O3 + 3C+ N2- >2BN+3CO
• the reaction temperature is preferably 1400-1600°C, more preferably 1450-1580°C. If the reaction temperature is low, the reaction time will be long, and if the reaction temperature is high, it will be difficult to make the primary particle size of the boron nitride powder uniform.
• the holding time is preferably 1-10 hours, more preferably 2-8 hours. If the holding time is short, it is difficult to make the primary particle size of the boron nitride powder uniform.
• the heating temperature is increased to 1700-2100°C. As the temperature rises, the crystallization of the boron nitride particles progresses and the primary particle size increases.
• the maximum temperature is more preferably 1730 to 2000°C, more preferably 1750 to 1950°C. If the maximum temperature is too low, the primary particles of the boron nitride powder will not grow to a size suitable for cosmetics, and if the maximum temperature is too high, they will grow excessively beyond the size preferable for cosmetics.
• Heating after the reaction is maintained at a temperature of 1700 to 2100°C (preferably 1730°C to 2000°C, more preferably 1750°C to 1950°C) continuously for at least 0.5 hours (preferably 1 hour). preferable.
• the holding time at the above temperature is preferably 7 hours or less, more preferably 4 hours or less.
• Nitrogen gas is necessary as a nitrogen source in the reductive nitriding reaction, and is preferably supplied by circulating in the heating furnace.
• the flow path of the nitrogen gas may be designed so that the raw material mixture placed in the heating furnace and the flowing nitrogen gas come into contact with each other (for example, flow through the upper space of the raw material mixture layer).
• the flow rate of nitrogen gas is preferably 0.1 to 20 L/min, more preferably 0.2 to 15 L/min, and more preferably 0.3 to 10 L/min, per 1 kg of mixed raw material. More preferred. If the amount of nitrogen gas is insufficient, the reductive nitriding reaction will not be completed, and unreacted carbon will undesirably remain as black foreign matter in the boron nitride powder.
• the raw material mixture may be filled in a carbon container, a boron nitride-coated carbon container, a boron nitride sintered body container, or the like, and placed in a heating furnace.
• the shape of the container is preferably a shape that does not prevent contact between the raw material mixture and the flowing nitrogen gas.
• the raw material mixture is preferably filled in the container at a height of 1 to 20 cm. If the filling layer is too low, the productivity will decrease, and if the filling layer is too high, the reaction of the raw material mixture at the bottom of the container will not proceed, and unreacted carbon will unfavorably remain as black foreign matter in the boron nitride powder.
• the height of the packed bed of the raw material mixture is more preferably 2 to 15 cm, even more preferably 3 to 10 cm.
• the reaction product obtained in the reductive nitriding step contains impurities other than hexagonal boron nitride, such as unreacted raw materials (B 2 O 3 , CaO). can be obtained to obtain a high-purity hexagonal boron nitride powder suitable for cosmetic applications.
• the acid cleaning method is not particularly limited, and known methods can be applied without limitation.
• the reaction product obtained in the reductive nitriding step is manually loosened and put into a container, then diluted hydrochloric acid (5 to 20% by mass HCl) is added in an amount 3 to 10 times the amount of the reaction product, and stirred for 1 to 20 hours. and methods to do so.
• the acid cleaning After the acid cleaning, it is cleaned with pure water for the purpose of removing the acid.
• pure water water having an electric conductivity of 1 mS/m or less can be used from the viewpoint of avoiding secondary contamination of impurities.
• washing method after filtering the acid used for acid washing, the same amount of pure water as the acid used is added and filtered again. Further, washing with pure water and filtration are repeated until the filtrate becomes neutral.
• hexagonal boron nitride powder in cosmetics it is desired that it conforms to the Standards for Quasi-drug Ingredients 2021, and has a purity of 95% or more, a pH of 5.0 to 8.0, and an eluted boron amount of 20 ppm or less. Since there are standards such as these, it is necessary to wash so as to satisfy these standards.
• the method of solid-liquid separation is not particularly limited. can be used.
• drying equipment that can be used in the drying process of hexagonal boron nitride powder after solid-liquid separation include tray dryers, fluid bed dryers, spray dryers, rotary dryers, belt dryers, and vacuum drying. machine, vibrating dryer, etc. or a combination thereof.
• the ambient temperature in the dryer is preferably 50-300°C, more preferably 100-250°C.
• the drying time is not particularly specified, but it is preferable to dry until the moisture content approaches 0%, and it is generally recommended to carry out drying at the above temperature for 1 to 48 hours. Washing, solid-liquid separation, and drying may each be performed once, or may be performed multiple times by combining the same method or different methods.
• boron nitride is hydrolyzed, and the amount of eluted boron may exceed 20 ppm.
• Vacuum drying is preferable as a drying method for suppressing hydrolysis of boron nitride.
• Classification is preferably performed for the purpose of controlling the D95 of the hexagonal boron nitride powder.
• the classification method is not particularly limited, and known methods can be applied without limitation. Specific examples include vibrating sieving machines, wet sieving machines, wind classifiers, cyclones, and liquid cyclones.
• the invention is illustrated by the following examples.
• the low-purity product before washing is referred to as nitriding powder
• the high-purity product after cleaning is referred to as h-BN powder.
• (S) was written on the powder for seed crystals.
• ⁇ Cumulative distribution of volume-based particle size measured by laser diffraction/scattering method> The particle size distribution of the h-BN powder was measured using a particle size distribution measuring device MT3000 manufactured by Nikkiso Co., Ltd. for a sample that was not ultrasonically treated or an ultrasonically treated sample prepared by the method shown below. Ethanol was used as the solvent. The refractive index was 1.36 for ethanol and 1.74 for hexagonal boron nitride, and the measurement time was 30 seconds.
• a measurement sample was prepared by adding 20 g of ethanol as a dispersion medium to a 50 mL screw tube bottle and dispersing 1 g of h-BN powder in ethanol.
• ⁇ Ultrasonic treated sample The measurement sample was ultrasonically treated by the method shown below. First, 20 g of ethanol was added as a dispersion medium to a 50 mL screw vial, and 1 g of h-BN powder was dispersed in the ethanol. Then, using an ultrasonic homogenizer (SONIFIER SFX250) manufactured by BRANSON, the tip (20 kHz microchip 1/4 inch) is placed at 1 to 5 mm from the bottom of the screw tube, and sonicated for 20 minutes at an amplitude of 40%. gone. Then, the particle size distribution measurement of the measurement sample subjected to ultrasonic treatment was performed.
• SONIFIER SFX250 ultrasonic homogenizer manufactured by BRANSON
• MIU and MMD are infinite numbers measured using a friction tester (manufactured by Kato Tech Co., Ltd., trade name: KES-SE). Specifically, h-BN powder is placed on an artificial leather (manufactured by Idemitsu Techno Fine Co., Ltd., trade name: Suprale PBZ13001 BK) that looks like skin, and is thinly stretched so that the amount is 0.5 mg / cm 2 . The sensor portion (10 mm square silicon) of the friction tester is applied to the surface, and MIU and MMD can be measured.
• the measurement conditions of the friction tester are sensitivity: H, test table moving speed: 1 mm/sec, and static load: 25 gf. Measurement is performed once. Sample preparation (spreading h-BN powder on artificial leather) and measurement with a friction tester are repeated five times, and the average value of the five measurement results obtained is used as the MIU and MMD of the h-BN powder. bottom.
• a raw material mixture (S) was prepared by mixing 30 g of boron oxide (B 2 O 3 ) as an oxygen-containing boron compound and 50 g of melamine as an organic compound containing nitrogen in a ball mill. B/N was 0.36 in the prepared raw material mixture (S). Using a batch-type firing furnace for the raw material mixture (S) prepared, in the heating step, the temperature is raised at 15 ° C./min under nitrogen gas flow and heated at a temperature of 1000 ° C. for 10 hours. ) was made.
• the nitrided powder (S) produced was pulverized with a stone mill, acid-washed with a 5% hydrochloric acid aqueous solution, filtered, washed with water, and dried to obtain h-BN powder (S) (melamine 1). got
• a raw material mixture (S) was prepared by mixing 30 g of boron oxide (B 2 O 3 ) as an oxygen-containing boron compound and 50 g of melamine as an organic compound containing nitrogen in a ball mill. B/N was 0.36 in the prepared raw material mixture (S). Using a batch-type firing furnace for the raw material mixture (S) prepared, in the heating step, the temperature is raised at 15 ° C./min under nitrogen gas flow and heated at a temperature of 700 ° C. for 10 hours. ) was made.
• the nitrided powder (S) produced was pulverized with a stone mill, acid-washed with a 5% hydrochloric acid aqueous solution, filtered, washed with water, and dried to obtain h-BN powder (S) (melamine 2). got
• a raw material mixture (S) was prepared by mixing 30 g of boron oxide (B 2 O 3 ) as an oxygen-containing boron compound and 50 g of melamine as an organic compound containing nitrogen in a ball mill. B/N was 0.36 in the prepared raw material mixture (S).
• the raw material mixture (S) thus prepared is heated at a rate of 15° C./min under nitrogen gas flow using a batch-type firing furnace, and heated at a temperature of 1000° C. for 6 hours to produce a nitrided powder (S ) was made.
• nitrided powder (S) was pulverized with a stone mill, acid-washed with a 5% hydrochloric acid aqueous solution, filtered, washed with water, and dried to obtain h-BN powder (S) (melamine 3). got
• a raw material mixture (S) was prepared by mixing 50 g of boric acid (H 3 BO 3 ) as an oxygen-containing boron compound and 50 g of urea as an organic compound containing nitrogen in a ball mill. B/N was 0.49 in the prepared raw material mixture (S). Using a batch-type firing furnace for the raw material mixture (S) prepared, in the heating step, the temperature is raised at 15 ° C./min under nitrogen gas flow and heated at a temperature of 800 ° C. for 10 hours. ) was made.
• the nitrided powder (S) produced was pulverized with a stone mill, acid-washed with a 5% hydrochloric acid aqueous solution, filtered, washed with water, and dried to obtain h-BN powder (S) (melamine 4). got
• BN seed crystal (reduction nitriding)> 50 g of boron oxide (B 2 O 3 ) as an oxygen-containing boron compound, 8 g of calcium carbonate (CaCO 3 ) as an oxygen-containing alkaline earth metal compound, and 24 g of carbon black (C) as a carbon source compound were mixed in a ball mill.
• a raw material mixture (S) was prepared.
• B/C (molar ratio) was 0.72
• CaO/B 2 O 3 (molar ratio) was 0.11.
• the raw material mixture (S) thus prepared is heated at a rate of 15° C./min under nitrogen gas flow using a batch-type firing furnace, and heated at a temperature of 1500° C.
• nitrided powder (S ) was made.
• the nitrided powder (S) produced was pulverized with a stone mill, acid-washed with a 5% hydrochloric acid aqueous solution, filtered, washed with water, and dried to obtain h-BN powder (S) (reductive nitriding). got
• ⁇ Raw material mixture 50 g of boron oxide (B 2 O 3 ) as an oxygen-containing boron compound, 8 g of calcium carbonate (CaCO 3 ) as an oxygen-containing alkaline earth metal compound, 25 g of carbon black (C) as a carbon source compound, and seed crystals as described above.
• a raw material mixture was obtained by mixing 40 g of seed crystals (melamine 1) with a ball mill.
• B/C (atomic ratio) was 0.72
• CaO/B 2 O 3 (molar ratio) was 0.11
• B S /C (atomic ratio) was 0.81. there were.
• ⁇ Reduction nitridation process> Using a batch-type firing furnace, the prepared raw material mixture was heated at a temperature of 1500° C. for 6 hours under nitrogen gas flow, and then further heated at a temperature of 1800° C. for 2 hours to produce nitrided powder.
• ⁇ Purification process> The nitrided powder thus produced was acid-washed with a 5% hydrochloric acid aqueous solution, filtered, washed with water, and vacuum-dried at 200° C. to obtain h-BN powder.
• the obtained h-BN powder was classified with a vibrating sieve having an opening of 45 ⁇ m.
• Table 1 shows the D95, coefficient of dynamic friction (MIU), and coefficient of dynamic friction (MMD) of the h-BN powder, which is a mixture containing particles.
• h-BN powder was mixed with each of the following cosmetic components to prepare a cosmetic (powder foundation).
• Component (mixing amount %) ⁇ h-BN powder 20.0 ⁇ Mica 15.0 ⁇ Synthetic phlogopite 12.0 ⁇ Ethylhexyl methoxycinnamate 8.0 ⁇ (vinyl dimethicone/methicone silsesquioxane) crosspolymer 8.0 (Diphenyl dimethicone/vinyl diphenyl dimethicone/silsesquioxane) crosspolymer 8.0 ⁇ Nylon 12, 3.0 ⁇ Silica 3.0 ⁇ Talc 3.0 ⁇ Acrylate Crosspolymer 3.0 ⁇ Perfluorooctyltriethoxysilane 3.0 ⁇ Zinc oxide 3.0 ⁇ Polymethyl methacrylate polymer 3.0 ⁇ Silicone-treated red iron oxide (red iron
• Table 1 shows the results of examination of slipperiness, roughness, and moistness of the obtained powder foundation.
• the above various properties were evaluated by having 20 research panels specializing in cosmetic evaluation use the products of the present invention and the comparative products, and when less than 30% of the panelists felt that they were good, ⁇ , 30% or more and less than 60%.
• a case of ⁇ is indicated, a case of 60% or more and less than 80% is indicated by ⁇ , and a case of 80% or more is indicated by ⁇ .
• Example 2 An h-BN powder was obtained in the same manner as in Example 1, except that melamine 2 was used as seed crystals.
• Table 1 shows the particle size distribution, coefficient of dynamic friction (MIU), and coefficient of dynamic friction (MMD) of the obtained h-BN powder.
• a powder foundation was prepared in the same manner as in Example 1 using the obtained h-BN powder. The properties of the obtained powder foundation were evaluated in the same manner as in Example 1. Table 1 shows the results.
• Example 3 An h-BN powder was obtained in the same manner as in Example 1, except that melamine 3 was used as seed crystals.
• Table 1 shows the particle size distribution, coefficient of dynamic friction (MIU), and coefficient of dynamic friction (MMD) of the obtained h-BN powder.
• a powder foundation was prepared in the same manner as in Example 1 using the obtained h-BN powder. The properties of the obtained powder foundation were evaluated in the same manner as in Example 1. Table 1 shows the results.
• Example 4 h-BN powder was produced in the same manner as in Example 1, except that the composition ratio of the raw material mixture was changed as shown in Table 1, and the firing temperature in the reduction-nitriding step was changed as shown in Table 1. got Table 1 shows the particle size distribution, coefficient of dynamic friction (MIU), and coefficient of dynamic friction (MMD) of the obtained h-BN powder.
• MIU coefficient of dynamic friction
• MMD coefficient of dynamic friction
• Example 5 h-BN powder was produced in the same manner as in Example 1, except that the composition ratio of the raw material mixture was changed as shown in Table 1, and the firing temperature in the reduction-nitriding step was changed as shown in Table 1. got Table 1 shows the particle size distribution, coefficient of dynamic friction (MIU), and coefficient of dynamic friction (MMD) of the obtained h-BN powder.
• MIU coefficient of dynamic friction
• MMD coefficient of dynamic friction
• Example 6 An h-BN powder was obtained in the same manner as in Example 1, except that melamine 4 was used as seed crystals.
• Table 1 shows the particle size distribution, coefficient of dynamic friction (MIU), and coefficient of dynamic friction (MMD) of the obtained h-BN powder.
• a powder foundation was prepared in the same manner as in Example 1 using the obtained h-BN powder. The properties of the obtained powder foundation were evaluated in the same manner as in Example 1. Table 1 shows the results.
• Example 7 h-BN powder was obtained in the same manner as in Example 1, except that the composition ratio of the raw material mixture was changed as shown in Table 1.
• Table 1 shows the particle size distribution, coefficient of dynamic friction (MIU), and coefficient of dynamic friction (MMD) of the obtained h-BN powder.
• MIU coefficient of dynamic friction
• MMD coefficient of dynamic friction
• Example 1 An h-BN powder was produced under the same conditions as in Example 1, except that no seed crystal was used. Table 1 shows the production conditions and the properties of the obtained h-BN powder. A powder foundation was prepared in the same manner as in Example 1 using the obtained h-BN powder. The properties of the obtained powder foundation were evaluated in the same manner as in Example 1. Table 1 shows the results.
• h-BN powder was produced under the same conditions as in Comparative Example 1 except that a sieve with an opening of 90 ⁇ m was used in the classification step.
• Table 1 shows the production conditions and the properties of the obtained h-BN powder.
• a powder foundation was prepared in the same manner as in Example 1 using the obtained h-BN powder.
• the properties of the obtained powder foundation were evaluated in the same manner as in Example 1. Table 1 shows the results.
• Example 3 An h-BN powder was obtained in the same manner as in Example 1, except that a seed crystal (reduction nitriding) obtained by a reduction nitriding method was used as the seed crystal.
• Table 1 shows the particle size distribution, coefficient of dynamic friction (MIU), and coefficient of dynamic friction (MMD) of the obtained h-BN powder.
• a powder foundation was prepared in the same manner as in Example 1 using the obtained h-BN powder. The properties of the obtained powder foundation were evaluated in the same manner as in Example 1. Table 1 shows the results.
• Example 4 h-BN powder was obtained in the same manner as in Example 1, except that the composition ratio of the raw material mixture was changed as shown in Table 1.
• Table 1 shows the particle size distribution, coefficient of dynamic friction (MIU), and coefficient of dynamic friction (MMD) of the obtained h-BN powder.
• MIU coefficient of dynamic friction
• MMD coefficient of dynamic friction

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Veterinary Medicine (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Epidemiology (AREA)
• Birds (AREA)
• Physics & Mathematics (AREA)
• Geometry (AREA)
• Cosmetics (AREA)
• Ceramic Products (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=86902097

Family Applications (1)

Country Status (7)

Citations (11)

Family Cites Families (5)

• 2022
  • 2022-12-01 JP JP2023569237A patent/JPWO2023120092A1/ja active Pending
  • 2022-12-01 KR KR1020247015109A patent/KR20240122746A/ko active Pending
  • 2022-12-01 WO PCT/JP2022/044322 patent/WO2023120092A1/ja not_active Ceased
  • 2022-12-01 CN CN202280078415.3A patent/CN118302382A/zh active Pending
  • 2022-12-01 EP EP22910809.7A patent/EP4455077A4/en active Pending
  • 2022-12-01 US US18/721,253 patent/US20250059039A1/en active Pending
  • 2022-12-15 TW TW111148179A patent/TW202332420A/zh unknown

Patent Citations (11)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events