JP7372141B2 - Hexagonal boron nitride powder and its manufacturing method, and cosmetics and its manufacturing method - Google Patents
Hexagonal boron nitride powder and its manufacturing method, and cosmetics and its manufacturing method Download PDFInfo
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- 229910052582 BN Inorganic materials 0.000 claims description 35
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- 239000002994 raw material Substances 0.000 claims description 30
- 238000000137 annealing Methods 0.000 claims description 27
- 239000011164 primary particle Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 17
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
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Description
本開示は、六方晶窒化ホウ素粉末及びその製造方法、並びに化粧料及びその製造方法に関する。 The present disclosure relates to a hexagonal boron nitride powder and a method for producing the same, and a cosmetic and a method for producing the same.
窒化ホウ素は、潤滑性、高熱伝導性、及び絶縁性等を有しており、固体潤滑剤、離型剤、樹脂及びゴムの充填材、化粧料（化粧品ともいう）の原料、並びに耐熱性を有する絶縁性焼結体等、幅広い用途に利用されている。 Boron nitride has lubricity, high thermal conductivity, and insulation properties, and is used as a solid lubricant, mold release agent, resin and rubber filler, raw material for cosmetics (also referred to as cosmetics), and has heat resistance. It is used in a wide range of applications, such as insulating sintered bodies.
化粧料に配合される六方晶窒化ホウ素粉末の機能としては、化粧料への滑り性、伸び性、隠ぺい性の向上、及び、光沢性の付与等が挙げられる。特に、六方晶窒化ホウ素粉末は、同様の機能を有するタルク粉末及びマイカ粉末に比べて滑り性に優れているため、優れた滑り性が求められる化粧料に汎用されている。特許文献１では、六方晶窒化ホウ素粉末の滑り性を改善するために、平均粒子径と最大粒子径を所定の数値範囲にすることが提案されている。
Functions of the hexagonal boron nitride powder blended into cosmetics include improving slipperiness, spreadability, and concealment properties of cosmetics, and imparting glossiness to the cosmetics. In particular, hexagonal boron nitride powder has superior slip properties compared to talc powder and mica powder, which have similar functions, and is therefore widely used in cosmetics that require excellent slip properties. In
化粧料に対する顧客の要求レベルの高水準化に対応するため、化粧料に用いられる原料特性もさらなる向上が求められている。例えば、ファンデーション等に用いられる原料は、一層優れた伸び性を有することが必要であると考えられる。伸び性を改善するためには、粉末をある程度嵩高くすることが有効であると考えられる。 In order to meet the increasingly high level of customer demands for cosmetics, there is a need for further improvements in the properties of raw materials used in cosmetics. For example, it is thought that raw materials used for foundations and the like need to have even better elongation properties. In order to improve extensibility, it is considered effective to make the powder bulky to some extent.
本開示では、伸び性に優れる化粧料を製造することが可能な六方晶窒化ホウ素粉末及びその製造方法を提供する。また、本開示では、上述の六方晶窒化ホウ素粉末を用いることによって伸び性に優れる化粧料及びその製造方法を提供する。 The present disclosure provides a hexagonal boron nitride powder and a method for producing the same that can produce cosmetics with excellent extensibility. Further, the present disclosure provides a cosmetic that has excellent extensibility by using the above-described hexagonal boron nitride powder, and a method for producing the same.
本開示の一側面に係る六方晶窒化ホウ素粉末は、六方晶窒化ホウ素の一次粒子が凝集して形成される二次粒子を含み、レーザー回折・散乱法によって測定される体積基準の粒子径の累積分布において、小粒径からの積算値が全体の１０％、５０％及び９０％に達したときの粒子径を、それぞれＤ１０、Ｄ５０及びＤ９０としたときに、Ｄ５０が３～３０μｍであり、Ｄ９０／Ｄ１０が４．０以上である。 The hexagonal boron nitride powder according to one aspect of the present disclosure includes secondary particles formed by agglomeration of primary particles of hexagonal boron nitride, and has a cumulative volume-based particle diameter measured by a laser diffraction/scattering method. In the distribution, when the particle diameters when the integrated value from small particle diameters reaches 10%, 50%, and 90% of the whole are D10, D50, and D90, respectively, D50 is 3 to 30 μm, and D90 /D10 is 4.0 or more.
上記六方晶窒化ホウ素粉末は、Ｄ５０が３～３０μｍであることから、伸び性に好適なサイズの一次粒子を含有する。このように、一次粒子が伸び性に好適なサイズを有しつつも、Ｄ９０／Ｄ１０が大きいため、一次粒子が凝集して構成される二次粒子の体積割合を大きくすることができる。二次粒子は、一次粒子に比べて粒子内の空隙を大きくすることができる。したがって、二次粒子の体積割合が大きい六方晶窒化ホウ素粉末は嵩高くなり、ふわふわとした外観を有する。このような六方晶窒化ホウ素粉末を塗り伸ばすと、凝集していた二次粒子が破壊されながら塗り伸ばされる。このため、伸び性に優れる。このような六方晶窒化ホウ素粉末は、化粧料の原料用として好適である。 Since the hexagonal boron nitride powder has a D50 of 3 to 30 μm, it contains primary particles of a size suitable for elongation. In this way, although the primary particles have a size suitable for extensibility, D90/D10 is large, so it is possible to increase the volume ratio of secondary particles formed by agglomeration of primary particles. Secondary particles can have larger voids within the particles than primary particles. Therefore, hexagonal boron nitride powder with a large volume proportion of secondary particles becomes bulky and has a fluffy appearance. When such hexagonal boron nitride powder is spread, the agglomerated secondary particles are destroyed and spread. Therefore, it has excellent elongation properties. Such hexagonal boron nitride powder is suitable for use as a raw material for cosmetics.
上記六方晶窒化ホウ素粉末のＤ９０／Ｄ５０は１．７以上であってよい。これによって、二次粒子の比率を一層大きくして、塗り伸ばしの際の二次粒子による伸び性向上作用を一層大きくすることができる。したがって、伸び性に一層優れる六方晶窒化ホウ素粉末とすることができる。 D90/D50 of the hexagonal boron nitride powder may be 1.7 or more. Thereby, the ratio of the secondary particles can be further increased, and the elongation-improving effect of the secondary particles upon spreading can be further increased. Therefore, it is possible to obtain a hexagonal boron nitride powder that has even better elongation properties.
上記六方晶窒化ホウ素粉末のＤ９０は５０μｍ以下であってよい。これによって、一次粒子が過度に凝集して形成される粗大粒子を低減し、化粧料の原料用としたときに、ざらつき感を低減することができる。 The hexagonal boron nitride powder may have a D90 of 50 μm or less. This reduces coarse particles formed by excessive agglomeration of primary particles, and reduces roughness when used as a raw material for cosmetics.
上記六方晶窒化ホウ素粉末は、化粧料の原料用であってよい。上記六方晶窒化ホウ素粉末は、伸び性に優れることから、化粧料の原料用に好適である。 The hexagonal boron nitride powder may be used as a raw material for cosmetics. The hexagonal boron nitride powder has excellent elongation properties and is therefore suitable for use as a raw material for cosmetics.
本開示の一側面に係る六方晶窒化ホウ素粉末の製造方法は、ホウ素を含む化合物の粉末と窒素を含む化合物の粉末を含有する原料粉末を、不活性ガス、アンモニアガス又はこれらの混合ガスの雰囲気中、６００～１３００℃で焼成して、六方晶窒化ホウ素を含む仮焼物を得る仮焼工程と、仮焼物と助剤とを含む混合粉末を、不活性ガス、アンモニアガス又はこれらの混合ガスの雰囲気中、１９００～２１００℃で焼成して、上記仮焼物における六方晶窒化ホウ素よりも高い結晶性を有する六方晶窒化ホウ素を含む焼成物を得る焼成工程と、焼成物を洗浄及び乾燥して乾燥粉末を得る精製工程と、乾燥粉末を、不活性ガス、アンモニアガス又はこれらの混合ガスの雰囲気中、１９００～２１００℃でアニールして六方晶窒化ホウ素の一次粒子が凝集して形成される二次粒子を含む加熱処理物を得るアニール工程と、加熱処理物を解砕して前記二次粒子を含む六方晶窒化ホウ素粉末を得る解砕工程と、を有する。 A method for producing hexagonal boron nitride powder according to one aspect of the present disclosure includes raw material powder containing a boron-containing compound powder and a nitrogen-containing compound powder in an atmosphere of an inert gas, ammonia gas, or a mixed gas thereof. A calcination step in which a calcined product containing hexagonal boron nitride is obtained by firing at a temperature of 600 to 1300°C; A firing step of firing at 1900 to 2100°C in an atmosphere to obtain a fired product containing hexagonal boron nitride having higher crystallinity than the hexagonal boron nitride in the above calcined product, and washing and drying the fired product. A purification process to obtain a powder, and annealing of the dry powder at 1900 to 2100°C in an atmosphere of inert gas, ammonia gas, or a mixture of these gases to form a secondary particle formed by agglomeration of primary particles of hexagonal boron nitride. The method includes an annealing step for obtaining a heat-treated product containing particles, and a crushing step for obtaining a hexagonal boron nitride powder containing the secondary particles by crushing the heat-treated product.
上記製造方法は、焼成工程よりも低い温度で焼成する仮焼工程と、助剤を用いて焼成する焼成工程を有することによって、粒径が小さく且つ結晶性が高い六方晶窒化ホウ素の一次粒子を形成することができる。そして、精製工程によって焼成物に残存する助剤等が低減され、その後のアニール工程の粒成長を抑制できる。アニール工程後に解砕工程を行うことによって、一次粒子が凝集した二次粒子を維持しつつ粗大粒子を適度な大きさを有する二次粒子に解砕することができる。 The above manufacturing method includes a calcination step in which the calcination is performed at a lower temperature than the calcination step, and a calcination step in which the calcination is performed using an auxiliary agent, thereby producing primary particles of hexagonal boron nitride having a small particle size and high crystallinity. can be formed. Further, the amount of auxiliary agents remaining in the fired product is reduced by the purification process, and grain growth in the subsequent annealing process can be suppressed. By performing the crushing process after the annealing process, coarse particles can be crushed into secondary particles having an appropriate size while maintaining secondary particles in which primary particles are aggregated.
このようにして得られる六方晶窒化ホウ素粉末は、一次粒子が凝集した二次粒子の体積割合を大きくすることができる。二次粒子は、一次粒子に比べて粒子内の空隙を大きい。したがって、二次粒子の体積割合が大きい六方晶窒化ホウ素粉末は嵩高くなり、ふわふわとした外観を有する。このような六方晶窒化ホウ素粉末を塗り伸ばすと、凝集していた二次粒子が破壊されながら塗り伸ばされる。このため、伸び性に優れる。このような六方晶窒化ホウ素粉末は、化粧料の原料用として好適である。 In the hexagonal boron nitride powder obtained in this way, the volume ratio of secondary particles in which primary particles are aggregated can be increased. Secondary particles have larger voids within the particles than primary particles. Therefore, hexagonal boron nitride powder with a large volume proportion of secondary particles becomes bulky and has a fluffy appearance. When such hexagonal boron nitride powder is spread, the agglomerated secondary particles are destroyed and spread. Therefore, it has excellent elongation properties. Such hexagonal boron nitride powder is suitable for use as a raw material for cosmetics.
上記製造方法の解砕工程で得られる六方晶窒化ホウ素粉末は、レーザー回折・散乱法によって測定される体積基準の粒子径の累積分布において、小粒径からの積算値が全体の１０％、５０％及び９０％に達したときの粒子径を、それぞれＤ１０，Ｄ５０，Ｄ９０としたときに、Ｄ５０が３～３０μｍであり、Ｄ９０／Ｄ１０が４．０以上であってよい。 In the hexagonal boron nitride powder obtained in the crushing step of the above manufacturing method, in the cumulative distribution of volume-based particle diameters measured by laser diffraction/scattering method, the cumulative value from small particle diameters is 10% of the total, 50% of the total. % and the particle diameter when reaching 90% are respectively D10, D50, and D90, D50 may be 3 to 30 μm, and D90/D10 may be 4.0 or more.
本開示の一側面に係る化粧料は、上述の六方晶窒化ホウ素粉末を含む。上述の六方晶窒化ホウ素粉末は、塗り伸ばしたときに優れた伸び性を有する。このため、このような六方晶窒化ホウ素粉末を含む化粧料は、優れた伸び性を有する。 A cosmetic according to one aspect of the present disclosure includes the hexagonal boron nitride powder described above. The hexagonal boron nitride powder described above has excellent elongation properties when spread. Therefore, cosmetics containing such hexagonal boron nitride powder have excellent elongation properties.
本開示の一側面に係る化粧料の製造方法は、上述のいずれかの製造方法で得られる六方晶窒化ホウ素粉末を原料として用いて化粧料を製造する。上述の製造方法で得られる六方晶窒化ホウ素粉末は、塗り伸ばしたときに優れた伸び性を有する。このため、このような六方晶窒化ホウ素粉末を原料として用いて製造された化粧料は、優れた伸び性を有する。 A method for producing a cosmetic according to one aspect of the present disclosure produces a cosmetic using hexagonal boron nitride powder obtained by any of the above-mentioned production methods as a raw material. The hexagonal boron nitride powder obtained by the above production method has excellent elongation properties when spread. Therefore, cosmetics produced using such hexagonal boron nitride powder as a raw material have excellent elongation properties.
本開示によれば、伸び性に優れる化粧料を製造することが可能な六方晶窒化ホウ素粉末及びその製造方法を提供することができる。また、本開示によれば、上述の六方晶窒化ホウ素粉末を用いることによって伸び性に優れる化粧料及びその製造方法を提供することができる。 According to the present disclosure, it is possible to provide a hexagonal boron nitride powder and a method for producing the same that can produce cosmetics with excellent extensibility. Further, according to the present disclosure, it is possible to provide a cosmetic that has excellent extensibility by using the above-described hexagonal boron nitride powder, and a method for producing the same.
以下、本開示の実施形態を説明する。ただし、以下の実施形態は、本開示を説明するための例示であり、本開示を以下の内容に限定する趣旨ではない。 Embodiments of the present disclosure will be described below. However, the following embodiments are examples for explaining the present disclosure, and are not intended to limit the present disclosure to the following contents.
六方晶窒化ホウ素の一次粒子が凝集して形成される二次粒子を含み、レーザー回折・散乱法によって測定される体積基準の粒子径の累積分布において、小粒径からの積算値が全体の１０％、５０％及び９０％に達したときの粒子径を、それぞれＤ１０，Ｄ５０，Ｄ９０としたときに、Ｄ５０が３～３０μｍであり、Ｄ９０／Ｄ１０が４．０以上である。 Including secondary particles formed by agglomeration of primary particles of hexagonal boron nitride, in the cumulative distribution of volume-based particle diameters measured by laser diffraction/scattering method, the cumulative value from small particle diameters is 10% of the total. %, 50%, and 90% are respectively defined as D10, D50, and D90, D50 is 3 to 30 μm, and D90/D10 is 4.0 or more.
本開示におけるＤ１０，Ｄ５０，Ｄ９０は、市販のレーザー回折式粒子径分布測定装置で測定される。Ｄ１０，Ｄ５０，Ｄ９０の大小関係は、Ｄ１０＜Ｄ５０＜Ｄ９０の関係を有する。Ｄ５０は、化粧料の原料として用いたときの滑り性を一層向上する観点から、５μｍ以上であってよいし、７μｍ以上であってもよい。Ｄ５０は、化粧料の原料として用いたときに外観上のぎらつきを低減する観点から、２５μｍ以下であってもよいし、２０μｍ以下であってもよい。 D10, D50, and D90 in the present disclosure are measured using a commercially available laser diffraction particle size distribution measuring device. The magnitude relationship of D10, D50, and D90 is D10<D50<D90. D50 may be 5 μm or more, or 7 μm or more from the viewpoint of further improving slipperiness when used as a raw material for cosmetics. D50 may be 25 μm or less or 20 μm or less from the viewpoint of reducing glare in appearance when used as a raw material for cosmetics.
Ｄ９０は、５０μｍ以下であってよく、４５μｍ以下であってよく、４０μｍ以下であってもよい。これによって、一次粒子が過度に凝集して形成される粗大粒子を低減し、化粧料の原料用としたときに、ざらつき感を低減することができる。Ｄ９０は、伸び性を一層向上する観点から、１８μｍ以上であってよく、１９μｍ以上であってもよい。 D90 may be 50 μm or less, 45 μm or less, or 40 μm or less. This reduces coarse particles formed by excessive agglomeration of primary particles, and reduces roughness when used as a raw material for cosmetics. D90 may be 18 μm or more, or 19 μm or more from the viewpoint of further improving elongation.
Ｄ１０は、２μｍ以上であってよく、３μｍ以上であってよい。これによって、伸び性を一層向上することができる。Ｄ１０は、１０μｍ以下であってよく、８μｍ以下であってよい。これによって、化粧料の原料として用いたときに外観上のぎらつきを低減することができる。Ｄ１０，Ｄ５０，Ｄ９０は、例えば、原料粉末の粒度分布、仮焼温度及び仮焼時間、焼成温度及び焼成時間、並びにアニール温度及びアニール時間等によって調整することができる。 D10 may be 2 μm or more, or 3 μm or more. This can further improve elongation. D10 may be 10 μm or less, and may be 8 μm or less. This makes it possible to reduce glare in appearance when used as a raw material for cosmetics. D10, D50, and D90 can be adjusted by, for example, the particle size distribution of the raw material powder, the calcination temperature and time, the calcination temperature and time, and the annealing temperature and time.
Ｄ９０／Ｄ１０は、４．５以上であってよく、５．０以上であってよく、６．０以上であってもよい。このようにＤ９０／Ｄ１０を大きくすることによって、一次粒子に対する二次粒子の割合及びサイズを十分に大きくすることができる。これによって、二次粒子に含まれる空隙が多くなって外観が一層ふわふわになり、塗り伸ばしたときの伸び性を一層向上することができる。Ｄ９０／Ｄ１０の上限は、製造コスト低減の観点から、１０であってよく、８．０であってもよい。Ｄ９０／Ｄ１０は、例えば、焼成工程の焼成温度と焼成時間、及び、アニール工程のアニール温度とアニール時間を変えることによって調整することができる。 D90/D10 may be 4.5 or more, 5.0 or more, or 6.0 or more. By increasing D90/D10 in this manner, the ratio and size of secondary particles to primary particles can be sufficiently increased. As a result, the number of voids contained in the secondary particles increases, resulting in a fluffier appearance and further improved elongation when spread. The upper limit of D90/D10 may be 10 or 8.0 from the viewpoint of reducing manufacturing costs. D90/D10 can be adjusted, for example, by changing the firing temperature and firing time of the firing process, and the annealing temperature and annealing time of the annealing process.
Ｄ９０／Ｄ５０は、１．７以上であってよく、１．８以上であってよく、２．０以上であってもよい。これによって、二次粒子の比率を一層大きくして、塗り伸ばしの際の二次粒子による伸び性向上作用を一層大きくすることができる。したがって、伸び性に一層優れる六方晶窒化ホウ素粉末とすることができる。Ｄ９０／Ｄ５０の上限は、製造コスト低減の観点から、６．０であってよく、４．０であってもよい。Ｄ９０／Ｄ５０は、例えば、アニール工程のアニール温度及びアニール時間を変えることによって調整することができる。 D90/D50 may be 1.7 or more, 1.8 or more, or 2.0 or more. Thereby, the ratio of the secondary particles can be further increased, and the elongation-improving effect of the secondary particles upon spreading can be further increased. Therefore, it is possible to obtain a hexagonal boron nitride powder that has even better elongation properties. The upper limit of D90/D50 may be 6.0 or 4.0 from the viewpoint of manufacturing cost reduction. D90/D50 can be adjusted, for example, by changing the annealing temperature and annealing time of the annealing step.
Ｄ５０／Ｄ１０は、４．０以下であってよく、３．０以下であってよく、２．８以下であってもよい。これによって、一次粒子の粒径のばらつきを小さくして、隠蔽性を十分に高くすることができる。Ｄ５０／Ｄ１０の下限は、製造コスト低減の観点から、１．５以上であってよく、２．０以上であってもよい。Ｄ５０／Ｄ１０は、例えば、焼成工程の焼成時間を変えることによって調整することができる。 D50/D10 may be 4.0 or less, 3.0 or less, or 2.8 or less. This makes it possible to reduce the variation in the particle size of the primary particles and to sufficiently increase the hiding power. The lower limit of D50/D10 may be 1.5 or more, or may be 2.0 or more from the viewpoint of manufacturing cost reduction. D50/D10 can be adjusted, for example, by changing the firing time of the firing process.
六方晶窒化ホウ素粉末のかさ密度は、０．４５ｇ／ｃｍ３以下であってよく、０．４１ｃｍ３以下であってよく、０．３５ｃｍ３以下であってもよい。このように低いかさ密度を有することによって、一層ふわふわとした外観を有する六方晶窒化ホウ素粉末とすることができる。かさ密度は、ＪＩＳ Ｒ１６２８－１９９７の「ファインセラミックス粉末のかさ密度測定方法」に準拠して測定することができる。 The bulk density of the hexagonal boron nitride powder may be 0.45 g/cm 3 or less, 0.41 cm 3 or less, or 0.35 cm 3 or less. Having such a low bulk density allows the hexagonal boron nitride powder to have a fluffier appearance. The bulk density can be measured in accordance with JIS R1628-1997 "Method for Measuring Bulk Density of Fine Ceramic Powders."
本実施形態に係る六方晶窒化ホウ素は、一次粒子が伸び性に好適なサイズを有しつつも、Ｄ９０／Ｄ１０が大きいため、一次粒子が凝集して構成される二次粒子の体積割合を大きくすることができる。二次粒子は、一次粒子に比べて粒子内の空隙を大きくすることができる。したがって、二次粒子を多く含む六方晶窒化ホウ素粉末は嵩高くなり、ふわふわとした外観を有する。このような六方晶窒化ホウ素粉末を塗り伸ばすと、凝集していた二次粒子が破壊されながら塗り伸ばされる。このため、伸び性に優れる。このような六方晶窒化ホウ素粉末は、化粧料の原料用として好適である。すなわち、本開示は、六方晶窒化ホウ素を化粧料の原料として使用する使用方法も提供することができる。 In the hexagonal boron nitride according to this embodiment, although the primary particles have a suitable size for extensibility, D90/D10 is large, so the volume ratio of secondary particles composed of agglomerated primary particles is increased. can do. Secondary particles can have larger voids within the particles than primary particles. Therefore, hexagonal boron nitride powder containing many secondary particles becomes bulky and has a fluffy appearance. When such hexagonal boron nitride powder is spread, the agglomerated secondary particles are destroyed and spread. Therefore, it has excellent elongation properties. Such hexagonal boron nitride powder is suitable for use as a raw material for cosmetics. That is, the present disclosure can also provide a method of using hexagonal boron nitride as a raw material for cosmetics.
一実施形態に係る化粧料は、上述の六方晶窒化ホウ素粉末を含有する。したがって、この六方晶窒化ホウ素粉末を含有する化粧料は、伸び性に優れる。化粧料としては、例えば、ファンデーション（パウダーファンデーション、リキッドファンデーション、クリームファンデーション）、フェイスパウダー、ポイントメイク、アイシャドー、アイライナー、マニュキュア、口紅、頬紅、及びマスカラ等が挙げられる。これらのうち、ファンデーション及びアイシャドーには、六方晶窒化ホウ素粉末が特に良く適合する。化粧料における六方晶窒化ホウ素粉末の含有量は、例えば０．１～７０質量％である。化粧料は公知の方法によって製造することができる。化粧料の製造方法は、例えば、六方晶窒化ホウ素粉末と他の原料とを配合して混合する工程を有する。 A cosmetic according to one embodiment contains the above-described hexagonal boron nitride powder. Therefore, cosmetics containing this hexagonal boron nitride powder have excellent elongation properties. Examples of cosmetics include foundations (powder foundation, liquid foundation, cream foundation), face powder, point makeup, eye shadow, eyeliner, nail polish, lipstick, blush, mascara, and the like. Among these, hexagonal boron nitride powder is particularly well suited for foundations and eye shadows. The content of hexagonal boron nitride powder in the cosmetic is, for example, 0.1 to 70% by mass. Cosmetics can be manufactured by known methods. A method for producing cosmetics includes, for example, a step of blending and mixing hexagonal boron nitride powder and other raw materials.
一実施形態に係る六方晶窒化ホウ素粉末の製造方法は、ホウ素を含む化合物の粉末と窒素を含む化合物の粉末を含有する原料粉末を、不活性ガス、アンモニアガス又はこれらの混合ガスの雰囲気中、６００～１３００℃で焼成して、六方晶窒化ホウ素を含む仮焼物を得る仮焼工程と、六方晶窒化ホウ素と助剤とを含む混合粉末を、不活性ガス、アンモニアガス又はこれらの混合ガスの雰囲気中、１９００～２１００℃で焼成して、混合粉末における六方晶窒化ホウ素よりも高い結晶性を有する六方晶窒化ホウ素を含む焼成物を得る焼成工程と、焼成物を洗浄及び乾燥して乾燥粉末を得る精製工程と、乾燥粉末を、不活性ガス、アンモニアガス又はこれらの混合ガスの雰囲気中、１９００～２１００℃でアニールして六方晶窒化ホウ素の一次粒子が凝集して形成される二次粒子を含む加熱処理物を得るアニール工程と、加熱処理物を解砕して二次粒子を含む六方晶窒化ホウ素粉末を得る解砕工程と、を有する。 A method for producing hexagonal boron nitride powder according to one embodiment includes raw material powder containing powder of a boron-containing compound and powder of a compound containing nitrogen in an atmosphere of an inert gas, ammonia gas, or a mixed gas thereof. A calcination step in which a calcined product containing hexagonal boron nitride is obtained by firing at 600 to 1300°C, and a mixed powder containing hexagonal boron nitride and an auxiliary agent is heated in an inert gas, ammonia gas, or a mixed gas thereof. A firing step in which the fired product is fired at 1900 to 2100°C in an atmosphere to obtain a fired product containing hexagonal boron nitride having higher crystallinity than hexagonal boron nitride in the mixed powder, and a dry powder is obtained by washing and drying the fired product. and secondary particles formed by agglomeration of primary particles of hexagonal boron nitride by annealing the dry powder at 1900 to 2100°C in an atmosphere of inert gas, ammonia gas, or a mixture thereof. and a crushing step of crushing the heat-treated product to obtain hexagonal boron nitride powder containing secondary particles.
ホウ素を含む化合物としては、ホウ酸、酸化ホウ素及びホウ砂等が挙げられる。窒素を含む化合物としては、ジシアンジアミド、メラミン、及び尿素が挙げられる。ホウ素を含む化合物の粉末と窒素を含む化合物の粉末を含有する原料粉末におけるホウ素原子と窒素原子のモル比は、ホウ素原子：窒素原子＝２：８～８：２であってよく、３：７～７：３であってもよい。原料粉末は、上記化合物以外の成分を含んでもよい。例えば、仮焼用助剤として炭酸リチウム及び炭酸ナトリウムなどの炭酸塩を含んでよい。また、炭素等の還元性物質を含んでよい。 Examples of compounds containing boron include boric acid, boron oxide, and borax. Compounds containing nitrogen include dicyandiamide , melamine, and urea. The molar ratio of boron atoms to nitrogen atoms in the raw material powder containing powder of a boron-containing compound and powder of a compound containing nitrogen may be boron atoms:nitrogen atoms=2:8 to 8:2, and 3:7. It may be 7:3. The raw material powder may contain components other than the above-mentioned compounds. For example, carbonates such as lithium carbonate and sodium carbonate may be included as calcination aids. Further, it may contain a reducing substance such as carbon.
上述の成分を含有する原料粉末を、例えば電気炉を用いて、窒素ガス、ヘリウムガス、又はアルゴンガス等の不活性雰囲気中、アンモニア雰囲気中、或いはこれらを混合した混合ガス雰囲気中で仮焼する。仮焼温度は、６００～１３００℃であってよく、８００～１２００℃であってよく、９００～１１００℃であってもよい。仮焼時間は、例えば０．５～５時間であってよく、１～４時間であってもよい。 The raw material powder containing the above-mentioned components is calcined in an inert atmosphere such as nitrogen gas, helium gas, or argon gas, an ammonia atmosphere, or a mixed gas atmosphere of these by using, for example, an electric furnace. . The calcination temperature may be 600 to 1300°C, 800 to 1200°C, or 900 to 1100°C. The calcination time may be, for example, 0.5 to 5 hours, or 1 to 4 hours.
仮焼によって得られる仮焼物は、低結晶性の六方晶窒化ホウ素、及び非晶質の六方晶窒化ホウ素からなる群より選ばれる少なくとも一方を含む。仮焼工程は、後述の焼成工程よりも低温で窒化ホウ素の反応を進行させる。このため、粒成長を抑制し、最終的に得られる窒化ホウ素粉末における一次粒子の粒径を小さくすることができる。 The calcined material obtained by calcining contains at least one selected from the group consisting of low-crystalline hexagonal boron nitride and amorphous hexagonal boron nitride. In the calcination step, the reaction of boron nitride proceeds at a lower temperature than in the calcination step described below. Therefore, grain growth can be suppressed and the particle size of primary particles in the finally obtained boron nitride powder can be reduced.
次に、得られた仮焼物と助剤とを配合して混合し、混合粉末を得る。助剤としては、ホウ酸ナトリウム等のホウ酸塩、並びに、炭酸ナトリウム、炭酸カルシウム及び炭酸リチウム等の炭酸塩が挙げられる。六方晶窒化ホウ素を含む仮焼物１００質量部に対する、助剤の配合量は２～２０質量部であってよく、２～８質量部であってもよい。このような混合粉末を、例えば電気炉中、窒素ガス、ヘリウムガス、又はアルゴンガス等の不活性雰囲気中、アンモニア雰囲気中、或いはこれらを含む混合ガス雰囲気中で焼成する。 Next, the obtained calcined product and an auxiliary agent are blended and mixed to obtain a mixed powder. Auxiliary agents include borates such as sodium borate, and carbonates such as sodium carbonate, calcium carbonate, and lithium carbonate. The blending amount of the auxiliary agent may be 2 to 20 parts by mass, or 2 to 8 parts by mass, based on 100 parts by mass of the calcined material containing hexagonal boron nitride. Such a mixed powder is fired, for example, in an electric furnace, in an inert atmosphere such as nitrogen gas, helium gas, or argon gas, in an ammonia atmosphere, or in a mixed gas atmosphere containing these.
焼成工程では、助剤の存在下、窒化ホウ素の生成及び結晶化が進行する。これによって、仮焼物に含まれる窒化ホウ素の結晶性を高めることができる。焼成温度は、１９００～２１００℃である。この焼成温度は、１９５０～２０５０℃であってもよい。焼成時間は、例えば０．５～５時間であってよく、１～４時間であってもよい。 In the firing step, the production and crystallization of boron nitride progress in the presence of an auxiliary agent. Thereby, the crystallinity of boron nitride contained in the calcined product can be improved. The firing temperature is 1900 to 2100°C. This firing temperature may be 1950 to 2050°C. The firing time may be, for example, 0.5 to 5 hours, or 1 to 4 hours.
焼成温度が低くなり過ぎると、六方晶窒化ホウ素の二次粒子が十分に生成し難くなる傾向にある。二次粒子の体積割合が小さくなると、化粧料の原料に用いた場合に滑り性が低下する傾向にある。焼成時間が短くなり過ぎたときも同様の傾向にある。一方、焼成温度が高くなり過ぎると、六方晶窒化ホウ素の結晶成長及び凝集が進み過ぎて、化粧料の原料に用いた場合にぎらつきが強くなる傾向にある。 If the firing temperature becomes too low, it tends to be difficult to sufficiently generate secondary particles of hexagonal boron nitride. As the volume ratio of secondary particles decreases, slipperiness tends to decrease when used as a raw material for cosmetics. A similar tendency occurs when the firing time becomes too short. On the other hand, if the firing temperature is too high, the crystal growth and aggregation of hexagonal boron nitride will proceed too much, and when used as a raw material for cosmetics, there will be a tendency for glare to become stronger.
焼成工程で得られた焼成物は、六方晶窒化ホウ素以外に不純物を含む場合がある。不純物としては、残存する助剤、及び水溶性ホウ素化合物等が挙げられる。精製工程では、このような不純物を、洗浄によって低減する。洗浄後、固液分離して乾燥し、乾燥粉末を得る。洗浄に用いる洗浄液としては、水、酸性物質を含む水溶液、有機溶媒、有機溶媒と水との混合液等が挙げられる。不純物の二次的な混入を避ける観点から、電気伝導度が１ｍＳ／ｍ以下の水を使用してよい。酸性物質としては、例えば塩酸、硝酸等の無機酸が挙げられる。有機溶媒としては、例えば、メタノール、エタノール、プロパノール、イソプロピルアルコール及びアセトン等の水溶性の有機溶媒が挙げられる。洗浄方法に特に制限はなく、例えば、焼成物を洗浄液中に浸漬し撹拌して洗浄してよく、焼成物に洗浄液をスプレーして洗浄してもよい。 The fired product obtained in the firing process may contain impurities other than hexagonal boron nitride. Examples of impurities include remaining auxiliary agents and water-soluble boron compounds. In the purification process, such impurities are reduced by washing. After washing, solid-liquid separation is performed and dried to obtain a dry powder. Examples of the cleaning liquid used for cleaning include water, an aqueous solution containing an acidic substance, an organic solvent, and a mixed solution of an organic solvent and water. From the viewpoint of avoiding secondary contamination of impurities, water having an electrical conductivity of 1 mS/m or less may be used. Examples of acidic substances include inorganic acids such as hydrochloric acid and nitric acid. Examples of the organic solvent include water-soluble organic solvents such as methanol, ethanol, propanol, isopropyl alcohol, and acetone. There are no particular restrictions on the cleaning method; for example, the fired product may be immersed in a cleaning solution and stirred for cleaning, or the fired product may be sprayed with a cleaning solution for cleaning.
洗浄終了後、デカンテーション、吸引ろ過機、加圧ろ過機、回転式ろ過機、沈降分離機又はこれらを組み合わせた装置を用いて洗浄液を固液分離してよい。分離した固形分を通常の乾燥機で乾燥して乾燥粉末を得てもよい。乾燥機は、例えば、棚式乾燥機、流動層乾燥機、噴霧乾燥機、回転型乾燥機、ベルト式乾燥機、及びこれらの組み合わせが挙げられる。乾燥後に、粗大粒子を除去するために、例えば篩による分級を行ってもよい。 After the washing is completed, the washing liquid may be separated into solid and liquid using decantation, a suction filter, a pressure filter, a rotary filter, a sedimentation separator, or a combination thereof. The separated solids may be dried in a conventional dryer to obtain a dry powder. Dryers include, for example, tray dryers, fluidized bed dryers, spray dryers, rotary dryers, belt dryers, and combinations thereof. After drying, classification using a sieve may be performed, for example, in order to remove coarse particles.
アニール工程では、乾燥粉末を、例えば電気炉を用いて、窒素ガス、ヘリウムガス、又はアルゴンガス等の不活性雰囲気中、アンモニア雰囲気中、或いはこれらを混合した混合ガス雰囲気中で１９００～２１００℃に加熱する。このアニール温度は、一次粒子を十分に凝集させる観点から、１９５０℃以上であってよい。また、アニール温度は、一次粒子の粒成長を抑制する観点から２０５０℃以下であってよい。アニール工程では、焼成工程と同等の温度に加熱していることから、一次粒子が凝集した二次粒子を含む加熱処理物を得ることができる。アニール時間は、酸素量を十分に低減するとともに粒子の成長を抑制する観点から、例えば０．５～５時間であってよく、１～４時間であってもよい。 In the annealing step, the dry powder is heated to 1900 to 2100°C in an inert atmosphere such as nitrogen gas, helium gas, or argon gas, in an ammonia atmosphere, or in a mixed gas atmosphere of these, using an electric furnace, for example. Heat. This annealing temperature may be 1950° C. or higher from the viewpoint of sufficiently agglomerating the primary particles. Further, the annealing temperature may be 2050° C. or lower from the viewpoint of suppressing grain growth of primary particles. In the annealing step, since heating is performed to a temperature equivalent to that in the firing step, it is possible to obtain a heated product containing secondary particles in which primary particles are aggregated. The annealing time may be, for example, 0.5 to 5 hours, or 1 to 4 hours, from the viewpoint of sufficiently reducing the amount of oxygen and suppressing particle growth.
解砕工程では、アニール工程で得られる加熱処理物を解砕する。解砕工程は、凝集した二次粒子が破壊されない程度の衝撃を与える方法で行うことが好ましい。このような観点から、解砕工程は、溶媒に分散した加熱処理物に超音波振動を与えるホモジナイザを用いることが好ましい。溶媒としては、精製工程の洗浄液として例示したものを用いることができる。このような解砕工程によって、粗大粒子を低減しつつ、ふわふわ感を付与する二次粒子を十分に残存させることができる。また、加熱処理物に残存する不純物の洗浄を円滑に行うことができる。 In the crushing process, the heat-treated material obtained in the annealing process is crushed. It is preferable that the crushing step is carried out by applying an impact to an extent that the aggregated secondary particles are not destroyed. From this point of view, the crushing step preferably uses a homogenizer that applies ultrasonic vibration to the heat-treated material dispersed in the solvent. As the solvent, those exemplified as the washing liquid in the purification step can be used. Through such a crushing step, it is possible to reduce coarse particles while sufficiently leaving secondary particles that impart a fluffy feel. Further, impurities remaining in the heat-treated product can be smoothly cleaned.
六方晶窒化ホウ素粉末のＤ９０／Ｄ１０の値は、アニール工程後のホモジナイザによる解砕時間で調整することができる。具体的には、解砕時間を長くすると、Ｄ９０／Ｄ１０の値が小さくなる。また、解砕時間を短くすると、Ｄ９０／Ｄ１０の値が大きくなる。このように、アニール工程等を行った後に解砕工程のホモジナイザによる解砕時間を調整することで、Ｄ９０／Ｄ１０の値を所望の範囲に調整することができる。
The value of D90/D10 of the hexagonal boron nitride powder can be adjusted by the crushing time using a homogenizer after the annealing process. Specifically, when the crushing time is increased, the value of D90/D10 becomes smaller. Moreover, when the crushing time is shortened, the value of D90/D10 increases. In this way, by adjusting the crushing time by the homogenizer in the crushing process after performing the annealing process etc., the value of D90/D10 can be adjusted to a desired range.
このようにして、上述の六方晶窒化ホウ素粉末を得ることができる。上記製造方法には、六方晶窒化ホウ素粉末の実施形態に係る説明を適用することができる。 In this way, the above-mentioned hexagonal boron nitride powder can be obtained. The explanation regarding the embodiment of hexagonal boron nitride powder can be applied to the above manufacturing method.
以上、本開示の幾つかの実施形態について説明したが、本開示は上記実施形態に何ら限定されるものではない。 Although several embodiments of the present disclosure have been described above, the present disclosure is not limited to the above embodiments.
実施例及び比較例を参照して本開示の内容をより詳細に説明するが、本開示は下記の実施例に限定されるものではない。 The contents of the present disclosure will be explained in more detail with reference to Examples and Comparative Examples, but the present disclosure is not limited to the following Examples.
（実施例１）
［六方晶窒化ホウ素粉末の調製］
＜仮焼工程＞
ホウ酸粉末（純度９９．８質量％以上、関東化学社製）１００．０ｇ、及びメラミン粉末（純度９９．０質量％以上、和光純薬社製）９０．０ｇを、アルミナ製乳鉢を用いて１０分間混合し混合原料を得た。乾燥後の混合原料を、六方晶窒化ホウ素製の容器に入れ、電気炉内に配置した。電気炉内に窒素ガスを流通させながら、１０℃／分の速度で室温から１０００℃に昇温した。１０００℃で２時間保持した後、加熱を止めて自然冷却した。温度が１００℃以下になった時点で電気炉を開放した。このようにして、低結晶性の六方晶窒化ホウ素を含む仮焼物を得た。
(Example 1)
[Preparation of hexagonal boron nitride powder]
<Calcination process>
100.0 g of boric acid powder (purity of 99.8% by mass or more, manufactured by Kanto Kagaku Co., Ltd.) and 90.0 g of melamine powder (purity of 99.0% by mass or more, manufactured by Wako Pure Chemical Industries, Ltd.) were added using an alumina mortar. The mixture was mixed for 10 minutes to obtain a mixed raw material. The mixed raw material after drying was placed in a container made of hexagonal boron nitride and placed in an electric furnace. While flowing nitrogen gas into the electric furnace, the temperature was raised from room temperature to 1000°C at a rate of 10°C/min. After holding at 1000°C for 2 hours, heating was stopped and the mixture was allowed to cool naturally. The electric furnace was opened when the temperature became 100°C or lower. In this way, a calcined product containing hexagonal boron nitride with low crystallinity was obtained.
＜焼成工程＞
仮焼物１００．０ｇに、助剤として炭酸ナトリウム（純度９９．５質量％以上）を３．０ｇ添加し、アルミナ製乳鉢を用いて１０分間混合した。混合物を、上述の電気炉内に配置した。電気炉内に窒素ガスを流通させながら、１０℃／分の速度で室温から２０００℃に昇温した。２０００℃の焼成温度で４時間保持した後、加熱を止めて自然冷却した。温度が１００℃以下になった時点で電気炉を開放した。得られた焼成物を回収し、アルミナ製乳鉢で３分間粉砕して、六方晶窒化ホウ素の粗粉を得た。
<Baking process>
3.0 g of sodium carbonate (purity: 99.5% by mass or more) was added as an auxiliary agent to 100.0 g of the calcined material, and the mixture was mixed for 10 minutes using an alumina mortar. The mixture was placed in the electric furnace described above. While flowing nitrogen gas into the electric furnace, the temperature was raised from room temperature to 2000°C at a rate of 10°C/min. After maintaining the firing temperature at 2000° C. for 4 hours, heating was stopped and the product was allowed to cool naturally. The electric furnace was opened when the temperature became 100°C or less. The obtained fired product was collected and ground in an alumina mortar for 3 minutes to obtain a coarse powder of hexagonal boron nitride.
＜精製工程＞
六方晶窒化ホウ素の粗粉中に含まれる不純物を除くため、希硝酸５００ｇ（硝酸濃度：５質量％）に、粗粉を３０ｇ投入し、室温で６０分間撹拌した。撹拌後、吸引ろ過によって固液分離し、ろ液が中性になるまで水（電気伝導度１ｍＳ／ｍ）を入れ替えて洗浄した。洗浄後、乾燥機を用いて１２０℃で３時間乾燥して乾燥粉末を得た。
<Refining process>
In order to remove impurities contained in the hexagonal boron nitride coarse powder, 30 g of the coarse powder was added to 500 g of dilute nitric acid (nitric acid concentration: 5% by mass) and stirred at room temperature for 60 minutes. After stirring, solid-liquid separation was performed by suction filtration, and water (electrical conductivity: 1 mS/m) was replaced and washed until the filtrate became neutral. After washing, it was dried at 120° C. for 3 hours using a drier to obtain a dry powder.
＜アニール工程＞
粗粒を除去した乾燥粉末を、上述の電気炉内に配置した。電気炉内に窒素ガスを流通させながら、１０℃／分の速度で室温から２０００℃に昇温した。２０００℃で４時間保持した後、加熱を止めて自然冷却した。温度が１００℃以下になった時点で電気炉を開放した。得られた焼成物を回収し、六方晶窒化ホウ素粉末の粗粉を得た。
<Annealing process>
The dry powder from which coarse particles had been removed was placed in the electric furnace described above. While flowing nitrogen gas into the electric furnace, the temperature was raised from room temperature to 2000°C at a rate of 10°C/min. After holding at 2000°C for 4 hours, heating was stopped and the mixture was allowed to cool naturally. The electric furnace was opened when the temperature became 100°C or lower. The obtained fired product was collected to obtain coarse hexagonal boron nitride powder.
＜解砕工程＞
アニール工程で得られた六方晶窒化ホウ素の粗粉３０ｇを水３００ｍｌに投入し、ホモジナイザ（ＳＯＮＩＣ ＆ ＭＡＴＥＲＩＡＬＳ，ＩＮＣ．製、商品名：ＶＣ５０５）を用いて、５００Ｗ、２０ｋＨｚの条件で５分間超音波分散させた。その後、粗粉中に含まれる不純物を除くため、希硝酸５００ｇ（硝酸濃度：５質量％）を加え、室温で６０分間撹拌した。撹拌後、吸引ろ過によって固液分離し、ろ液が中性になるまで水（電気伝導度：１ｍＳ／ｍ）を入れ替えて洗浄した。洗浄後、乾燥機を用いて１２０℃で３時間乾燥して乾燥粉末を得た。得られた乾燥粉末から、超音波振動篩（株式会社興和工業所社製、商品名：ＫＦＳ－１０００、目開き２５０μｍ）を用いて、粗粒を除去した。これを実施例１の六方晶窒化ホウ素粉末とした。
<Crushing process>
30 g of hexagonal boron nitride coarse powder obtained in the annealing process was added to 300 ml of water, and subjected to ultrasonication for 5 minutes at 500 W and 20 kHz using a homogenizer (manufactured by SONIC & MATERIALS, INC., product name: VC505). Dispersed. Thereafter, in order to remove impurities contained in the coarse powder, 500 g of dilute nitric acid (nitric acid concentration: 5% by mass) was added, and the mixture was stirred at room temperature for 60 minutes. After stirring, solid-liquid separation was performed by suction filtration, and water (electrical conductivity: 1 mS/m) was replaced and washed until the filtrate became neutral. After washing, it was dried at 120° C. for 3 hours using a drier to obtain a dry powder. Coarse particles were removed from the obtained dry powder using an ultrasonic vibrating sieve (manufactured by Kowa Kogyo Co., Ltd., trade name: KFS-1000, mesh size 250 μm). This was used as the hexagonal boron nitride powder of Example 1.
［六方晶窒化ホウ素粉末の評価］
＜粒度分布の測定＞
実施例１で調製した六方晶窒化ホウ素粉末の体積基準の粒度分布を、レーザー回折式粒子径分布測定装置（日機装株式会社製、装置名：ＭＴ３３００ＥＸ）を用いて測定した。図１は、この測定によって得られた、体積基準の粒子径の累積分布を示すグラフである。図１に示す累積分布において、小粒径からの積算値が全体の１０％、５０％及び９０％に達したときの粒子径を、それぞれＤ１０，Ｄ５０，Ｄ９０としたとき、Ｄ１０，Ｄ５０，Ｄ９０のそれぞれの値は表２に示すとおりであった。表２には、Ｄ９０／Ｄ１０、Ｄ９０／Ｄ５０、及びＤ５０／Ｄ１０の値も併せて示した。
[Evaluation of hexagonal boron nitride powder]
<Measurement of particle size distribution>
The volume-based particle size distribution of the hexagonal boron nitride powder prepared in Example 1 was measured using a laser diffraction particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., device name: MT3300EX). FIG. 1 is a graph showing the cumulative distribution of volume-based particle diameters obtained by this measurement. In the cumulative distribution shown in Figure 1, when the particle diameters when the cumulative value from small particle diameters reaches 10%, 50%, and 90% of the total are D10, D50, and D90, respectively, D10, D50, D90 The respective values of were as shown in Table 2. Table 2 also shows the values of D90/D10, D90/D50, and D50/D10.
＜伸び性の評価＞
人工皮膚（縦×横＝１０ｍｍ×５０ｍｍ）の一端に、六方晶窒化ホウ素粉末０．２ｇを載せた。人工皮膚の表面に六方晶窒化ホウ素粉末を塗り付けるように、ヘラを用いて六方晶窒化ホウ素粉末を縦方向に沿って伸ばした。市販の画像解析ソフトウェア（ＷｉｎＲＯＯＦ）を用いて画像解析を行って、人工皮膚の全面積に対する、六方晶窒化ホウ素粉末の塗布面積の割合を求めた。この面積割合が大きいほど伸び性が優れている。伸び性の評価基準は、面積割合に応じて表１に示すとおりとした。伸び性の評価結果は表２に示すとおりであった。
<Evaluation of extensibility>
0.2 g of hexagonal boron nitride powder was placed on one end of the artificial skin (length x width = 10 mm x 50 mm). The hexagonal boron nitride powder was stretched in the vertical direction using a spatula so as to spread the hexagonal boron nitride powder onto the surface of the artificial skin. Image analysis was performed using commercially available image analysis software (WinROOF) to determine the ratio of the area of the hexagonal boron nitride powder applied to the total area of the artificial skin. The larger this area ratio is, the better the elongation property is. The evaluation criteria for elongation were as shown in Table 1 according to the area ratio. The elongation evaluation results were as shown in Table 2.
（実施例２）
アニール工程の加熱温度を２０５０℃にしたこと以外は、実施例１と同様にして六方晶窒化ホウ素粉末を調製した。そして、実施例１と同様にして、六方晶窒化ホウ素粉末の各測定及び評価を行った。結果は図１及び表２に示すとおりであった。
(Example 2)
Hexagonal boron nitride powder was prepared in the same manner as in Example 1, except that the heating temperature in the annealing step was 2050°C. Then, in the same manner as in Example 1, each measurement and evaluation of the hexagonal boron nitride powder was performed. The results were as shown in FIG. 1 and Table 2.
（実施例３）
アニール工程の保持時間を５時間にしたこと以外は、実施例１と同様にして六方晶窒化ホウ素粉末を調製した。そして、実施例１と同様にして、六方晶窒化ホウ素粉末の各測定及び評価を行った。結果は図１及び表２に示すとおりであった。
(Example 3)
Hexagonal boron nitride powder was prepared in the same manner as in Example 1 except that the holding time in the annealing step was 5 hours. Then, in the same manner as in Example 1, each measurement and evaluation of the hexagonal boron nitride powder was performed. The results were as shown in FIG. 1 and Table 2.
（実施例４）
解砕工程におけるホモジナイザの時間を８分間に変更したこと以外は、実施例１と同様にして六方晶窒化ホウ素粉末を調製した。そして、実施例１と同様にして、六方晶窒化ホウ素粉末の各測定及び評価を行った。結果は表２に示すとおりであった。
(Example 4)
Hexagonal boron nitride powder was prepared in the same manner as in Example 1, except that the homogenizer time in the crushing step was changed to 8 minutes. Then, in the same manner as in Example 1, each measurement and evaluation of the hexagonal boron nitride powder was performed. The results were as shown in Table 2.
（比較例１）
アニール工程における加熱温度を１７００℃としたこと以外は実施例１と同様にして六方晶窒化ホウ素粉末を調製した。実施例１と同様にして六方晶窒化ホウ素粉末の各測定及び評価を行った。結果は図１及び表２に示すとおりであった。
(Comparative example 1)
Hexagonal boron nitride powder was prepared in the same manner as in Example 1 except that the heating temperature in the annealing step was 1700°C. The hexagonal boron nitride powder was measured and evaluated in the same manner as in Example 1. The results were as shown in FIG. 1 and Table 2.
実施例１～４は、いずれも一次粒子が凝集した二次粒子を含有していた。実施例１～４は、比較例１よりも、Ｄ９０／Ｄ１０の値が大きく且つふわふわ感のある外観を有していた。このため、実施例１～４の方が、比較例１よりも、二次粒子を多く含有しており、優れた伸び性を示した。最も凝集していた実施例１の六方晶窒化ホウ素粉末は、最も優れた伸び性を有していた。 Examples 1 to 4 all contained secondary particles that were aggregates of primary particles. Examples 1 to 4 had larger D90/D10 values than Comparative Example 1 and a fluffy appearance. Therefore, Examples 1 to 4 contained more secondary particles than Comparative Example 1, and exhibited excellent elongation properties. The hexagonal boron nitride powder of Example 1, which was the most aggregated, had the best extensibility.
本開示によれば、伸び性に優れる化粧料を製造することが可能な六方晶窒化ホウ素粉末及びその製造方法が提供される。また、上述の六方晶窒化ホウ素粉末を用いることによって伸び性に優れる化粧料及びその製造方法が提供される。 According to the present disclosure, a hexagonal boron nitride powder and a method for producing the same are provided that allow production of cosmetics with excellent extensibility. Further, by using the above-described hexagonal boron nitride powder, a cosmetic with excellent extensibility and a method for producing the same are provided.
Claims (10)
レーザー回折・散乱法によって測定される体積基準の粒子径の累積分布において、小粒径からの積算値が全体の１０％、５０％及び９０％に達したときの粒子径を、それぞれＤ１０、Ｄ５０及びＤ９０としたときに、Ｄ１０が２μｍ以上、Ｄ５０が５～２０μｍ、Ｄ９０が４０μｍ以下であり、
Ｄ９０／Ｄ１０が４．５～１０である、化粧料の原料用の六方晶窒化ホウ素粉末。 Contains secondary particles formed by agglomeration of primary particles of hexagonal boron nitride,
In the volume-based cumulative distribution of particle diameters measured by laser diffraction/scattering method, the particle diameters when the cumulative value from small particle diameters reaches 10%, 50%, and 90% of the total are D10 and D50, respectively. and D90, D10 is 2 μm or more, D50 is 5 to 20 μm , and D90 is 40 μm or less,
A hexagonal boron nitride powder for use as a raw material for cosmetics , having a D90/D10 of 4.5 to 10 .
前記仮焼物と助剤とを含む混合粉末を、不活性ガス、アンモニアガス又はこれらの混合ガスの雰囲気中、１９００～２１００℃で焼成して、前記仮焼物における六方晶窒化ホウ素よりも高い結晶性を有する六方晶窒化ホウ素を含む焼成物を得る焼成工程と、
前記焼成物を洗浄及び乾燥して乾燥粉末を得る精製工程と、
前記乾燥粉末を、不活性ガス、アンモニアガス又はこれらの混合ガスの雰囲気中、１９００～２１００℃でアニールして六方晶窒化ホウ素の一次粒子が凝集して形成される二次粒子を含む加熱処理物を得るアニール工程と、
前記加熱処理物を解砕して前記二次粒子を含む六方晶窒化ホウ素粉末を得る解砕工程と、を有する、六方晶窒化ホウ素粉末の製造方法。 Raw material powder containing boron-containing compound powder and nitrogen-containing compound powder is fired at 600 to 1300°C in an atmosphere of inert gas, ammonia gas, or a mixed gas of these to produce a powder containing hexagonal boron nitride. a calcination step for obtaining a calcined product;
The mixed powder containing the calcined material and the auxiliary agent is calcined at 1900 to 2100° C. in an atmosphere of inert gas, ammonia gas, or a mixed gas thereof to obtain crystallinity higher than that of hexagonal boron nitride in the calcined material. a firing step for obtaining a fired product containing hexagonal boron nitride having
a purification step of washing and drying the fired product to obtain a dry powder;
A heat-treated product containing secondary particles formed by agglomeration of primary particles of hexagonal boron nitride by annealing the dry powder at 1900 to 2100°C in an atmosphere of inert gas, ammonia gas, or a mixed gas thereof. an annealing process to obtain
A method for producing hexagonal boron nitride powder, comprising a crushing step of crushing the heat-treated product to obtain hexagonal boron nitride powder containing the secondary particles.
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