JP7360962B2 - 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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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims description 163
- 239000002537 cosmetic Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 229910052582 BN Inorganic materials 0.000 claims description 57
- 239000000843 powder Substances 0.000 claims description 47
- 239000011164 primary particle Substances 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 37
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 34
- 229910052796 boron Inorganic materials 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 238000010304 firing Methods 0.000 claims description 27
- 238000010521 absorption reaction Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
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- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001873 dinitrogen Inorganic materials 0.000 description 7
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- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000006870 function Effects 0.000 description 3
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- 229910052618 mica group Inorganic materials 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
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- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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- Cosmetics (AREA)
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、及び絶縁性を有しており、固体潤滑材、離型材、樹脂及びゴムに対する充填材、化粧料の原料、並びに、耐熱性を有する絶縁性焼結体等の種々の用途に利用されている。 Boron nitride has lubricity, high thermal conductivity, and insulation properties, and can be used as solid lubricants, mold release materials, fillers for resins and rubbers, raw materials for cosmetics, and heat-resistant insulating sintered bodies. It is used for various purposes such as
六方晶窒化ホウ素粉末は、化粧料の滑り性、伸び性、及び隠ぺい性等を向上させる機能、並びに化粧料に光沢性等を付与するといった機能を有する。タルク粉末及びマイカ粉末等も六方晶窒化ホウ素粉末と同様の機能を発揮し得る体質顔料として使用されるが、これらは天然鉱物であり、粒径や厚みのバラツキが大きい。特に六方晶窒化ホウ素粉末は、タルク粉末及びマイカ粉末に比べて滑り性に優れており、優れた滑り性が要求される化粧料によく使用されている。特許文献１では、滑り性を改善するために、せん断応力と加圧力の比を所定の数値範囲内とする六方晶窒化ホウ素粉末が提案されている。 The hexagonal boron nitride powder has the function of improving the slipperiness, spreadability, concealment property, etc. of cosmetics, and the function of imparting glossiness, etc., to cosmetics. Talc powder, mica powder, and the like are also used as extender pigments that can perform the same functions as hexagonal boron nitride powder, but these are natural minerals and have large variations in particle size and thickness. In particular, hexagonal boron nitride powder has superior slip properties compared to talc powder and mica powder, and is often used in cosmetics that require excellent slip properties. Patent Document 1 proposes a hexagonal boron nitride powder in which the ratio of shear stress to pressing force is within a predetermined numerical range in order to improve slipperiness.
化粧料に対する要求特性も多岐にわたり、原料である六方晶窒化ホウ素粉末への要求特性も更に高まっている。例えば、薄膜での皮膜形成性に優れ、冷感や透明性（素肌感）を向上させた化粧料用の六方晶窒化ホウ素粉末として、特許文献２では、表面における親水性の官能基を低減し、吸油量を増大させた六方晶窒化ホウ素粉末が提案されている。 The characteristics required for cosmetics are wide-ranging, and the characteristics required for the raw material hexagonal boron nitride powder are also increasing. For example, Patent Document 2 discloses a hexagonal boron nitride powder for cosmetics that has excellent thin film-forming properties and improved cooling sensation and transparency (bare skin feel) by reducing hydrophilic functional groups on the surface. , hexagonal boron nitride powder with increased oil absorption has been proposed.
本開示は、化粧料用の原料に適する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を目的とする。本開示はまた、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を目的とする。 The present disclosure aims to provide a hexagonal boron nitride powder suitable as a raw material for cosmetics and a method for producing the same. The present disclosure also aims to provide a cosmetic with excellent spreadability and a method for producing the same.
本開示の一側面は、六方晶窒化ホウ素の一次粒子を含み、比表面積が２．５ｍ２／ｇ未満であり、全酸素量が０．３０質量％以下であり、且つ吸油量が４０ｍＬ／１００ｇ以上１００ｍＬ／１００ｇ未満である、六方晶窒化ホウ素粉末を提供する。 One aspect of the present disclosure includes primary particles of hexagonal boron nitride, has a specific surface area of less than 2.5 m 2 /g, has a total oxygen content of 0.30% by mass or less, and has an oil absorption of 40 mL/100 g. Provided is a hexagonal boron nitride powder having a volume of at least 100 mL/100 g.
上記六方晶窒化ホウ素粉末は、所定の比表面積を有する一次粒子を含み吸油量が所定の範囲となることから、優れた伸び性を発揮し得る。上記効果が奏される理由は、上記六方晶窒化ホウ素粉末において、全酸素量が少なく高純度であり、比表面積が小さく、更に吸油量も比較的に小さくなっており、水分吸着量又は表面に発生する静電気量を低減でき、一次粒子の凝集が抑制されているためと考えられる。また、上記六方晶窒化ホウ素粉末は、一次粒子の全酸素量が所定の範囲であることによって、有機溶剤等への分散性が向上しており、化粧料の製造を円滑に行うことができる。 The hexagonal boron nitride powder contains primary particles having a predetermined specific surface area and has an oil absorption within a predetermined range, so that it can exhibit excellent elongation properties. The reason for the above effects is that the hexagonal boron nitride powder has a low total oxygen content, high purity, a small specific surface area, and a relatively small oil absorption amount. This is thought to be because the amount of static electricity generated can be reduced and aggregation of primary particles is suppressed. In addition, the hexagonal boron nitride powder has improved dispersibility in organic solvents and the like because the total oxygen content of the primary particles is within a predetermined range, and cosmetics can be manufactured smoothly.
上記一次粒子のアスペクト比が２０以下であってよい。アスペクト比が上記範囲内であることで、一次粒子は適度な厚みを有し、一次粒子の割れ等を抑制して、溶出ホウ素量の増加を十分に抑制することができる。 The aspect ratio of the primary particles may be 20 or less. When the aspect ratio is within the above range, the primary particles have an appropriate thickness, cracking of the primary particles, etc. can be suppressed, and an increase in the amount of eluted boron can be sufficiently suppressed.
上記六方晶窒化ホウ素粉末は、平均粒径が５～２０μｍであってよい。平均粒径が上記範囲内であると、六方晶窒化ホウ素粉末を用いて得られる化粧料の伸び性を十分なものとすることができ、光沢感を適度なものとすることができる。 The hexagonal boron nitride powder may have an average particle size of 5 to 20 μm. When the average particle size is within the above range, the cosmetics obtained using the hexagonal boron nitride powder can have sufficient spreadability and have an appropriate glossiness.
上記六方晶窒化ホウ素粉末は、溶出ホウ素量が２０質量ｐｐｍ以下であってよい。溶出ホウ素量が上記範囲内であることで、皮膚への刺激をより低減することができる。 The hexagonal boron nitride powder may have an eluted boron amount of 20 mass ppm or less. When the amount of eluted boron is within the above range, irritation to the skin can be further reduced.
本開示の一側面は、炭素含有化合物及びホウ素含有化合物を含む原料粉末を、窒素含有化合物を含むガス雰囲気、且つ０．２５ＭＰａ以上５．０ＭＰａ未満の圧力下において、１６００℃以上の温度で加熱処理して第一の加熱処理物を得る第一工程と、上記第一工程よりも高く、１８５０℃未満の温度で上記第一の加熱処理物を加熱処理して第二の加熱処理物を得る第二工程と、上記第二工程よりも高い温度で、上記第二の加熱処理物を焼成して焼成体を得る第三工程と、上記焼成体を水及び酸の少なくとも一方で処理する第四工程と、を有する、六方晶窒化ホウ素粉末の製造方法を提供する。 One aspect of the present disclosure is to heat-process raw material powder containing a carbon-containing compound and a boron-containing compound at a temperature of 1600° C. or higher in a gas atmosphere containing a nitrogen-containing compound and under a pressure of 0.25 MPa or more and less than 5.0 MPa. a first step of heating the first heat-treated product to obtain a first heat-treated product; and a second step of heat-treating the first heat-treated product at a temperature higher than the first step and less than 1850°C to obtain a second heat-treated product. a third step of firing the second heat-treated product at a higher temperature than the second step to obtain a fired body; and a fourth step of treating the fired body with at least one of water and acid. Provided is a method for producing a hexagonal boron nitride powder having the following.
上記六方晶窒化ホウ素粉末の製造方法は、第一工程及び第二工程において原料粉末を加熱処理し、その後、より高温で焼成する工程を含むことによって、上述のような六方晶窒化ホウ素粉末を製造することができる。また第四工程において水処理及び酸処理の少なくとも一方を行うことで溶出ホウ素量を低減することができる。さらに上記六方晶窒化ホウ素粉末の製造方法によれば、従来の製造方法に比べて、粒径及び粒子形状等の点で均一性に優れる六方晶窒化ホウ素粉末を製造することができる。 The method for producing the hexagonal boron nitride powder described above includes the steps of heat-treating the raw material powder in the first step and the second step, and then firing it at a higher temperature, thereby producing the hexagonal boron nitride powder as described above. can do. Moreover, the amount of eluted boron can be reduced by performing at least one of water treatment and acid treatment in the fourth step. Further, according to the above method for producing hexagonal boron nitride powder, it is possible to produce hexagonal boron nitride powder that is more uniform in terms of particle size, particle shape, etc. than conventional production methods.
上記第三工程における焼成温度が１８５０～２１００℃であってよい。第三工程における焼成温度を上記範囲内とすることによって、六方晶窒化ホウ素の純度をより向上させると共に、一次粒子の成長を促進して、六方晶窒化ホウ素粉末の比表面積をより小さなものとすることができる。 The firing temperature in the third step may be 1850 to 2100°C. By setting the firing temperature in the third step within the above range, the purity of the hexagonal boron nitride is further improved, the growth of primary particles is promoted, and the specific surface area of the hexagonal boron nitride powder is made smaller. be able to.
本開示の一側面は、上述の六方晶窒化ホウ素粉末を含む、化粧料を提供する。 One aspect of the present disclosure provides a cosmetic containing the hexagonal boron nitride powder described above.
上記化粧料は、上述の六方晶窒化ホウ素粉末を含むことから、優れた伸び性を発揮し得る。 Since the above-mentioned cosmetic contains the above-mentioned hexagonal boron nitride powder, it can exhibit excellent elongation properties.
本開示の一側面は、上述の六方晶窒化ホウ素粉末を配合することを含む、化粧料の製造方法を提供する。 One aspect of the present disclosure provides a method for manufacturing a cosmetic that includes blending the hexagonal boron nitride powder described above.
上記化粧料の製造方法は、上述の六方晶窒化ホウ素粉末を配合することから優れた伸び性を発揮し得る化粧料を容易に製造することができる。 The above method for producing a cosmetic can easily produce a cosmetic that exhibits excellent elongation properties by incorporating the above-mentioned hexagonal boron nitride powder.
本開示によれば、化粧料用の原料に適する六方晶窒化ホウ素粉末及びその製造方法を提供できる。本開示によればまた、伸び性に優れる化粧料及びその製造方法を提供できる。 According to the present disclosure, it is possible to provide a hexagonal boron nitride powder suitable as a raw material for cosmetics and a method for producing the same. According to the present disclosure, it is also possible to provide a cosmetic with excellent extensibility and a method for producing the same.
以下、本開示の実施形態について説明する。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.
本明細書において例示する材料は特に断らない限り、１種を単独で又は２種以上を組み合わせて用いることができる。組成物中の各成分の含有量は、組成物中の各成分に該当する物質が複数存在する場合には、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。 Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more. If there are multiple substances corresponding to each component in the composition, the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified. .
六方晶窒化ホウ素粉末の一実施形態は、六方晶窒化ホウ素の一次粒子を含み、比表面積が２．５ｍ２／ｇ未満であり、全酸素量が０．３０質量％以下であり、且つ吸油量が４０ｍＬ／１００ｇ以上１００ｍＬ／１００ｇ未満である。 One embodiment of the hexagonal boron nitride powder includes primary particles of hexagonal boron nitride, has a specific surface area of less than 2.5 m 2 /g, has a total oxygen content of 0.30% by mass or less, and has an oil absorption amount. is 40 mL/100 g or more and less than 100 mL/100 g.
六方晶窒化ホウ素の比表面積の上限値は２．５ｍ２／ｇ未満であるが、例えば、２．３ｍ２／ｇ以下、２．０ｍ２／ｇ以下、１．８ｍ２／ｇ以下、１．５ｍ２／ｇ以下、又は１．０ｍ２／ｇ以下であってよい。比表面積の上限値が上記範囲内であることで、滑り性により優れる。比表面積の上限値が上記範囲内であることで、六方晶窒化ホウ素粉末の溶出ホウ素量をより低減することができる。さらに比表面積の上限値を上記範囲内であることで、六方晶窒化ホウ素粉末を化粧料用の体質顔料として用いた場合、得られる化粧料は優れた隠蔽性（カバー力）を発揮し得る。上記比表面積の下限値は、例えば、０．２０ｍ２／ｇ以上、０．３０ｍ２／ｇ以上、０．４０ｍ２／ｇ以上、又は０．５０ｍ２／ｇ以上であってよい。比表面積の下限値が上記範囲内である場合、六方晶窒化ホウ素の一次粒子を適度に小さなものであることから、密着性に優れる。六方晶窒化ホウ素の比表面積は上述の範囲内で調整することができ、例えば、０．０１～２．５ｍ２／ｇ、又は０．５０～１．０ｍ２／ｇであってよい。六方晶窒化ホウ素の比表面積は、例えば、六方晶窒化ホウ素粉末を製造時における加熱温度（例えば、後述する第三工程の温度）等の条件を調整することによって制御できる。 The upper limit of the specific surface area of hexagonal boron nitride is less than 2.5 m 2 /g, for example, 2.3 m 2 /g or less, 2.0 m 2 /g or less, 1.8 m 2 /g or less, 1. It may be 5 m 2 /g or less, or 1.0 m 2 /g or less. When the upper limit of the specific surface area is within the above range, the slip property is more excellent. By setting the upper limit of the specific surface area within the above range, the amount of boron eluted from the hexagonal boron nitride powder can be further reduced. Further, by setting the upper limit of the specific surface area within the above range, when the hexagonal boron nitride powder is used as an extender pigment for cosmetics, the resulting cosmetics can exhibit excellent hiding power (covering power). The lower limit of the specific surface area may be, for example, 0.20 m 2 /g or more, 0.30 m 2 /g or more, 0.40 m 2 /g or more, or 0.50 m 2 /g or more. When the lower limit of the specific surface area is within the above range, the primary particles of hexagonal boron nitride are appropriately small, so that excellent adhesion is achieved. The specific surface area of hexagonal boron nitride can be adjusted within the above-mentioned range, and may be, for example, 0.01 to 2.5 m 2 /g, or 0.50 to 1.0 m 2 /g. The specific surface area of hexagonal boron nitride can be controlled, for example, by adjusting conditions such as the heating temperature (for example, the temperature in the third step described below) during production of the hexagonal boron nitride powder.
本明細書における「比表面積」は、ＪＩＳ Ｚ ８８３０：２０１３「ガス吸着による粉体（固体）の比表面積測定方法」に記載の方法に準拠し、窒素ガスを使用してＢＥＴ一点法により測定される値である。 "Specific surface area" in this specification is measured by the BET single point method using nitrogen gas in accordance with the method described in JIS Z 8830:2013 "Method for measuring specific surface area of powder (solid) by gas adsorption". is the value.
六方晶窒化ホウ素の全酸素量の上限値は０．３０質量％以下であるが、例えば、０．２５質量％以下、０．２０質量％以下、０．１５質量％以下、又は０．１２質量％以下であってよい。全酸素量の上限値が上記範囲内であることで、粒子表面への水分の吸着を抑制することができる。全酸素量の下限値は、例えば、０．０１質量％以上、０．０２質量％以上、０．０３質量％以上、０．０４質量％以上、又は０．０５質量％以上であってよい。全酸素量の下限値が上記範囲内であることで、極性溶媒中への分散性等をより向上させることができる。このため、例えば、六方晶窒化ホウ素粉末を体質顔料として用い、化粧料を調製する場合に、他の顔料等との混合が容易でとなり、化粧料の製造を円滑に行うことができる。六方晶窒化ホウ素の全酸素量は上述の範囲内で調整することができ、例えば、０．０１～０．３０質量％、０．０３～０．２０質量％、又は０．０５～０．１５質量％であってよい。全酸素量は例えば、六方晶窒化ホウ素粉末の製造時における加熱温度等の条件を調整することで制御できる。 The upper limit of the total oxygen content of hexagonal boron nitride is 0.30% by mass or less, for example, 0.25% by mass or less, 0.20% by mass or less, 0.15% by mass or less, or 0.12% by mass. % or less. When the upper limit of the total oxygen amount is within the above range, adsorption of moisture onto the particle surface can be suppressed. The lower limit of the total oxygen amount may be, for example, 0.01% by mass or more, 0.02% by mass or more, 0.03% by mass or more, 0.04% by mass or more, or 0.05% by mass or more. When the lower limit of the total oxygen content is within the above range, the dispersibility in polar solvents, etc. can be further improved. Therefore, for example, when preparing cosmetics using hexagonal boron nitride powder as an extender pigment, it can be easily mixed with other pigments, etc., and the cosmetics can be manufactured smoothly. The total oxygen content of hexagonal boron nitride can be adjusted within the above range, for example, 0.01 to 0.30% by mass, 0.03 to 0.20% by mass, or 0.05 to 0.15% by mass. It may be mass %. The total amount of oxygen can be controlled, for example, by adjusting conditions such as heating temperature during production of hexagonal boron nitride powder.
本明細書における「全酸素量」とは、六方晶窒化ホウ素粉末の全酸素量を意味する。全酸素量は以下の手順で求めることができる。六方晶窒化ホウ素粉末の酸素量及び窒素量を、酸素・窒素分析装置を用いて分析する。測定用の試料を、ヘリウムガスの雰囲気中、２０℃から２５００℃程度まで、すなわち窒化ホウ素の反応分解温度以上まで昇温する。昇温に伴って脱離する酸素を検知する。昇温当初は、六方晶窒化ホウ素粉末の表面に結合している酸素が脱離する。脱離する酸素を定量することで表面酸素量が求められる。その後、温度が１４００℃近傍に到達すると、六方晶窒化ホウ素が分解をし始める。六方晶窒化ホウ素の分解開始は、窒素が検出され始めることによって把握することができる。六方晶窒化ホウ素が分解をし始めると、六方晶窒化ホウ素の粒子の内部にある酸素が脱離する。この段階で脱離する酸を定量することで、内部酸素量が求められる。このようにして得られた表面酸素量と、内部酸素量との合計値が全酸素量である。 The "total amount of oxygen" in this specification means the total amount of oxygen in the hexagonal boron nitride powder. The total amount of oxygen can be determined by the following procedure. Analyze the amount of oxygen and nitrogen in the hexagonal boron nitride powder using an oxygen/nitrogen analyzer. A sample for measurement is heated in a helium gas atmosphere from 20° C. to about 2500° C., that is, to a temperature higher than the reaction decomposition temperature of boron nitride. Detects oxygen that is released as the temperature rises. At the beginning of temperature rise, oxygen bonded to the surface of the hexagonal boron nitride powder is desorbed. The amount of surface oxygen can be determined by quantifying the amount of oxygen released. Thereafter, when the temperature reaches around 1400° C., hexagonal boron nitride begins to decompose. The start of decomposition of hexagonal boron nitride can be determined by the fact that nitrogen begins to be detected. When hexagonal boron nitride begins to decompose, the oxygen inside the hexagonal boron nitride particles is eliminated. By quantifying the amount of acid released at this stage, the amount of internal oxygen can be determined. The total value of the surface oxygen amount obtained in this way and the internal oxygen amount is the total oxygen amount.
六方晶窒化ホウ素粉末は、吸油量が４０ｍＬ／１００ｇ以上１００ｍＬ／１００ｇ未満である。上記吸油量の下限値は、例えば、５０ｍＬ／１００ｇ以上、６０ｍＬ／１００ｇ以上、６５ｍＬ／１００ｇ以上、又は７０ｍＬ／１００ｇ以上であってよい。吸油量の下限値が上記範囲内であることによって、化粧もちをより十分に確保できる。上記吸油量の上限値は、９５ｍＬ／１００ｇ以下、９５ｍＬ／１００ｇ未満、９０ｍＬ／１００ｇ以下、８５ｍＬ／１００ｇ以下、又は８０ｍＬ／１００ｇ以下であってよい。吸油量の上限値が上記範囲内であることによって、凝集等の発生を抑制することができる。また吸油量の上限値が上記範囲内である六方晶窒化ホウ素粉末を化粧料用の体質顔料として用いた場合、得られる化粧料は伸び性により優れ、またよりさらさらした触感（ｐｏｗｄｅｒｙ）を呈する。吸油量は上述の範囲内で調整することができ、例えば、４０～９５ｍＬ／１００ｇ、５０～９０ｍＬ／１００ｇ、又は５０～８０ｍＬ／１００ｇであってよい。六方晶窒化ホウ素粉末の吸油量は、例えば、一次粒子のＢＥＴ比表面積を調整することで制御することができ、六方晶窒化ホウ素粉末の製造時における加熱温度（例えば、後述する第三工程の温度）等の条件を調整することによって制御できる。 The hexagonal boron nitride powder has an oil absorption of 40 mL/100 g or more and less than 100 mL/100 g. The lower limit of the oil absorption amount may be, for example, 50 mL/100 g or more, 60 mL/100 g or more, 65 mL/100 g or more, or 70 mL/100 g or more. When the lower limit of the oil absorption amount is within the above range, sufficient makeup retention can be ensured. The upper limit of the oil absorption amount may be 95 mL/100 g or less, less than 95 mL/100 g, 90 mL/100 g or less, 85 mL/100 g or less, or 80 mL/100 g or less. By setting the upper limit of the oil absorption amount within the above range, occurrence of aggregation and the like can be suppressed. Furthermore, when hexagonal boron nitride powder having an upper limit of oil absorption within the above range is used as an extender pigment for cosmetics, the resulting cosmetics have excellent extensibility and a smoother powdery feel. The oil absorption amount can be adjusted within the above-mentioned range, and may be, for example, 40-95 mL/100 g, 50-90 mL/100 g, or 50-80 mL/100 g. The oil absorption amount of the hexagonal boron nitride powder can be controlled, for example, by adjusting the BET specific surface area of the primary particles, and can be controlled by adjusting the heating temperature during the production of the hexagonal boron nitride powder (for example, the temperature in the third step described below). ) can be controlled by adjusting conditions such as
本明細書における「吸油量」は、ＪＩＳ Ｋ ５１０１－１３－１：２００４「顔料試験方法－第１３部：吸油量－第１節：精製あまに油法」に記載の方法に準拠して測定される値である。 "Oil absorption" in this specification is measured in accordance with the method described in JIS K 5101-13-1:2004 "Pigment test method - Part 13: Oil absorption - Section 1: Refined linseed oil method" is the value to be used.
六方晶窒化ホウ素粉末は比較的大きな粒子径を有する。六方晶窒化ホウ素粉末において、平均粒径の下限値は、例えば、５μｍ以上、７μｍ以上、又は８μｍ以上であってよい。平均粒径の下限値が上記範囲内であることで、十分なのび性を確保できる。上記５０％累積径の上限値は、例えば、２０μｍ以下、１８μｍ以下、又は１６μｍ以下であってよい。平均粒径の上限値が上記範囲内であることで、強すぎる光沢感を抑えることができる。平均粒径は上述の範囲内で調整することができ、例えば、５～２０μｍ、又は８～１６μｍであってよい。平均粒径は、例えば、六方晶窒化ホウ素粉末を製造時における加熱温度（例えば、後述する第三工程の温度）等の条件を調整することによって制御できる。 Hexagonal boron nitride powder has a relatively large particle size. In the hexagonal boron nitride powder, the lower limit of the average particle size may be, for example, 5 μm or more, 7 μm or more, or 8 μm or more. When the lower limit of the average particle diameter is within the above range, sufficient spreadability can be ensured. The upper limit of the 50% cumulative diameter may be, for example, 20 μm or less, 18 μm or less, or 16 μm or less. By setting the upper limit of the average particle diameter within the above range, excessive glossiness can be suppressed. The average particle size can be adjusted within the above-mentioned range and may be, for example, from 5 to 20 μm, or from 8 to 16 μm. The average particle size can be controlled, for example, by adjusting conditions such as the heating temperature (for example, the temperature in the third step described below) during production of the hexagonal boron nitride powder.
本明細書における平均粒径は、体積基準の累積粒度分布における５０％累積径（メディアン径）を意味する。本明細書における「体積基準の累積粒度分布における５０％累積径」は、六方晶窒化ホウ素粉末に対するレーザー回折散乱法で粒度分布を測定したときの体積基準の累積粒度分布における累積値が５０％となったときの粒子径（Ｄ５０）を意味する。レーザー解析散乱法は、ＪＩＳ Ｚ ８８２５：２０１３「粒子径解析－レーザー回折・散乱法」に記載の方法に準拠して測定できる。測定には、レーザー回折散乱法粒度分布測定装置（ベックマンコールター社製、商品名：ＬＳ－１３ ３２０）等を使用することができる。 The average particle size in this specification means a 50% cumulative diameter (median diameter) in a volume-based cumulative particle size distribution. In this specification, "50% cumulative diameter in volume-based cumulative particle size distribution" means that the cumulative value in volume-based cumulative particle size distribution is 50% when the particle size distribution is measured by laser diffraction scattering method for hexagonal boron nitride powder. It means the particle diameter (D50) when The laser analysis scattering method can be measured in accordance with the method described in JIS Z 8825:2013 "Particle size analysis - laser diffraction/scattering method". For the measurement, a laser diffraction scattering particle size distribution analyzer (manufactured by Beckman Coulter, trade name: LS-13 320) or the like can be used.
六方晶窒化ホウ素の一次粒子の形状は、いわゆる鱗片形状である。上記一次粒子のアスペクト比の下限値は、例えば、５以上、又は７以上であってよい。アスペクト比の下限値が上記範囲内であることで、滑り性をより向上させることができる。またアスペクト比の下限値が上記範囲内であることで、六方晶窒化ホウ素粉末を化粧料用の体質顔料として用いた場合、得られる化粧料は優れた隠蔽性（カバー力）を発揮し得る。上記一次粒子のアスペクト比の上限値は、例えば、２０以下、１５以下、１３以下、又は１０以下であってよい。アスペクト比の上限値が上記範囲内であることで、一次粒子は適度な厚みを有し、一次粒子の割れ等を抑制して、溶出ホウ素量の増加を十分に抑制することができる。 The shape of the primary particles of hexagonal boron nitride is a so-called scale shape. The lower limit of the aspect ratio of the primary particles may be, for example, 5 or more, or 7 or more. When the lower limit of the aspect ratio is within the above range, slipperiness can be further improved. Further, since the lower limit of the aspect ratio is within the above range, when the hexagonal boron nitride powder is used as an extender pigment for cosmetics, the resulting cosmetics can exhibit excellent hiding power (covering power). The upper limit of the aspect ratio of the primary particles may be, for example, 20 or less, 15 or less, 13 or less, or 10 or less. When the upper limit of the aspect ratio is within the above range, the primary particles have an appropriate thickness, cracking of the primary particles, etc. can be suppressed, and an increase in the amount of eluted boron can be sufficiently suppressed.
一次粒子のアスペクト比は、粒子の最も長い箇所（長径）と短い箇所（短径）の比率（（長径）／（短径））で表わされる。六方晶窒化ホウ素の場合、一次粒子が鱗片形状の粒子であるから、鱗片形状の粒子の厚みが、粒子の最も短い箇所（短径）となる。つまり、本明細書における「一次粒子のアスペクト比」は、六方晶窒化ホウ素の一次粒子の断面写真画像から粒子長径と粒子厚みとを実測し算出することで得られる値を意味する。すなわち、六方晶窒化ホウ素の一次粒子のアスペクト比は、六方晶窒化ホウ素の一次粒子の（長径）／（厚さ）比で表される値である。 The aspect ratio of a primary particle is expressed by the ratio of the longest part (major axis) to the shortest part (breadth axis) of the particle ((major axis)/(breadth axis)). In the case of hexagonal boron nitride, the primary particles are scale-shaped particles, so the thickness of the scale-shaped particles is the shortest point (breadth axis) of the particle. That is, the "aspect ratio of primary particles" in this specification means a value obtained by actually measuring and calculating the particle length and particle thickness from a cross-sectional photographic image of a primary particle of hexagonal boron nitride. That is, the aspect ratio of the primary particles of hexagonal boron nitride is a value expressed by the (length)/(thickness) ratio of the primary particles of hexagonal boron nitride.
六方晶窒化ホウ素のような鱗片形状の粒子においてアスペクト比を測定する際、例えば、電子顕微短径比(長径／短径)を算出した。測定は、任意に選択した１００個の一次粒子に対して行う。得られた長径短径比に基づいて累積分布を作成し、累積分布の平均値に相当する長径短径比を求め、これをアスペクト比とする。 When measuring the aspect ratio of scale-shaped particles such as hexagonal boron nitride, for example, the short axis ratio (major axis/breadth axis) under an electron microscope was calculated. The measurement is performed on 100 arbitrarily selected primary particles. A cumulative distribution is created based on the obtained length-to-breadth-axis ratio, and the length-to-breadth ratio corresponding to the average value of the cumulative distribution is determined, and this is defined as the aspect ratio.
六方晶窒化ホウ素粉末は溶出ホウ素量が十分に低減されている。六方晶窒化ホウ素粉末の溶出ホウ素量は、例えば、２０質量ｐｐｍ以下、１５質量ｐｐｍ以下、１０質量ｐｐｍ以下、８質量ｐｐｍ以下、又は６質量ｐｐｍ以下とすることができる。六方晶窒化ホウ素粉末の溶出ホウ素量を低減することで、皮膚への刺激を低減することができることから、化粧料に用いる体質顔料としてより有用である。 The hexagonal boron nitride powder has a sufficiently reduced amount of eluted boron. The amount of eluted boron in the hexagonal boron nitride powder can be, for example, 20 mass ppm or less, 15 mass ppm or less, 10 mass ppm or less, 8 mass ppm or less, or 6 mass ppm or less. By reducing the amount of eluted boron in hexagonal boron nitride powder, irritation to the skin can be reduced, making it more useful as an extender pigment used in cosmetics.
本明細書における「溶出ホウ素量」とは、医薬部外品原料規格２００６に準拠して測定される値を意味する。 As used herein, the term "eluted boron amount" refers to a value measured in accordance with the Quasi-drug Ingredient Standards 2006.
上述の六方晶窒化ホウ素粉末は、例えば、以下のような方法で製造することができる。六方晶窒化ホウ素粉末の製造方法の一実施形態は、炭素含有化合物及びホウ素含有化合物を含む原料粉末を、窒素含有化合物を含むガス雰囲気、且つ０．２５ＭＰａ以上５．０ＭＰａ未満の圧力下において、１６００℃以上の温度で加熱処理して第一の加熱処理物を得る第一工程と、上記第一工程よりも高く、１８５０℃未満の温度で第一の加熱処理物を加熱処理して第二の加熱処理物を得る第二工程と、上記第二工程よりも高い温度で、上記第二の加熱処理物を焼成して焼成体を得る第三工程と、上記焼成体を水及び酸の少なくとも一方で処理する第四工程と、を有する。 The above-mentioned hexagonal boron nitride powder can be produced, for example, by the following method. In one embodiment of the method for producing hexagonal boron nitride powder, raw material powder containing a carbon-containing compound and a boron-containing compound is heated at 1,600 MPa in a gas atmosphere containing a nitrogen-containing compound and under a pressure of 0.25 MPa or more and less than 5.0 MPa. A first step of heat-treating the first heat-treated product at a temperature of 1850°C or higher, and a second step of heat-treating the first heat-treated product at a temperature higher than the first step but less than 1850°C. a second step of obtaining a heat-treated product; a third step of obtaining a fired product by firing the second heat-treated product at a higher temperature than in the second step; and a step of heating the fired product with at least one of water and acid. and a fourth step of processing.
第一工程は、原料粉末を、構成元素として窒素原子を有する化合物の存在下で、加圧及び加熱することで窒化ホウ素を生成させる工程である。原料粉末は、炭素含有化合物及びホウ素含有化合物を含む。 The first step is a step in which boron nitride is produced by pressurizing and heating the raw material powder in the presence of a compound having a nitrogen atom as a constituent element. The raw material powder contains a carbon-containing compound and a boron-containing compound.
炭素含有化合物は構成元素として炭素原子を有する化合物である。炭素含有化合物は、ホウ素含有化合物及び構成元素として窒素原子を有する化合物と反応して窒化ホウ素を形成する。炭素含有化合物としては、純度が高く比較的安価な原料を用いることができる。このような炭素含有化合物としては、例えば、カーボンブラック及びアセチレンブラック等が挙げられる。 A carbon-containing compound is a compound having carbon atoms as a constituent element. The carbon-containing compound reacts with a boron-containing compound and a compound having a nitrogen atom as a constituent element to form boron nitride. As the carbon-containing compound, a highly pure and relatively inexpensive raw material can be used. Examples of such carbon-containing compounds include carbon black and acetylene black.
ホウ素含有化合物は構成元素としてホウ素を有する化合物である。ホウ素含有化合物は、炭素含有化合物及び構成元素として窒素原子を有する化合物と反応して窒化ホウ素を形成する化合物である。ホウ素含有化合物としては、純度が高く比較的安価な原料を用いることができる。このようなホウ素含有化合物としては、例えば、ホウ酸及び酸化ホウ素などが挙げられる。ホウ素含有化合物は、好ましくはホウ酸を含む。この場合、ホウ酸は加熱によって脱水し酸化ホウ素となり、原料粉末の加熱処理中に液相を形成すると共に粒成長を促す助剤としても働くことができる。 A boron-containing compound is a compound having boron as a constituent element. A boron-containing compound is a compound that reacts with a carbon-containing compound and a compound having a nitrogen atom as a constituent element to form boron nitride. As the boron-containing compound, a highly pure and relatively inexpensive raw material can be used. Examples of such boron-containing compounds include boric acid and boron oxide. The boron-containing compound preferably includes boric acid. In this case, boric acid is dehydrated by heating to become boron oxide, which forms a liquid phase during the heat treatment of the raw material powder and can also act as an auxiliary agent for promoting grain growth.
上述の製造方法は、例えば、原料粉末の調製工程を備えてもよい。ホウ素含有化合物がホウ酸を含む場合、当該原料粉末の調製工程は、更にホウ素含有化合物を脱水する工程を含んでいてもよい。ホウ素含有化合物を脱水する工程を有することで、第一工程で得られる窒化ホウ素の収量を向上させることができる。 The above-mentioned manufacturing method may include, for example, a step of preparing raw material powder. When the boron-containing compound contains boric acid, the step of preparing the raw material powder may further include a step of dehydrating the boron-containing compound. By including the step of dehydrating the boron-containing compound, the yield of boron nitride obtained in the first step can be improved.
原料粉末は、炭素含有化合物及びホウ素含有化合物に加えて、その他の化合物を含有してもよい。その他の化合物としては、例えば、核剤としての窒化ホウ素等が挙げられる。原料粉末が核剤としての窒化ホウ素を含有することで、合成される六方晶窒化ホウ素粉末の平均粒径をより容易に制御することができる。原料粉末は、好ましくは核剤を含む。原料粉末が核剤を含む場合、比表面積の小さな六方晶窒化ホウ素粉末（例えば、比表面積が２．５ｍ２／ｇ未満である六方晶窒化ホウ素粉末）の製造がより容易となる。 The raw material powder may contain other compounds in addition to the carbon-containing compound and the boron-containing compound. Examples of other compounds include boron nitride as a nucleating agent. By containing boron nitride as a nucleating agent in the raw material powder, the average particle size of the hexagonal boron nitride powder to be synthesized can be more easily controlled. The raw material powder preferably contains a nucleating agent. When the raw material powder contains a nucleating agent, it becomes easier to produce hexagonal boron nitride powder with a small specific surface area (for example, hexagonal boron nitride powder with a specific surface area of less than 2.5 m 2 /g).
核剤としての窒化ホウ素の粉末を使用する場合には、上記核剤の含有量は、原料粉末１００質量部を基準として、例えば、０．０５～８質量部であってよい。上記核剤の含有量の下限値を０．０５質量部以上とすることで、核剤を含むことの効果をより向上させることができる。上記核剤の含有量の上限値を８質量部以下とすることで、六方晶窒化ホウ素粉末の収量を向上させることができる。 When boron nitride powder is used as a nucleating agent, the content of the nucleating agent may be, for example, 0.05 to 8 parts by mass based on 100 parts by mass of the raw material powder. By setting the lower limit of the content of the nucleating agent to 0.05 parts by mass or more, the effect of including the nucleating agent can be further improved. By setting the upper limit of the content of the nucleating agent to 8 parts by mass or less, the yield of hexagonal boron nitride powder can be improved.
窒素含有化合物は構成元素として窒素原子を有する化合物であり、炭素含有化合物及びホウ素含有化合物と反応して窒化ホウ素を形成する化合物である。構成元素として窒素原子を有する化合物としては、例えば、窒素及びアンモニア等が挙げられる。構成元素として窒素原子を有する化合物は、ガス（窒素含有ガスともいう）の形で供給されてよい。窒素含有ガスは、窒化反応による窒化ホウ素の形成を促進する観点、及びコストを低減する観点から、好ましくは窒素ガスを含み、より好ましくは窒素ガスである。窒素含有ガスとして複数の気体の混合ガスを用いる場合、混合ガス中における窒素ガスの割合が、好ましくは９５体積／体積％以上であってよい。 A nitrogen-containing compound is a compound having a nitrogen atom as a constituent element, and is a compound that reacts with a carbon-containing compound and a boron-containing compound to form boron nitride. Examples of the compound having a nitrogen atom as a constituent element include nitrogen and ammonia. The compound having a nitrogen atom as a constituent element may be supplied in the form of a gas (also referred to as nitrogen-containing gas). The nitrogen-containing gas preferably contains nitrogen gas, more preferably nitrogen gas, from the viewpoint of promoting the formation of boron nitride by nitriding reaction and from the viewpoint of reducing costs. When using a mixed gas of a plurality of gases as the nitrogen-containing gas, the proportion of nitrogen gas in the mixed gas may preferably be 95% by volume/volume or more.
第一工程は加圧下で行われる。第一工程における圧力の下限値は、０．２５ＭＰa以上であるが、例えば、０．３０ＭＰａ以上、又は０．５０ＭＰａ以上であってよい。第一工程における圧力の下限値を上記範囲内とすることで、ホウ素含有化合物等の原料の揮発をより抑制し、副生成物である炭化ホウ素の生成を抑制することができる。また第一工程における圧力の下限値を上記範囲内とすることで、窒化ホウ素粉末の比表面積の増加を抑制することができる。第一工程における圧力の上限値は、５．０ＭＰａ未満であるが、例えば、４．０ＭＰａ以下、３．０ＭＰａ以下、２．０ＭＰａ以下、１．０ＭＰａ以下、又は１．０ＭＰａ未満であってよい。第一工程における圧力の上限値を上記範囲内とすることで、窒化ホウ素の一次粒子の成長を促進することができる。第一工程における圧力は上記の範囲内で調整してよく、例えば、０．２５ＭＰａ以上５．０ＭＰａ未満、０．２５～１．０ＭＰａ、又は０．２５ＭＰａ以上１．０ＭＰａ未満であってよい。 The first step is performed under pressure. The lower limit of the pressure in the first step is 0.25 MPa or more, but may be, for example, 0.30 MPa or more, or 0.50 MPa or more. By setting the lower limit of the pressure in the first step within the above range, it is possible to further suppress the volatilization of raw materials such as boron-containing compounds, and to suppress the production of boron carbide as a by-product. Further, by setting the lower limit of the pressure in the first step within the above range, it is possible to suppress an increase in the specific surface area of the boron nitride powder. The upper limit of the pressure in the first step is less than 5.0 MPa, but may be, for example, 4.0 MPa or less, 3.0 MPa or less, 2.0 MPa or less, 1.0 MPa or less, or less than 1.0 MPa. By setting the upper limit of the pressure in the first step within the above range, growth of primary particles of boron nitride can be promoted. The pressure in the first step may be adjusted within the above range, and may be, for example, 0.25 MPa or more and less than 5.0 MPa, 0.25 to 1.0 MPa, or 0.25 MPa or more and less than 1.0 MPa.
第一工程は加熱下で行われる。第一工程における加熱温度の下限値は、１６００℃以上であるが、例えば、１６５０℃以上、又は１７００℃以上であってよい。第一工程における加熱温度の下限値を上記範囲内とすることで、反応を促進させ、第一工程で得られる窒化ホウ素の収量を向上させることができる。第一工程における加熱温度の上限値は、例えば、例えば、１８００℃未満、又は１７５０℃以下であってよい。第一工程における加熱温度の上限値を上記範囲内とすることで、副生成物の生成を十分に抑制することができる。第一工程における加熱温度は上述の範囲内で調整してよく、例えば、１６５０℃以上１８００℃未満、１６５０～１７５０℃であってよい。第一工程において、昇温速度は特に制限されるものでは無いが、例えば、０．５℃／分以上であってよい。 The first step is performed under heat. The lower limit of the heating temperature in the first step is 1600°C or higher, but may be, for example, 1650°C or higher or 1700°C or higher. By setting the lower limit of the heating temperature in the first step within the above range, the reaction can be promoted and the yield of boron nitride obtained in the first step can be improved. The upper limit of the heating temperature in the first step may be, for example, less than 1800°C or 1750°C or less. By setting the upper limit of the heating temperature in the first step within the above range, the generation of by-products can be sufficiently suppressed. The heating temperature in the first step may be adjusted within the above-mentioned range, and may be, for example, 1650°C or more and less than 1800°C, 1650 to 1750°C. In the first step, the temperature increase rate is not particularly limited, but may be, for example, 0.5° C./min or more.
第一工程における加熱時間は、例えば、１～１０時間、１～５時間、又は２～４時間であってよい。窒化ホウ素を合成する反応の序盤である第一工程において、比較的低温で所定時間の間、維持することで、反応系をより均質化することができ、ひいては第一工程で形成される窒化ホウ素をより均質化できる。なお、本明細書において加熱時間とは、加熱対象物の周囲環境の温度が所定の温度に到達してから当該温度で維持する時間（保持時間）を意味する。 The heating time in the first step may be, for example, 1 to 10 hours, 1 to 5 hours, or 2 to 4 hours. By maintaining the first step, which is the initial stage of the reaction to synthesize boron nitride, at a relatively low temperature for a certain period of time, the reaction system can be made more homogeneous, and the boron nitride formed in the first step can be can be more homogenized. Note that in this specification, the heating time refers to the time (holding time) during which the temperature of the surrounding environment of the object to be heated reaches a predetermined temperature and is maintained at that temperature.
第二工程は、第一工程で得られた第一の加熱処理物を、第一工程よりも高い温度で更に加熱処理して第二の加熱処理物を得る工程である。本工程において、結晶粒のより均一な成長を促すと共に、反応系における原料及び助剤をより十分に消費させることができる。 The second step is a step in which the first heat-treated product obtained in the first step is further heat-treated at a temperature higher than that in the first step to obtain a second heat-treated product. In this step, more uniform growth of crystal grains can be promoted, and raw materials and auxiliary agents in the reaction system can be consumed more fully.
第二工程における加熱温度は、上記第一工程よりも高く、１８５０℃未満の温度である。第二工程は、第一工程に連続して行ってもよく、第一工程における温度以外の条件は維持したままであってよい。すなわち、第二工程も窒素含有ガス等を含む加圧環境下で第一の加熱処理物を加熱する工程であってよい。 The heating temperature in the second step is higher than that in the first step, and is less than 1850°C. The second step may be performed consecutively to the first step, and the conditions other than the temperature in the first step may be maintained. That is, the second step may also be a step of heating the first heat-treated product in a pressurized environment containing a nitrogen-containing gas or the like.
第二工程における加熱時間は、例えば、１～１５時間、３～１０時間、又は６～９時間であってよい。 The heating time in the second step may be, for example, 1 to 15 hours, 3 to 10 hours, or 6 to 9 hours.
第三工程は、第二工程で得られた第二の加熱処理物を、更に高温で焼成して焼成体を得る工程である。本工程において、窒化ホウ素の結晶性が向上し、六方晶窒化ホウ素の一次粒子が形成される。得られる六方晶窒化ホウ素の一次粒子は、鱗片状の形状を有する。さらに本工程における加熱温度を高く設定することによって、助剤等の残存量を低減し、純度をより向上させることで、得られる焼成物の溶出ホウ素量を低減することができ、化粧料用の体質顔料としてより好適なものとすることができる。 The third step is a step of firing the second heat-treated product obtained in the second step at a higher temperature to obtain a fired body. In this step, the crystallinity of boron nitride is improved and primary particles of hexagonal boron nitride are formed. The obtained primary particles of hexagonal boron nitride have a scale-like shape. Furthermore, by setting a high heating temperature in this process, the amount of residual auxiliaries, etc. is reduced, and the purity is further improved, thereby reducing the amount of eluted boron in the baked product, which is suitable for cosmetics. It can be made more suitable as an extender pigment.
第三工程における圧力は第一工程及び第二工程と同じであっても、異なってもよい。第三工程における圧力が第一工程及び第二工程と異なる場合、第三工程の圧力は、第一工程及び第二工程における圧力よりも低くてよい。 The pressure in the third step may be the same as or different from the first and second steps. If the pressure in the third step is different from the first and second steps, the pressure in the third step may be lower than the pressure in the first and second steps.
第三工程の圧力の下限値は、例えば、０．２５ＭＰa以上、０．３０ＭＰａ以上、又は０．５０ＭＰａ以上であってよい。第三工程における圧力の下限値を上記範囲内とすることで、得られる焼成体における純度をより向上させることができる。第三工程における圧力の上限値は、特に制限されるものではないが、例えば、５．０ＭＰａ未満、４．０ＭＰａ以下、３．０ＭＰａ以下、２．０ＭＰａ以下、１．０ＭＰａ以下、又は１．０ＭＰａ未満であってよい。第三工程における圧力の上限値を上記範囲内とすることで、六方晶窒化ホウ素粉末の製造コストをより低減することができ、工業的に優位である。第三工程における圧力は上記の範囲内で調整してよく、例えば、０．２５ＭＰａ以上５．０ＭＰａ未満、０．２５～１．０ＭＰａ、又は０．２５ＭＰａ以上１．０ＭＰａ未満であってよい。 The lower limit of the pressure in the third step may be, for example, 0.25 MPa or more, 0.30 MPa or more, or 0.50 MPa or more. By setting the lower limit of the pressure in the third step within the above range, the purity of the obtained fired body can be further improved. The upper limit of the pressure in the third step is not particularly limited, but is, for example, less than 5.0 MPa, 4.0 MPa or less, 3.0 MPa or less, 2.0 MPa or less, 1.0 MPa or less, or 1.0 MPa. It may be less than By setting the upper limit of the pressure in the third step within the above range, the manufacturing cost of hexagonal boron nitride powder can be further reduced, which is industrially advantageous. The pressure in the third step may be adjusted within the above range, for example, 0.25 MPa or more and less than 5.0 MPa, 0.25 to 1.0 MPa, or 0.25 MPa or more and less than 1.0 MPa.
第三工程における焼成温度は第二工程における加熱温度よりも高い温度に設定する。第三工程における焼成温度の下限値は、例えば、１８５０℃以上、又は１９００℃以上であってよい。第三工程における焼成温度の下限値を上記範囲内とすることで、六方晶窒化ホウ素の純度をより向上させると共に、一次粒子の成長を促進して、六方晶窒化ホウ素粉末の比表面積をより小さなものとすることができる。焼成温度の下限値を上記範囲内とし、窒化ホウ素の結晶性をより向上させることで、化粧料原料に用いた場合の滑り性をより向上させることができる。第三工程における焼成温度の上限値は、例えば、２０１０℃以下、２０５０℃以下、又は２０００℃以下であってよい。第三工程における焼成温度の上限値を上記範囲内とすることで、六方晶窒化ホウ素の黄変化を抑制することができる。第三工程における焼成温度は上述の範囲内で調整してよく、例えば、１８５０～２１００℃、１８５０～２０５０℃、又は１９００～２０２５℃であってよい。 The firing temperature in the third step is set to a higher temperature than the heating temperature in the second step. The lower limit of the firing temperature in the third step may be, for example, 1850°C or higher, or 1900°C or higher. By setting the lower limit of the firing temperature in the third step within the above range, the purity of the hexagonal boron nitride is further improved, the growth of primary particles is promoted, and the specific surface area of the hexagonal boron nitride powder is made smaller. can be taken as a thing. By setting the lower limit of the firing temperature within the above range and further improving the crystallinity of boron nitride, it is possible to further improve the slipperiness when used as a cosmetic raw material. The upper limit of the firing temperature in the third step may be, for example, 2010°C or lower, 2050°C or lower, or 2000°C or lower. By setting the upper limit of the firing temperature in the third step within the above range, yellowing of hexagonal boron nitride can be suppressed. The firing temperature in the third step may be adjusted within the above-mentioned range, and may be, for example, 1850-2100°C, 1850-2050°C, or 1900-2025°C.
第三工程における焼成時間（高温での加熱時間）は、例えば、０．５時間以上、１時間以上、３時間以上、又は５時間以上であってよい。第三工程における焼成時間を上記範囲内とすることで、六方晶窒化ホウ素の純度をより向上させると共に、一次粒子の成長をより十分なものとすることができる。第三工程における焼成時間はまた、例えば、３０時間以下、２５時間以下、２０時間以下、１５時間以下、又は１０時間以下であってよい。第三工程における焼成時間を上記範囲内とすることで、より安価に六方晶窒化ホウ素粉末を製造することができる。第三工程における焼成時間は上述の範囲内で調整してよく、例えば、０．５～３０時間、１～２５時間、又は３～１０時間であってよい。 The firing time (heating time at high temperature) in the third step may be, for example, 0.5 hours or more, 1 hour or more, 3 hours or more, or 5 hours or more. By setting the firing time in the third step within the above range, it is possible to further improve the purity of hexagonal boron nitride and to achieve more sufficient growth of primary particles. The firing time in the third step may also be, for example, 30 hours or less, 25 hours or less, 20 hours or less, 15 hours or less, or 10 hours or less. By setting the firing time in the third step within the above range, hexagonal boron nitride powder can be produced at a lower cost. The firing time in the third step may be adjusted within the above-mentioned range, and may be, for example, 0.5 to 30 hours, 1 to 25 hours, or 3 to 10 hours.
第四工程は、上記焼成体を水及び酸の少なくとも一方で処理し、所望の六方晶窒化ホウ素粉末を得る工程である。本工程において、六方晶窒化ホウ素の溶出ホウ素量を低減して、化粧料用の体質顔料に好適な六方晶窒化ホウ素粉末が製造される。第三工程で得られる六方晶窒化ホウ素粉末を含む焼成体は水処理又は酸処理前であっても、他の製法で得られる六方晶窒化ホウ素粉末よりも溶出ホウ素量が小さいが、本工程によって溶出ホウ素量を更に低減することができる。第四工程における、水及び酸の少なくとも一方での処理は、水処理単独、酸処理単独、並びに、水処理及び酸処理の組合せであってよく、酸性溶液（例えば、酸性水溶液）による処理であってもよい。第四工程は、例えば、酸処理の後に水処理によって酸を除去する工程であってよい。 The fourth step is a step of treating the fired body with at least one of water and acid to obtain a desired hexagonal boron nitride powder. In this step, the amount of boron eluted from hexagonal boron nitride is reduced to produce hexagonal boron nitride powder suitable for extender pigments for cosmetics. The fired body containing hexagonal boron nitride powder obtained in the third step has a smaller amount of eluted boron than hexagonal boron nitride powder obtained by other manufacturing methods even before water treatment or acid treatment. The amount of eluted boron can be further reduced. The treatment with at least one of water and acid in the fourth step may be water treatment alone, acid treatment alone, or a combination of water treatment and acid treatment, and may be treatment with an acidic solution (for example, an acidic aqueous solution). You can. The fourth step may be, for example, a step of removing the acid by water treatment after the acid treatment.
上記焼成体の酸処理は、焼成体と酸性物質とを接触させて行う。焼成体と酸との接触の手段は、例えば、酸性物質を含む溶液中に焼成体を分散させる方法であってよい。酸性物質は、例えば、塩酸及び硝酸等の無機酸であってよい。酸性物質を含む溶液は、取扱いの容易性から、好ましくは水溶液である。酸性物質を含む溶液は、その他、例えば、有機溶媒を含んでもよい。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、イソプロパノール及びアセトン等の水溶性の有機溶媒が挙げられる。 The acid treatment of the fired body is performed by bringing the fired body into contact with an acidic substance. The means for contacting the fired body with the acid may be, for example, a method of dispersing the fired body in a solution containing an acidic substance. The acidic substance may be, for example, an inorganic acid such as hydrochloric acid and nitric acid. The solution containing the acidic substance is preferably an aqueous solution for ease of handling. The solution containing the acidic substance may also contain, for example, an organic solvent. Examples of the organic solvent include water-soluble organic solvents such as methanol, ethanol, propanol, isopropanol, and acetone.
水処理及び酸処理を行う際の温度は、例えば、２０～８０℃であってよい。酸処理に酸性物質を含む溶液を用いる場合、上記溶液の温度を４０～８０℃に調整してよい。酸処理工程における酸の温度の下限値は、例えば、４５℃以上、５０℃以上、又は６０℃以上であってよい。第四工程における酸の温度の上限値は、７５℃以下、又は７０℃以下であってよい。第四工程における酸の温度は上述の範囲内で調整してよく、例えば、４５～７５℃、又は５０～７０℃であってよい。 The temperature during water treatment and acid treatment may be, for example, 20 to 80°C. When a solution containing an acidic substance is used for acid treatment, the temperature of the solution may be adjusted to 40 to 80°C. The lower limit of the acid temperature in the acid treatment step may be, for example, 45°C or higher, 50°C or higher, or 60°C or higher. The upper limit of the temperature of the acid in the fourth step may be 75°C or lower, or 70°C or lower. The temperature of the acid in the fourth step may be adjusted within the above-mentioned range, for example, 45-75°C, or 50-70°C.
焼成体と酸性物質とを接触させる時間（酸処理時間）の下限値は、例えば、１．２時間以上、１．５時間以上、又は２．０時間以上であってよい。上記酸処理時間は、例えば、９．７時間以下、９．５時間以下、９．０時間以下、８．５時間以下、又は８．０時間以下であってよい。上記酸処理時間は上述の範囲内で調整してよく、例えば、１．２～９．７時間、又は２．０～８．０時間であってよい。 The lower limit of the time for contacting the fired body with the acidic substance (acid treatment time) may be, for example, 1.2 hours or more, 1.5 hours or more, or 2.0 hours or more. The acid treatment time may be, for example, 9.7 hours or less, 9.5 hours or less, 9.0 hours or less, 8.5 hours or less, or 8.0 hours or less. The acid treatment time may be adjusted within the above range, for example, from 1.2 to 9.7 hours, or from 2.0 to 8.0 hours.
酸処理後、六方晶窒化ホウ素粉末を水又は有機溶剤等で洗浄を行ってよい。洗浄終了後、例えば、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 acid treatment, the hexagonal boron nitride powder may be washed with water, an organic solvent, or the like. After the washing is completed, the washing liquid may be separated into solid and liquid using, for example, 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.
上述の製造方法は、第一工程、第二工程、第三工程及び第四工程の他に、その他の工程を有していてもよい。その他の工程としては、例えば、上述の原料粉末の調製工程、原料粉末の脱水工程、原料粉末の加圧成型工程、第一及び第二の加熱処理物の粉砕工程、焼成体の粉砕工程、並びに、六方晶窒化ホウ素の粉砕工程等が挙げられる。上述の製造方法が原料粉末の加圧成型工程を有する場合、原料粉末が高密度に存在する環境で焼成を行うことができ、第一の工程及び第二の工程で得られる窒化ホウ素の収量をより向上させることができる。粉砕工程は、通常の粉砕装置を用いて行うことができる。なお、本明細書における粉砕工程には、粉砕の他、解砕も含まれるものとする。 The above-mentioned manufacturing method may have other steps in addition to the first step, second step, third step, and fourth step. Other processes include, for example, the above-mentioned raw material powder preparation process, raw material powder dehydration process, raw material powder pressure molding process, first and second heat-treated product crushing process, fired body crushing process, and , a process of pulverizing hexagonal boron nitride, and the like. When the above-mentioned production method includes a pressure molding step of the raw material powder, the firing can be performed in an environment where the raw material powder is present at high density, and the yield of boron nitride obtained in the first step and the second step can be reduced. It can be further improved. The pulverization process can be performed using conventional pulverization equipment. Note that the crushing step in this specification includes crushing as well as crushing.
上述の六方晶窒化ホウ素粉末の製造方法は、いわゆる炭素還元法を応用した製造方法といえる。上述の製造方法によることで、一次粒子の平均粒径、粒子形状、及び比表面積が調製された、より均質な六方晶窒化ホウ素粉末を容易に得ることができる。得られる六方晶窒化ホウ素の一次粒子は他の製法を用いた場合に比べて比表面積の調整が容易であるが、これは、上述の製法であれば肉厚な一次粒子が得られる傾向にあるためと推測する。 The method for manufacturing hexagonal boron nitride powder described above can be said to be a manufacturing method applying a so-called carbon reduction method. By using the above-described manufacturing method, it is possible to easily obtain a more homogeneous hexagonal boron nitride powder in which the average particle size, particle shape, and specific surface area of the primary particles are adjusted. The specific surface area of the hexagonal boron nitride primary particles obtained is easier to adjust than when using other manufacturing methods, but this is because the above-mentioned manufacturing method tends to yield thick primary particles. I guess it's because.
上述の六方晶窒化ホウ素粉末は、化粧料用の体質顔料として有用である。化粧料の一実施形態は、上述の六方晶窒化ホウ素粉末を含む。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％であってよい。化粧料は、六方晶窒化ホウ素粉末に加えて、顔料、その他の体質顔料を含んでもよい。その他の体質顔料は、例えば、タルク粉末及びマイカ粉末等が挙げられる。 The hexagonal boron nitride powder described above is useful as an extender pigment for cosmetics. One embodiment of the cosmetic includes the hexagonal boron nitride powder described above. The content of hexagonal boron nitride powder in the cosmetic may be, for example, 0.1 to 70% by mass. In addition to the hexagonal boron nitride powder, the cosmetic may also contain pigments and other extender pigments. Examples of other extender pigments include talc powder and mica powder.
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。 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.
化粧料は公知の方法によって製造することができる。化粧料の製造方法の一実施形態は、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。 Cosmetics can be manufactured by known methods. One embodiment of the cosmetic manufacturing method includes a step of blending and mixing hexagonal boron nitride powder and other raw materials.
以上、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。また、上述した実施形態についての説明内容は、互いに適用することができる。 Although several embodiments have been described above, the present disclosure is not limited to the above embodiments. Further, the descriptions of the embodiments described above can be applied to each other.
以下、本開示について、実施例及び比較例を用いてより詳細に説明する。なお、本開示は以下の実施例に限定されるものではない。 Hereinafter, the present disclosure will be described in more detail using Examples and Comparative Examples. Note that 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］
ホウ酸（株式会社高純度化学研究所製）１００質量部と、アセチレンブラック（デンカ株式会社製、グレード名：ＨＳ１００）２５質量部とをヘンシェルミキサーを用いて混合して混合粉末（原料粉末）を得た。得られた混合粉末を２５０℃の乾燥機に入れ、３時間保持することでホウ酸の脱水を行った。脱水後の混合粉末２００ｇをプレス成型機の直径１００Φの型に入れ、加熱温度：２００℃及びプレス圧：３０ＭＰａの条件にて成型を行った。このようにして得られた原料粉末のペレットを以降の加熱処理に供した。
(Example 1)
[Preparation of hexagonal boron nitride powder]
100 parts by mass of boric acid (manufactured by Kojundo Kagaku Kenkyusho Co., Ltd.) and 25 parts by mass of acetylene black (manufactured by Denka Corporation, grade name: HS100) are mixed using a Henschel mixer to obtain a mixed powder (raw material powder). Obtained. The obtained mixed powder was placed in a dryer at 250°C and held for 3 hours to dehydrate the boric acid. 200 g of the dehydrated mixed powder was put into a mold with a diameter of 100 Φ of a press molding machine, and molding was performed under the conditions of heating temperature: 200° C. and press pressure: 30 MPa. The raw material powder pellets thus obtained were subjected to subsequent heat treatment.
まず、上記ペレットをカーボン雰囲気炉内に静置し、０．８ＭＰａに加圧された窒素雰囲気において昇温速度：５℃／分で１７３０℃まで昇温し、１７３０℃にて３時間保持して上記ペレットの加熱処理を行い、第一の加熱処理物を得た（第一工程）。次に、カーボン雰囲気炉内を昇温速度：５℃／分で１８１０℃まで更に昇温し、１８１０℃にて７時間保持して第一の加熱処理物を加熱処理し、第二の加熱処理物を得た（第二工程）。その後、カーボン雰囲気炉内を昇温速度：５℃／分で２０００℃まで更に昇温し、２０００℃にて７時間保持して第二の加熱処理物を高温で焼成した（第三工程）。焼成後の緩く凝集した窒化ホウ素をヘンシェルミキサーで解砕し、目開き：７５μｍの篩を通し、篩を通過した粉末を得た。 First, the pellets were placed in a carbon atmosphere furnace, heated to 1730°C at a rate of 5°C/min in a nitrogen atmosphere pressurized to 0.8 MPa, and held at 1730°C for 3 hours. The above pellets were heat-treated to obtain a first heat-treated product (first step). Next, the temperature in the carbon atmosphere furnace was further raised to 1810°C at a heating rate of 5°C/min, and the temperature was held at 1810°C for 7 hours to heat-treat the first heat-treated product, and then the second heat-treated product was heated. Obtained something (second step). Thereafter, the temperature in the carbon atmosphere furnace was further raised to 2000°C at a heating rate of 5°C/min, and the temperature was maintained at 2000°C for 7 hours to bake the second heat-treated product at a high temperature (third step). The loosely aggregated boron nitride after firing was crushed with a Henschel mixer and passed through a sieve with an opening of 75 μm to obtain a powder that passed through the sieve.
次に、得られた粉末に対して、以下のように湿式処理を行った。上記粉末中に含まれる不純物を除くため、希硝酸（硝酸濃度：１質量％）５００ｇに、上記粉末３０ｇを投入し、室温で６０分間攪拌した。攪拌後、吸引ろ過によって固液分離し、ろ液が中性になるまで水を入れ替えて、最終的に洗浄液の電気伝導度が１ｍＳ／ｍ以下になるまで洗浄した。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。当該乾燥粉末を実施例１の六方晶窒化ホウ素粉末とした。 Next, the obtained powder was subjected to wet processing as follows. In order to remove impurities contained in the powder, 30 g of the powder was added to 500 g of dilute nitric acid (nitric acid concentration: 1% by mass) and stirred at room temperature for 60 minutes. After stirring, solid-liquid separation was performed by suction filtration, water was replaced until the filtrate became neutral, and washing was performed until the electrical conductivity of the washing liquid finally became 1 mS/m or less. After washing, it was dried at 120° C. for 3 hours using a drier to obtain a dry powder. The dry powder was designated as the hexagonal boron nitride powder of Example 1.
＜六方晶窒化ホウ素粉末の評価＞
得られた六方晶窒化ホウ素粉末に対して、一次粒子の比表面積、全酸素量、アスペクト比、吸油量及び溶出ホウ素量を測定した。結果を表２に示す。
<Evaluation of hexagonal boron nitride powder>
The specific surface area, total oxygen amount, aspect ratio, oil absorption amount, and eluted boron amount of the primary particles of the obtained hexagonal boron nitride powder were measured. The results are shown in Table 2.
［一次粒子の比表面積］
六方晶窒化ホウ素の一次粒子の比表面積は、ＪＩＳ Ｚ ８８３０：２０１３「ガス吸着による粉体（固体）の比表面積測定方法」に記載の方法に準拠し、窒素ガスを使用してＢＥＴ一点法により測定した。
[Specific surface area of primary particles]
The specific surface area of the primary particles of hexagonal boron nitride was determined by the BET single point method using nitrogen gas in accordance with the method described in JIS Z 8830:2013 "Method for measuring the specific surface area of powder (solid) by gas adsorption". It was measured.
［全酸素量］
六方晶窒化ホウ素の一次粒子の全酸素量は、酸素／窒素同時分析装置（堀場製作所社製、装置名：ＥＭＧＡ－９２０）を用いて測定した。具体的には、六方晶窒化ホウ素粉末を、ヘリウム雰囲気中、２０℃から２５００℃まで加熱しながら測定を行った。
[Total oxygen amount]
The total oxygen content of the primary particles of hexagonal boron nitride was measured using an oxygen/nitrogen simultaneous analyzer (manufactured by Horiba, Ltd., device name: EMGA-920). Specifically, the measurement was performed while heating hexagonal boron nitride powder from 20° C. to 2500° C. in a helium atmosphere.
［アスペクト比］
３ｇの六方晶窒化ホウ素粉末をプレス成型機（例えば、株式会社リガク製、商品名：ＢＲＥ－３２）を用いて、５ＭＰａの圧力で円盤状（直径：３０ｍｍφ）に成型し、得られた成型体を樹脂（例えば、ＧＡＴＡＮ社製、商品名：Ｇ２エポキシ）を用いて包埋した。次に、圧力をかけた方向と並行方向に断面ミリング加工を行うことで、六方晶窒化ホウ素粒子の断面が露出した試料を調製した。この断面を走査型電子顕微鏡（例えば、日本電子株式会社製、商品名：ＪＳＭ－６０１０ＬＡ）によって撮影し、得られた粒子像を画像解析ソフトウェア（例えば、株式会社マウンテック製、商品名：Ｍａｃ－Ｖｉｅｗ）に取り込み、得られた写真から矩形粒子の短辺（粒子厚み、粒子短径に相当）を測定した。長径に関しては、成型物でなく、六方晶窒化ホウ素粉末を電子顕微鏡用試料台上カーボンテープの上にのせ、余分な粉末をエアスプレー等で除去したサンプルを走査型電子顕微鏡（例えば、日本電子株式会社製、商品名：ＪＳＭ－６０１０ＬＡ）によって撮影し、得られた粒子像を画像解析ソフトウェア（例えば、株式会社マウンテック製、商品名：Ｍａｃ－Ｖｉｅｗ）に取り込み、得られた写真から長辺（粒子長径に相当）を算出し、先の短径と併せアスペクト比(長径／短径)を算出した。測定は、任意に選択した１００個の一次粒子に対して行った。得られた長径短径比に基づいて累積分布を作成し、累積分布の平均値に相当する長径短径比を求め、これをアスペクト比とした。
[aspect ratio]
A molded body obtained by molding 3 g of hexagonal boron nitride powder into a disk shape (diameter: 30 mmφ) at a pressure of 5 MPa using a press molding machine (for example, manufactured by Rigaku Co., Ltd., product name: BRE-32) was embedded in a resin (for example, manufactured by GATAN, trade name: G2 epoxy). Next, cross-sectional milling was performed in a direction parallel to the direction in which pressure was applied, thereby preparing a sample in which the cross-section of the hexagonal boron nitride particles was exposed. This cross section is photographed using a scanning electron microscope (for example, JEOL Co., Ltd., product name: JSM-6010LA), and the resulting particle image is analyzed using image analysis software (for example, Mountec Co., Ltd., product name: Mac-View). ), and the short side of the rectangular particle (corresponding to the particle thickness and particle short axis) was measured from the obtained photograph. Regarding the major axis, place the hexagonal boron nitride powder on a carbon tape on an electron microscope sample stand, remove the excess powder with air spray, etc., and then place the sample using a scanning electron microscope (for example, JEOL Ltd.). The long side (particle The aspect ratio (long axis/breadth axis) was calculated by combining the short axis with the short axis. The measurement was performed on 100 arbitrarily selected primary particles. A cumulative distribution was created based on the obtained length/breadth ratio, and the length/breadth ratio corresponding to the average value of the cumulative distribution was determined, and this was taken as the aspect ratio.
［吸油量］
六方晶窒化ホウ素粉末の吸油量は、ＪＩＳ Ｋ ５１０１－１３－１：２００４「顔料試験方法－第１３部：吸油量－第１節：精製あまに油法」に記載の方法に準拠して測定した。
[Oil absorption amount]
The oil absorption of hexagonal boron nitride powder is measured according to the method described in JIS K 5101-13-1:2004 "Pigment test method - Part 13: Oil absorption - Section 1: Refined linseed oil method" did.
［溶出ホウ素量］
六方晶窒化ホウ素粉末の溶出ホウ素量は、医薬部外品原料規格２００６に準拠して測定した。
[Amount of eluted boron]
The amount of eluted boron in the hexagonal boron nitride powder was measured in accordance with the Quasi-drug Raw Materials Standards 2006.
＜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を幅１０ｍｍに載せた。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>
On one end of the artificial skin (length x width = 10 mm x 50 mm), 0.2 g of hexagonal boron nitride powder was placed in a width of 10 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）
第二工程の焼成条件を、加熱温度１８４０℃、保持時間１時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。得られた六方晶窒化ホウ素粉末について、実施例１と同様に評価を行った。結果を表２に示す。
(Example 2)
Hexagonal boron nitride powder was prepared in the same manner as in Example 1, except that the firing conditions in the second step were changed to a heating temperature of 1840° C. and a holding time of 1 hour. The obtained hexagonal boron nitride powder was evaluated in the same manner as in Example 1. The results are shown in Table 2.
（実施例３）
第三工程の焼成条件を、加熱温度１９００℃、保持時間３時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。得られた六方晶窒化ホウ素粉末について、実施例１と同様に評価を行った。結果を表２に示す。
(Example 3)
Hexagonal boron nitride powder was prepared in the same manner as in Example 1, except that the firing conditions in the third step were changed to a heating temperature of 1900° C. and a holding time of 3 hours. The obtained hexagonal boron nitride powder was evaluated in the same manner as in Example 1. The results are shown in Table 2.
（実施例４）
原料となる混合粉末に対して、当該混合粉末の全量を基準として、窒化ホウ素粉末（デンカ株式会社製、商品名：窒化ホウ素粉ＭＧＰ）を２質量％となるように更に追加したこと以外は、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。得られた六方晶窒化ホウ素粉末について、実施例１と同様に評価を行った。結果を表２に示す。
(Example 4)
Except for the fact that boron nitride powder (manufactured by Denka Co., Ltd., trade name: boron nitride powder MGP) was further added to the mixed powder as a raw material so that it was 2% by mass, based on the total amount of the mixed powder. Hexagonal boron nitride powder was prepared in the same manner as in Example 1. The obtained hexagonal boron nitride powder was evaluated in the same manner as in Example 1. The results are shown in Table 2.
（比較例１）
ホウ酸粉末（純度９９．８質量％以上、関東化学株式会社製）１００．０ｇ、及びメラミン粉末（純度９９．０質量％以上、富士フイルム和光純薬社製）９０．０ｇを、アルミナ製乳鉢を用いて１０分間混合し混合粉末を得た。乾燥後の混合粉末を、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。
(Comparative example 1)
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 Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in an alumina mortar. The mixture was mixed for 10 minutes to obtain a mixed powder. The dried mixed powder was placed in a hexagonal boron nitride container 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 less. In this way, a calcined product containing hexagonal boron nitride with low crystallinity was obtained.
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）３．０ｇを添加し、アルミナ製乳鉢を用いて１０分間混合した。得られた混合物を、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１７００℃に昇温した。１７００℃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、六方晶窒化ホウ素を含む粗粉を得た。 To 100.0 g of the calcined product, 3.0 g of sodium carbonate (purity of 99.5% by mass or more) was added as an auxiliary agent, and mixed for 10 minutes using an alumina mortar. The resulting 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 1700°C at a rate of 10°C/min. After maintaining the firing temperature at 1700° 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 containing hexagonal boron nitride.
次に、上記粗粉中に含まれる不純物を除くため、希硝酸（硝酸濃度：５質量％）５００ｇに、上記粗粉３０ｇを投入し、室温で６０分間攪拌した。攪拌後、吸引ろ過によって固液分離し、ろ液が中性になるまで水を入れ替えて、最終的に洗浄液の電気伝導度が１ｍＳ／ｍ以下になるまで洗浄した。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。当該乾燥粉末を比較例１の六方晶窒化ホウ素粉末とした。得られた六方晶窒化ホウ素粉末について、実施例１と同様に評価を行った。結果を表２に示す。 Next, in order to remove impurities contained in the 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, water was replaced until the filtrate became neutral, and washing was performed until the electrical conductivity of the washing liquid finally became 1 mS/m or less. After washing, it was dried at 120° C. for 3 hours using a drier to obtain a dry powder. The dry powder was designated as the hexagonal boron nitride powder of Comparative Example 1. The obtained hexagonal boron nitride powder was evaluated in the same manner as in Example 1. The results are shown in Table 2.
（比較例２）
第一工程及び第三工程の窒素雰囲気における圧力を０．０５Ｍａとし、第二工程を実施せず、第三工程の焼成温度を２０２０℃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。得られた六方晶窒化ホウ素粉末について、実施例１と同様に評価を行った。結果を表２に示す。
(Comparative example 2)
The same procedure as in Example 1 was carried out except that the pressure in the nitrogen atmosphere in the first and third steps was 0.05 Ma, the second step was not carried out, and the firing temperature in the third step was 2020°C. Crystalline boron nitride powder was prepared. The obtained hexagonal boron nitride powder was evaluated in the same manner as in Example 1. The results are shown in Table 2.
（比較例３）
仮焼物の焼成条件を、加熱温度１５５０℃、保持時間２０時間に変更したこと以外は、比較例１と同様にして、六方晶窒化ホウ素粉末を調製した。得られた六方晶窒化ホウ素粉末について、実施例１と同様に評価を行った。結果を表２に示す。
(Comparative example 3)
Hexagonal boron nitride powder was prepared in the same manner as in Comparative Example 1, except that the firing conditions for the calcined product were changed to a heating temperature of 1550° C. and a holding time of 20 hours. The obtained hexagonal boron nitride powder was evaluated in the same manner as in Example 1. The results are shown in Table 2.
（比較例４）
仮焼物の焼成条件を、加熱温度１６６０℃とし、助剤を炭酸カルシウム３．０ｇに変更したこと以外は、比較例１と同様にして、六方晶窒化ホウ素粉末を調製した。得られた六方晶窒化ホウ素粉末について、実施例１と同様に評価を行った。結果を表２に示す。
(Comparative example 4)
Hexagonal boron nitride powder was prepared in the same manner as in Comparative Example 1, except that the calcining conditions were a heating temperature of 1660° C. and an auxiliary agent of 3.0 g of calcium carbonate. The obtained hexagonal boron nitride powder was evaluated in the same manner as in Example 1. The results are shown in Table 2.
本開示によれば、化粧料用の原料に適する六方晶窒化ホウ素粉末及びその製造方法を提供できる。本開示によればまた、伸び性に優れる化粧料及びその製造方法を提供できる。 According to the present disclosure, it is possible to provide a hexagonal boron nitride powder suitable as a raw material for cosmetics and a method for producing the same. According to the present disclosure, it is also possible to provide a cosmetic with excellent extensibility and a method for producing the same.
Claims (7)
前記六方晶窒化ホウ素粉末の平均粒径が８～２０μｍであり、比表面積が１．５ｍ２／ｇ以下であり、全酸素量が０．３０質量％以下であり、且つ吸油量が４０ｍＬ／１００ｇ以上１００ｍＬ／１００ｇ未満である、六方晶窒化ホウ素粉末。 A hexagonal boron nitride powder comprising primary particles of hexagonal boron nitride ,
The average particle size of the hexagonal boron nitride powder is 8 to 20 μm, and the specific surface area is 1. A hexagonal boron nitride powder having an area of 5 m 2 /g or less , a total oxygen content of 0.30% by mass or less, and an oil absorption of 40 mL/100 g or more and less than 100 mL/100 g.
前記第一工程よりも高く、１８５０℃未満の温度に維持し１～１５時間前記第一の加熱処理物を加熱処理して第二の加熱処理物を得る第二工程と、
前記第二工程よりも高い温度に維持し１～２５時間、前記第二の加熱処理物を焼成して焼成体を得る第三工程と、
前記焼成体を水及び酸の少なくとも一方で処理する第四工程と、を有する、六方晶窒化ホウ素粉末の製造方法。 A raw material powder containing at least one of carbon black and acetylene black and at least one of boric acid and boron oxide is heated in a gas atmosphere containing at least one of nitrogen and ammonia and under a pressure of 0.25 MPa or more and less than 5.0 MPa. , a first step of maintaining a temperature of 1600° C. or higher and heat-treating for 2 to 4 hours to obtain a first heat-treated product;
a second step of heating the first heat-treated product for 1 to 15 hours at a temperature higher than the first step and less than 1850° C. to obtain a second heat-treated product;
a third step of obtaining a fired body by firing the second heat-treated product for 1 to 25 hours while maintaining the temperature higher than that of the second step;
A method for producing hexagonal boron nitride powder, comprising a fourth step of treating the fired body with at least one of water and acid.
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