WO2020031913A1 - 六方晶窒化ホウ素粉末 - Google Patents
六方晶窒化ホウ素粉末 Download PDFInfo
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- WO2020031913A1 WO2020031913A1 PCT/JP2019/030572 JP2019030572W WO2020031913A1 WO 2020031913 A1 WO2020031913 A1 WO 2020031913A1 JP 2019030572 W JP2019030572 W JP 2019030572W WO 2020031913 A1 WO2020031913 A1 WO 2020031913A1
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- 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
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- 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
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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
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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
- A61K8/0245—Specific shapes or structures not provided for by any of the groups of A61K8/0241
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- 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
- 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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- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
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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
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/62—L* (lightness axis)
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- C01P2006/90—Other properties not specified above
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
Definitions
- the present invention relates to a hexagonal boron nitride powder, and more particularly to a hexagonal boron nitride powder which has excellent glitter and can be suitably used for cosmetics.
- Hexagonal boron nitride is a compound having a layer structure similar to graphite in which hexagonal stitch-like layers composed of boron (B) and nitrogen (N) are laminated. Therefore, general hexagonal boron nitride particles have a flat plate-like (scale-like) structure. In addition, there is no covalent bond between the layers in the particle, and the force acting between the layers is only a very weak force, Van der Waals force. Therefore, slippage occurs between the layers with a slight force, and as a result, the hexagonal boron nitride powder has extremely excellent lubricity.
- hexagonal boron nitride is chemically stable and does not adversely affect the human body. Taking advantage of the lubricity described above, hexagonal boron nitride is used as an extender for cosmetics that excels in “spread” when applied to the skin surface. It is widely used (Patent Documents 1 and 2).
- the present invention has been made in view of the above-mentioned circumstances, and has both a smooth feel and excellent glitter, which are characteristics of boron nitride powder, and furthermore, has excellent glitter even when used in combination with a glitter pigment. It is intended to provide a hexagonal boron nitride powder that can be used.
- a hexagonal boron nitride powder that satisfies condition (1) can be produced.
- the present invention has been made based on the above findings, and the gist configuration thereof is as follows.
- a hexagonal boron nitride powder Among the hexagonal boron nitride particles contained in the hexagonal boron nitride powder, the number ratio of particles having a structure bent at an angle of 110 ° to 160 ° with respect to the crystal (1,0,0) plane of the particles is 30%. The above is the hexagonal boron nitride powder.
- the number ratio of particles having a structure bent at an angle of 110 ° to 130 ° with respect to the crystal (1,0,0) plane of the particles is 60%.
- the hexagonal boron nitride powder of the present invention has excellent luster in addition to the lubricating properties of the hexagonal boron nitride powder, and thus can be used extremely suitably for cosmetics.
- FIG. 2 is a schematic diagram illustrating an example of the shape of a particle according to an embodiment of the present invention.
- the ratio of the bent particles is set to 50% or more, preferably 70% or more, and more preferably 80% or more.
- the upper limit of the ratio of the bent particles is not particularly limited, and may be 100%. However, if the ratio of the bent particles exceeds 90%, the effect is saturated. Therefore, the ratio of the bent particles may be 90% or less.
- the bent particle ratio can be measured by the method described in Examples.
- the hexagonal boron nitride powder satisfying the above conditions can be manufactured by a manufacturing method described later.
- the number ratio of particles having a structure bent at an angle of 110 ° to 130 ° with respect to the crystal (1,0,0) plane of the particles (hereinafter, referred to as “second bent particle ratio”) is preferably 60% or more.
- the second bent particle ratio can be increased by, for example, increasing the amount of the additive in the manufacturing method described below.
- the length of the bent portion of the particle having a structure bent at an angle of 110 ° to 160 ° with respect to the crystal (1,0,0) plane of the particle is not particularly limited, but is preferably 3 ⁇ m or more. If the thickness is less than 3 ⁇ m, there is no bending effect.
- the term "length of the bent portion" refers to the average distance from the top of the bend to the end face closer to the top, on the outer surface of the bend when observing the particles under a microscope visual field. Shall point to.
- the length L of the bend is preferably 3 ⁇ m or more.
- the average distance from the vertex of the bend to the end face farther from the vertex is 3 ⁇ m or more.
- the length L 1 of the bend portion for the bend closest to one end face preferably, at least one of the bent portion of the length L 2 of the bending closest to the other end face is 3 ⁇ m or more, and preferably both is 3 ⁇ m or more.
- the bend of the particles is caused by the inhibition of crystal growth on the (100) plane by impurities, as described later, and the bend angle is theoretically determined. However, since the angle varies industrially due to various factors, the bending angle is set to 110 ° to 160 ° here.
- the full width at half maximum of the reflectance peak of the hexagonal boron nitride powder measured by a goniophotometer at an incident light angle of 45 ° is preferably 80 ° or less, more preferably 60 ° or less. preferable.
- the glitter of the hexagonal boron nitride powder can be enhanced. This is considered to be because the reflected light is more strongly reflected when reflected at a narrow angle than when reflected light is reflected (scattered) at a wide angle.
- the lower limit of the full width at half maximum is not particularly limited, but may be usually 10 ° or more.
- the full width at half maximum can be measured by a method described in Examples using a goniophotometer.
- the average particle size of the hexagonal boron nitride powder is preferably 6 to 100 ⁇ m.
- the average particle size is less than 6 ⁇ m, the hexagonal boron nitride powder forms an extremely dense film when applied to the skin. May impair the brilliancy.
- Increasing the average particle size also contributes to increasing the ratio of the bent particles described above. Therefore, it is preferable that the average particle diameter is 6 ⁇ m or more.
- the average particle diameter is 15 ⁇ m or more, the reflection of light per particle becomes more remarkable, and as a result, the glitter can be further improved. For this reason, it is more preferable that the average particle diameter be 15 ⁇ m or more.
- the average particle size is 100 ⁇ m or less, the adhesion to the skin is further improved. Therefore, the average particle size is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less.
- the average particle size refers to the average particle size of the primary particles, and can be measured by the method described in Examples. The average particle size can be controlled by the conditions during secondary heating (heating temperature, processing time, etc.).
- ratio of coarse particles is preferably 0.5% by mass or less.
- Coarse particles having a particle size of 200 ⁇ m or more are agglomerated particles in which a plurality of particles adhere to each other. can do.
- the proportion of coarse particles can be controlled by selecting a crushing means or a classification means.
- the apparent thickness of the particles constituting the hexagonal boron nitride powder is preferably 0.5 to 3.0 ⁇ m.
- the apparent thickness is 0.5 ⁇ m or more, the glitter is further improved.
- the apparent thickness is 3.0 ⁇ m or less, roughness when applied to the skin can be further reduced.
- the apparent thickness can be controlled by adjusting the heat treatment conditions during production.
- the apparent thickness refers to the average value of the apparent thickness of the particles observed under a microscope visual field. The apparent thickness can be measured by the method described in Examples.
- the average aspect ratio of the hexagonal boron nitride powder is 5 to 30.
- the aspect ratio indicates the average value of the aspect ratio of each particle obtained by observing particles constituting the hexagonal boron nitride powder with an electron microscope.
- the major axis and the thickness of the particle when calculating the aspect ratio of each particle, an apparent major axis and an apparent thickness under a microscope visual field can be used, respectively.
- the hexagonal boron nitride powder of the present invention can be manufactured by sequentially performing the following processes (1) to (6). Hereinafter, each process will be specifically described. (1) mixing (2) first heating (3) cooling (4) second heating (5) crushing (6) washing and drying
- the raw materials used for producing the hexagonal boron nitride powder and the additives are mixed.
- a boron compound as a boron source and a nitrogen compound as a nitrogen source are used.
- the boron compound one or both of boric acid and boron oxide (B 2 O 3 ) is used.
- the boron compound may further include boron carbide.
- One or both of urea and a urea compound are used as the nitrogen compound.
- the urea compound for example, one or both of dicyandiamide and melamine can be used.
- the additive one or two or more selected from the group consisting of Na 2 CO 3 , K 2 CO 3 , MgCO 3 , CaCO 3 , BaCO 3 , MgO, CaO, and BaO are used. It is considered that by using the additive, the crystal growth on the (100) plane is inhibited, and as a result, boron nitride particles having a bent structure are generated.
- the mixed raw materials and additives are heated to a heating temperature of 600 ° C. to 1200 ° C., and maintained at the heating temperature for 1 hour or more (first heating).
- first heating the raw material is changed into boron nitride (t-BN) having a turbostratic structure. If the heating temperature is less than 600 ° C., the reaction between the boron compound and the nitrogen compound as the raw materials to form a boron nitride having a turbostratic structure becomes insufficient, and as a result, the hexagonal boron nitride in the second heating is performed later. The yield decreases.
- the first heating may be performed in an inert gas atmosphere.
- the inert gas atmosphere for example, a nitrogen gas atmosphere can be used.
- turbulent layer structure refers to a state in which the crystal has not been completely crystallized.
- a sharp peak of hexagonal boron nitride does not appear but a broad peak indicating that it has not been completely crystallized appears.
- the obtained boron nitride powder having a turbostratic structure is once cooled.
- the cooling method is not particularly limited, it is usually air cooling. In the cooling, it is preferable to cool the turbostratic boron nitride powder to room temperature.
- the cooled boron nitride powder is heated to a heating temperature of 1500 to 2300 ° C. (second heating temperature) in an inert gas atmosphere, and is kept at the heating temperature for 2 hours or more. (Second heating).
- second heating temperature 1500 to 2300 ° C.
- crystallization of boron nitride proceeds, and boron nitride (t-BN) having a turbostratic structure changes to hexagonal boron nitride (h-BN).
- the average heating rate in the second heating be 20 ° C./min or less.
- the heating rate is 20 ° C./min or less, generation of bending and crystal growth due to the presence of the additive added to the raw material are promoted, and hexagonal satisfies the bending particle ratio condition defined in the present invention.
- a crystalline boron nitride powder can be obtained.
- the average heating rate in the second heating is preferably set to 10 ° C./min or less.
- the boron compound and the nitrogen compound which are the raw materials, react to generate boron nitride having a turbostratic structure.
- an additive is added to the raw material, “ammonium borate or the like containing an additive component (for example, Ca)” is generated in addition to boron nitride having a turbostratic structure.
- the presence of the “ammonium borate or the like containing an additive component” promotes generation of a bend and crystal growth in the second heating, and as a result, the ratio of the bent particles can be increased.
- the additive by adding the additive prior to the first heating, the melting and mixing of the raw material and the additive proceed, so that the generation of bending and the crystal growth in the second heating are promoted.
- the hexagonal crystal is formed from boron nitride having a turbostratic structure in the absence of “ammonium borate containing an additive component”. Since the change to boron nitride proceeds, the ratio of the bent particles cannot be 30% or more.
- the heating temperature in the first heating is lower than 600 ° C.
- sufficient boron nitride having a turbostratic structure cannot be obtained in the first heating.
- a hexagonal boron nitride powder having a bending ratio of 30% or more can be obtained because the generation reaction of hexagonal boron nitride due to crystallization of the turbostratic boron nitride does not sufficiently proceed. Can not.
- the hexagonal boron nitride after the second heating is turned into a bulk material by heating at a high temperature. Therefore, the bulk body is pulverized.
- the pulverizing method is not particularly limited, and may be performed according to a conventional method.
- Example 1 Hexagonal boron nitride powder was produced according to the following procedure, and its characteristics were evaluated.
- the mixed raw materials and additives were heated to a heating temperature shown in Table 1 under a nitrogen atmosphere, and were maintained at the heating temperature for 3 hours to obtain a boron nitride having a turbostratic structure (first heating). . After the first heating, it was cooled to room temperature.
- the obtained boron nitride having a turbostratic structure was heated in a nitrogen atmosphere to the heating temperature shown in Table 1, and kept at the heating temperature for 5 hours (second heating). Thereafter, the mixture was cooled to room temperature to obtain hexagonal boron nitride.
- the average heating rate in the second heating was as shown in Table 1.
- the obtained hexagonal boron nitride was pulverized, washed with water, wet-sieved, dehydrated and dried according to a conventional method. In the wet sieving, a sieve having an opening of 200 ⁇ m was used, and particles not passing through the sieve were excluded.
- the hexagonal boron nitride powder was observed with an electron microscope, and the number of particles having a bent structure was counted out of 50 randomly selected primary particles.
- the hexagonal boron nitride powder which is observed as “bent” by an electron microscope, is substantially without exception, and the crystals of the primary particles (1,0,0) ) Surface has a bending angle of 110 ° to 160 °. Therefore, under the visual field of the microscope, the particles whose bending is observed from the side of the particle and the particles whose bending line is observed from the top of the particle all have a structure bent at an angle of 110 ° to 160 °.
- the bent particle ratio can be calculated as (the number of particles having a bent structure / the number of target primary particles) ⁇ 100 (%). The observation was performed under the conditions of 2000 times magnification and 10 or more visual fields, and a total of 50 particles were observed.
- the hexagonal boron nitride powder was dispersed in water, and the particle size distribution of the hexagonal boron nitride powder was measured using a laser diffraction type particle size distribution analyzer (Spectris, Mastersizer 3000). The analysis conditions were as follows: measurement target: non-spherical, refractive index: 1.74, absorption: 0, density: 1 g / cm 3 , dispersion medium: ethanol (refractive index: 1.33). From the obtained particle size distribution, the 50% cumulative diameter (median diameter, D50) was defined as the average particle diameter.
- the hexagonal boron nitride powder was observed with an electron microscope, and the apparent thickness of the primary particles was measured. The observation was performed at a magnification of 10,000 times and in five visual fields, and the average value of the observed thicknesses of the primary particles was defined as the apparent thickness.
- the evaluation criteria were ⁇ Excellent, ⁇ Excellent, ⁇ Good, ⁇ Insufficient, and ⁇ Not possible according to the degree of glitter.
- the evaluation with the largest number among the evaluation results of the ten testers was the evaluation of the tested hexagonal boron nitride powder. However, when two or more evaluations were the same and maximum, the lowest evaluation was the evaluation of the tested hexagonal boron nitride powder.
- the evaluation criteria were, as in the case of the test of the hexagonal boron nitride powder alone, ⁇ Excellent, ⁇ Excellent, ⁇ Good, ⁇ Insufficient, ⁇ Not possible depending on the degree of glitter.
- the evaluation with the largest number among the evaluation results of the ten testers was the evaluation of the tested hexagonal boron nitride powder. However, when two or more evaluations were the same and maximum, the lowest evaluation was the evaluation of the tested hexagonal boron nitride powder.
- an example of the compounding ratio of the hexagonal boron nitride powder of 20% by mass is given, but it has been confirmed that the same effect as described in Table 1 can be obtained even with the usual compounding ratio of 3 to 30% by mass. .
- No. Powder No. 6 had a low ratio of bent particles because no predetermined additive was used at the time of production, and as a result, the glitter was inferior.
- the average particle diameter was less than 15 ⁇ m because the temperature during the second heating was high (2050 ° C.), and the volatilization rate of boron oxide involved in the particle growth was higher than the particle growth rate.
- No. The powder of No. 13 was excessively pulverized until the average particle diameter became 4 ⁇ m, so that the bending ratio was 5%.
- the powder having an average particle diameter of 6 to 100 ⁇ m is the same as the powder of No. 14 had better skin adhesion than powder.
- the powder having a ratio of coarse particles of 0.5% by mass or less in the powder having a coarse particle ratio of 0.8% by mass is No. 5 Roughness was suppressed as compared with the powder of No. 15.
- Example 2 Under the production conditions shown in Table 2, hexagonal boron nitride powder was produced. Manufacturing conditions other than those shown in Table 2 were the same as in Example 1. Next, the same evaluation as in Example 1 was performed for each of the obtained hexagonal boron nitride powders.
- the bent particle ratio the number ratio of particles having a structure bent at an angle of 110 ° to 130 ° with respect to the crystal (1,0,0) plane of the particle (the second bent particle ratio was measured.
- the second bent particle ratio was determined by image analysis (three-dimensional analysis) of an image obtained by observing a hexagonal boron nitride powder with an electron microscope according to a conventional method.
- the hexagonal boron nitride powder having the second bent particle ratio of 60% or more is smaller than the hexagonal boron nitride powder having the second bent particle ratio of less than 60%. , With even better glitter.
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Abstract
Description
前記六方晶窒化ホウ素粉末に含まれる六方晶窒化ホウ素粒子のうち、粒子の結晶(1,0,0)面に対し110°~160°の角度で折れ曲がった構造を有する粒子の個数割合が30%以上である、六方晶窒化ホウ素粉末。
本発明においては、六方晶窒化ホウ素粉末に含まれる六方晶窒化ホウ素粒子のうち、粒子の結晶(1,0,0)面に対し110°~160°の角度で折れ曲がった構造を有する粒子の個数割合(以下、「折れ曲がり粒子比率」という)を30%以上とすることが重要である。折れ曲がり粒子比率が30%未満であると、十分な光輝性を得ることができない。そのため、折れ曲がり粒子比率は50%以上、好ましくは70%以上、より好ましくは80%以上とする。一方、折れ曲がり粒子比率の上限は特に限定されず、100%であってもよい。しかし、折れ曲がり粒子比率が90%を超えると効果が飽和するため、折れ曲がり粒子比率は90%以下であってよい。前記折れ曲がり粒子比率は、実施例に記載した方法で測定することができる。上記条件を満たす六方晶窒化ホウ素粉末は、後述する製造方法により製造することが可能である。
粒子の結晶(1,0,0)面に対し110°~160°の角度で折れ曲がった構造を有する粒子における折れ曲がり部分の長さは、特に限定されないが、3μm以上であることが好ましい。3μm未満であると折れ曲がりの効果がないからである。ここで、「折れ曲がり部分の長さ」とは、顕微鏡視野下で粒子を観察した際の、折れ曲りの外側の面における、折れ曲りの頂点から、該頂点に近い方の端面までの平均距離を指すものとする。
前記六方晶窒化ホウ素粉末の、変角光度計によって入射光角度:45°の条件で測定される反射率ピークの半値全幅は、80°以下であることが好ましく、60°以下であることがより好ましい。前記半値全幅を80°以下とすることにより、六方晶窒化ホウ素粉末の光輝性を高めることができる。これは、反射光が幅広い角度で反射(散乱)されるよりも、狭い角度の幅で反射される方が、より強く光の反射が感じられるためであると考えられる。前記半値全幅の下限は特に限定されないが、通常は10°以上であってよい。前記半値全幅は、変角光度計を用いて、実施例に記載した方法で測定することができる。
六方晶窒化ホウ素粉末の平均粒径は、6~100μmとすることが好ましい。前記平均粒径が6μm未満であると、肌に塗布したときに六方晶窒化ホウ素粉末が極めて緻密な膜を形成するため、ガラスフレークなどの他の光輝性顔料を併用した際に該光輝性顔料の光輝性を損なう場合がある。また、前記平均粒径を大きくすることは、上述した折れ曲がり粒子比率を高めることにも資する。そのため、前記平均粒径を6μm以上とすることが好ましい。また、前記平均粒径を15μm以上とすることにより、1つの粒子当たりの光の反射がより顕著となり、その結果、光輝性をさらに向上させることができる。そのため、前記平均粒径は15μm以上とすることがより好ましい。一方、前記平均粒径が100μm以下であれば、肌への付着性がさらに向上する。そのため、前記平均粒径は100μm以下とすることが好ましく、50μm以下とすることがより好ましい。なお、ここで前記平均粒径は、一次粒子の平均粒径を指すものとし、実施例に記載の方法で測定することができる。平均粒径は2次加熱時の条件(加熱温度、処理時間等)により制御可能である。
本発明の六方晶窒化ホウ素粉末においては、粒径が200μm以上である粒子の割合(以下、「粗粒の割合」という)を0.5質量%以下とすることが好ましい。粒径が200μm以上である粗粒は複数の粒子が固着した凝集粒であり、そのような粗粒の割合を0.5質量%以下とすることにより、肌に塗布したときのざらつきをさらに低減することができる。粗粒の割合は、解砕手段や分級手段の選択によりコントロールすることができる。
本発明の六方晶窒化ホウ素粉末においては、該六方晶窒化ホウ素粉末を構成する粒子の見掛の厚みを0.5~3.0μmとすることが好ましい。前記見掛の厚みが0.5μm以上であれば、光輝性がさらに向上する。一方、前記見掛の厚みが3.0μm以下であれば、肌に塗布する際のざらつきをさらに低減できる。前記見掛の厚みは製造時の熱処理条件を調整することにより制御できる。なお、ここで見掛の厚みとは、顕微鏡視野下において観察される、粒子の見掛の厚みの平均値を指すものとする。前記見掛の厚みは、実施例に記載の方法で測定することができる。
六方晶窒化ホウ素粉末の滑らかさをさらに向上させるためには、六方晶窒化ホウ素粉末の平均アスペクト比(粒子の長径/粒子の厚み)を5~30とすることが好ましい。前記アスペクト比は、六方晶窒化ホウ素粉末を構成する粒子を電子顕微鏡で観察して得られる各粒子のアスペクト比の平均値を指すものとする。各粒子のアスペクト比を算出する際の粒子の長径および厚みとしては、それぞれ、顕微鏡視野下における見掛の長径と見掛の厚みを用いることができる。
本発明の六方晶窒化ホウ素粉末は、特に限定されないが、下記(1)~(6)の処理を順次実施することにより製造することができる。以下、各処理について具体的に説明する。
(1)混合
(2)第1加熱
(3)冷却
(4)第2加熱
(5)粉砕
(6)水洗および乾燥
まず、六方晶窒化ホウ素粉末の製造に用いる原料と添加剤とを混合する。前記原料としては、ホウ素源としてのホウ素化合物と、窒素源としての窒素化合物を用いる。前記ホウ素化合物としては、ホウ酸および酸化ホウ素(B2O3)の一方または両方を用いる。また、前記ホウ素化合物は、さらに炭化ホウ素を含むこともできる。前記窒素化合物としては、尿素および尿素化合物の一方または両方を用いる。前記尿素化合物としては、例えば、ジシアンジアミドおよびメラミンの一方または両方を用いることができる。前記添加剤としては、Na2CO3、K2CO3、MgCO3、CaCO3、BaCO3、MgO、CaO、およびBaOからなる群より選択される1または2以上を用いる。前記添加剤を用いることにより、(100)面における結晶成長が阻害された結果、折れ曲がった構造を有する窒化ホウ素粒子が生成すると考えられる。
次いで、混合された前記原料および添加剤を600℃~1200℃の加熱温度まで加熱し、前記加熱温度に1時間以上保持する(第1加熱)。前記第1加熱により、前記原料を乱層構造の窒化ホウ素(t-BN)とする。前記加熱温度が600℃未満では、原料であるホウ素化合物と窒素化合物とが反応して乱層構造の窒化ホウ素になる反応が不十分となり、その結果、後の第2加熱における六方晶窒化ホウ素の収率が低下する。また、後述するように、第1加熱における加熱温度が600℃未満であると、本発明の条件を満足する折れ曲がり粒子比率を有する六方晶窒化ホウ素粉末を得ることができない。一方、前記加熱温度が1200℃より高いと製造コストが増加するため、経済上不適である。前記第1加熱は、不活性ガス雰囲気中で行えばよく、前記不活性ガス雰囲気としては、例えば、窒素ガス雰囲気を用いることができる。
上記第1加熱後、得られた乱層構造の窒化ホウ素粉末を一旦冷却する。前記冷却の方法は特に限定されないが、通常は、空冷とすることができる。また、前記冷却では、乱層構造の窒化ホウ素粉末を室温まで冷却することが好ましい。
次いで、前記冷却後の窒化ホウ素粉末を、不活性ガス雰囲気中で、1500~2300℃の加熱温度(第2加熱温度)まで加熱し、前記加熱温度に2時間以上保持する(第2加熱)。前記第2加熱により、窒化ホウ素の結晶化が進み、乱層構造の窒化ホウ素(t-BN)が六方晶窒化ホウ素(h-BN)へ変化する。
上記第2加熱後の六方晶窒化ホウ素は、高温での加熱により塊状のバルク体となっている。そこで、前記バルク体を粉砕する。前記粉砕の方法は特に限定されず、常法にしたがって行えばよい。
上記粉砕後、六方晶窒化ホウ素を、水洗し、ふるい分けし、次いで乾燥する。
以下の手順で六方晶窒化ホウ素粉末を製造し、その特性を評価した。
得られた六方晶窒化ホウ素粉末のそれぞれについて、以下に述べる方法で折れ曲がり粒子比率、平均粒径、見掛の厚み、粗粒の割合、および反射率ピークの半値全幅を測定した。さらに、以下に述べる方法で官能試験を実施して、六方晶窒化ホウ素粉末の光輝性、ざらつき、および肌付着性と、前記六方晶窒化ホウ素粉末を光輝性顔料と併用した場合の光輝性を評価した。評価結果を表1に併記する。
六方晶窒化ホウ素粉末を電子顕微鏡で観察し、無作為に選択した50個の一次粒子のうち折れ曲がり構造を持つ粒子の数を数えた。六方晶窒化ホウ素の一次粒子において折れ曲りが生じた場合、電子顕微鏡で「折れ曲がり有」と観察される六方晶窒化ホウ素粉末は、実質的に例外なく、1次粒子の結晶(1,0,0)面に対し110°~160°の折れ曲がり角度を有している。したがって、顕微鏡視野下において、粒子の側面から見て折れ曲がりが確認される粒子、および粒子の上面から見て折れ曲がり線が観察される粒子は、すべて110°~160°の角度で折れ曲がった構造を有する粒子と見なすことができる。そこで、折れ曲がり粒子比率は、(折れ曲がり構造を持つ粒子の個数/対象とした一次粒子の個数)×100(%)として求めることができる。前記観察は、倍率2000倍、視野数10以上の条件で行い、合計で50個の粒子を観察対象とした。
六方晶窒化ホウ素粉末を水に分散させ、レーザー回折式粒度分布測定装置(スペクトリス社、マスターサイザー3000)を使用して前記六方晶窒化ホウ素粉末の粒度分布を測定した。解析条件は、測定対象:非球形、屈折率:1.74、吸収率:0、密度:1g/cm3、分散媒:エタノール(屈折率1.33)とした。得られた粒度分布から50%累積径(メジアン径、D50)を平均粒径とした。
六方晶窒化ホウ素粉末を電子顕微鏡で観察し、一次粒子の見掛の厚みを測定した。観察は、倍率:10000倍、5視野で行い、観察された一次粒子の厚みの平均値を前記見掛の厚みとした。
粒径が200μm以上である粒子の割合として定義される「粗粒の割合」は、以下の手順で測定した。まず、六方晶窒化ホウ素粉末の全重量を測定した。次に、前記六方晶窒化ホウ素粉末を全量エタノールに分散させ、超音波を10分間付与して分散液を得た。次いで、目開き200μmのふるいを用いて前記分散液を吸引ろ過した後、前記ふるいを120℃で10分間乾燥させ、デシケーター内で冷却した。前記冷却後のふるい上重量と最初に測定した六方晶窒化ホウ素粉末の全重量から前記粗粒の割合を求めた。すなわち、粗粒の割合=(ふるい上重量/全重量)×100(%)である。
人工皮革に窒化ホウ素粉末を塗布し、変角光度計(村上色彩技術研究所製、GP-200(水平回転))を用いて-45°の入射光に対する-90°~90°の反射光強度を測定した。X軸に反射光の角度、Y軸に反射光の強度としてグラフ化したときのピークの半値全幅を反射光ピークの半値全幅とした。
10mgの六方晶窒化ホウ素粉末を試験者10人の手の甲に塗布し、光輝性の有無を判定した。光輝性の有無は、手の甲を傾けたときに目視で光輝性が認められるかどうかにより評価した。評価基準は、光輝性の程度により、◎◎秀、◎優、○良、△不十分、×不可とした。試験者10人の評価結果のうち最も数が多かった評価を、試験した六方晶窒化ホウ素粉末の評価とした。ただし、2つ以上の評価が同数で最大であった場合には、そのうち最も低い評価を試験した六方晶窒化ホウ素粉末の評価とした。
10mgの六方晶窒化ホウ素粉末を試験者10人の手の甲にとり、指で塗布したときにざらつきを感じるかを評価した。評価基準は、ざらつきをまったく感じない場合を◎、◎よりもやや劣るが合格レベルを○、ざらつきありを×とした。
10mgの六方晶窒化ホウ素粉末を試験者10人の手の甲にとり、指で一度塗布した時、手の甲への付着の量を目視で評価した。評価基準は、◎優、○良、△不十分、×不可とした。試験者10人の評価結果のうち最も数が多かった評価を、試験した六方晶窒化ホウ素粉末の評価とした。ただし、2つ以上の評価が同数で最大であった場合には、そのうち最も低い評価を試験した六方晶窒化ホウ素粉末の評価とした。
六方晶窒化ホウ素粉末を光輝性顔料と併用した際の光輝性を評価するために、実際の化粧料に近い条件で光輝性の官能試験を行った。具体的には、六方晶窒化ホウ素粉末20質量%、タルク60質量%、光輝性顔料(ガラスフレーク)20質量%を乳鉢で混合し、試験用組成物を得た。前記試験用組成物10mgを試験者10人の手の甲に塗布し、光輝性の有無を判定した。光輝性の有無は、手の甲を傾けたときに目視で光輝性が認められるかどうかにより評価した。評価基準は、六方晶窒化ホウ素粉末単体の試験の場合と同様、光輝性の程度により、◎◎秀、◎優、○良、△不十分、×不可とした。試験者10人の評価結果のうち最も数が多かった評価を、試験した六方晶窒化ホウ素粉末の評価とした。ただし、2つ以上の評価が同数で最大であった場合には、そのうち最も低い評価を試験した六方晶窒化ホウ素粉末の評価とした。なお、上記では六方晶窒化ホウ素粉末20質量%の配合率の例を挙げたが、通常の配合率である3~30質量%であっても表1に記す同様の効果を有することを確認した。
表2に示す製造条件で六方晶窒化ホウ素粉末を製造した。表2に示した以外の製造条件は実施例1と同様とした。次いで、得られた六方晶窒化ホウ素粉末のそれぞれについて、実施例1と同様の評価を実施した。ただし、折れ曲がり粒子比率としては、粒子の結晶(1,0,0)面に対し110°~130°の角度で折れ曲がった構造を有する粒子の個数割合(第2の折れ曲がり粒子比率を測定した。前記第2の折れ曲がり粒子比率は、六方晶窒化ホウ素粉末を電子顕微鏡で観察して得た画像を、常法に従って画像解析(3次元解析)することによって求めた。
Claims (5)
- 六方晶窒化ホウ素粉末であって、
前記六方晶窒化ホウ素粉末に含まれる六方晶窒化ホウ素粒子のうち、粒子の結晶(1,0,0)面に対し110°~160°の角度で折れ曲がった構造を有する粒子の個数割合が30%以上である、六方晶窒化ホウ素粉末。 - 前記六方晶窒化ホウ素粉末に含まれる六方晶窒化ホウ素粒子のうち、粒子の結晶(1,0,0)面に対し110°~130°の角度で折れ曲がった構造を有する粒子の個数割合が60%以上である、請求項1に記載の六方晶窒化ホウ素粉末。
- 変角光度計によって入射光角度:45°の条件で測定される反射率ピークの半値全幅が80°以下である、請求項1または2に記載の六方晶窒化ホウ素粉末。
- 平均粒径が6~100μmである、請求項1~3のいずれか一項に記載の六方晶窒化ホウ素粉末。
- 化粧料用である、請求項1~4のいずれか一項に記載の六方晶窒化ホウ素粉末。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05186205A (ja) * | 1992-01-08 | 1993-07-27 | Kawasaki Steel Corp | 六方晶窒化ほう素粉末およびその製造方法 |
JP2001011340A (ja) | 1999-04-28 | 2001-01-16 | Nippon Sheet Glass Co Ltd | 真珠光沢顔料およびそれを配合した化粧料 |
JP2010163371A (ja) | 2009-01-13 | 2010-07-29 | Kao Corp | 固形粉末化粧料 |
WO2012027194A2 (en) * | 2010-08-25 | 2012-03-01 | Saint-Gobain Ceramics And Plastics, Inc. | Boron nitride with attached mettalic particles, methods of making, and uses thereof |
JP2012176910A (ja) * | 2011-02-25 | 2012-09-13 | Mizushima Ferroalloy Co Ltd | 化粧料用の六方晶窒化ホウ素粉末およびその製造方法ならびに化粧料 |
WO2013065556A1 (ja) | 2011-11-02 | 2013-05-10 | 株式会社カネカ | 窒化ホウ素粉末の連続的製造方法 |
WO2014049956A1 (ja) | 2012-09-28 | 2014-04-03 | 水島合金鉄株式会社 | 高撥水性・高吸油性窒化ホウ素粉末およびその製造方法ならびに化粧料 |
JP2015140337A (ja) * | 2014-01-30 | 2015-08-03 | 水島合金鉄株式会社 | 化粧料用の六方晶窒化ホウ素粉末ならびに化粧料 |
JP2017160086A (ja) * | 2016-03-09 | 2017-09-14 | デンカ株式会社 | 六方晶窒化ホウ素粉末及びその製造方法並びに化粧料 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6645612B2 (en) * | 2001-08-07 | 2003-11-11 | Saint-Gobain Ceramics & Plastics, Inc. | High solids hBN slurry, hBN paste, spherical hBN powder, and methods of making and using them |
JP4673644B2 (ja) * | 2005-03-04 | 2011-04-20 | 水島合金鉄株式会社 | 黒鉛―六方晶窒化ほう素複合焼結体 |
WO2014049955A1 (ja) * | 2012-09-28 | 2014-04-03 | 水島合金鉄株式会社 | 親水性・高吸油性窒化ホウ素粉末およびその製造方法ならびに化粧料 |
WO2016092951A1 (ja) * | 2014-12-08 | 2016-06-16 | 昭和電工株式会社 | 六方晶窒化ホウ素粉末、その製造方法、樹脂組成物及び樹脂シート |
JP6516553B2 (ja) * | 2015-05-14 | 2019-05-22 | 株式会社トクヤマ | 六方晶窒化硼素粉末 |
JP6516594B2 (ja) * | 2015-07-01 | 2019-05-22 | 株式会社トクヤマ | 六方晶窒化硼素粒子及びその製造方法 |
KR102033328B1 (ko) * | 2015-09-03 | 2019-10-17 | 쇼와 덴코 가부시키가이샤 | 육방정 질화붕소 분말, 그 제조 방법, 수지 조성물 및 수지 시트 |
JP7002196B2 (ja) * | 2017-01-05 | 2022-01-20 | デンカ株式会社 | 六方晶窒化ホウ素粉末及び化粧料 |
-
2019
- 2019-08-02 CN CN201980052367.9A patent/CN112566868A/zh active Pending
- 2019-08-02 WO PCT/JP2019/030572 patent/WO2020031913A1/ja unknown
- 2019-08-02 EP EP19847034.6A patent/EP3835259A4/en active Pending
- 2019-08-02 US US17/266,106 patent/US20210253425A1/en active Pending
- 2019-08-02 KR KR1020217004046A patent/KR102541031B1/ko active IP Right Grant
- 2019-08-06 TW TW108127950A patent/TW202014376A/zh unknown
- 2019-08-06 TW TW110105583A patent/TWI777414B/zh active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05186205A (ja) * | 1992-01-08 | 1993-07-27 | Kawasaki Steel Corp | 六方晶窒化ほう素粉末およびその製造方法 |
JP2001011340A (ja) | 1999-04-28 | 2001-01-16 | Nippon Sheet Glass Co Ltd | 真珠光沢顔料およびそれを配合した化粧料 |
JP2010163371A (ja) | 2009-01-13 | 2010-07-29 | Kao Corp | 固形粉末化粧料 |
WO2012027194A2 (en) * | 2010-08-25 | 2012-03-01 | Saint-Gobain Ceramics And Plastics, Inc. | Boron nitride with attached mettalic particles, methods of making, and uses thereof |
JP2012176910A (ja) * | 2011-02-25 | 2012-09-13 | Mizushima Ferroalloy Co Ltd | 化粧料用の六方晶窒化ホウ素粉末およびその製造方法ならびに化粧料 |
WO2013065556A1 (ja) | 2011-11-02 | 2013-05-10 | 株式会社カネカ | 窒化ホウ素粉末の連続的製造方法 |
WO2014049956A1 (ja) | 2012-09-28 | 2014-04-03 | 水島合金鉄株式会社 | 高撥水性・高吸油性窒化ホウ素粉末およびその製造方法ならびに化粧料 |
JP2015140337A (ja) * | 2014-01-30 | 2015-08-03 | 水島合金鉄株式会社 | 化粧料用の六方晶窒化ホウ素粉末ならびに化粧料 |
JP2017160086A (ja) * | 2016-03-09 | 2017-09-14 | デンカ株式会社 | 六方晶窒化ホウ素粉末及びその製造方法並びに化粧料 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3835259A4 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022039236A1 (ja) * | 2020-08-20 | 2022-02-24 | デンカ株式会社 | 窒化ホウ素粒子、樹脂組成物、及び樹脂組成物の製造方法 |
JPWO2022039236A1 (ja) * | 2020-08-20 | 2022-02-24 | ||
JP7216872B2 (ja) | 2020-08-20 | 2023-02-01 | デンカ株式会社 | 窒化ホウ素粒子、樹脂組成物、及び樹脂組成物の製造方法 |
CN115768720A (zh) * | 2020-08-20 | 2023-03-07 | 电化株式会社 | 氮化硼粒子、树脂组合物及树脂组合物的制造方法 |
Also Published As
Publication number | Publication date |
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TW202126574A (zh) | 2021-07-16 |
CN112566868A (zh) | 2021-03-26 |
US20210253425A1 (en) | 2021-08-19 |
EP3835259A1 (en) | 2021-06-16 |
KR20210028712A (ko) | 2021-03-12 |
EP3835259A4 (en) | 2021-10-27 |
KR102541031B1 (ko) | 2023-06-08 |
TW202014376A (zh) | 2020-04-16 |
TWI777414B (zh) | 2022-09-11 |
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