JP6734239B2 - Hexagonal boron nitride powder and cosmetics - Google Patents
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims description 117
- 239000002537 cosmetic Substances 0.000 title claims description 42
- 239000000843 powder Substances 0.000 claims description 47
- 229910052582 BN Inorganic materials 0.000 claims description 46
- 238000010304 firing Methods 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 23
- 238000003825 pressing Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000005087 graphitization Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 238000001228 spectrum Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
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- 239000007858 starting material Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
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- 239000012298 atmosphere Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
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- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- -1 etc. are preferable Chemical compound 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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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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- 239000000314 lubricant Substances 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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Landscapes
- Cosmetics (AREA)
Description
本発明は、化粧料として必要な加圧力範囲において滑り性に優れた六方晶窒化ホウ素粉末、並びに該六方晶窒化ホウ素粉末を含む化粧料に関する。 TECHNICAL FIELD The present invention relates to a hexagonal boron nitride powder having excellent slidability in a pressure range required as a cosmetic, and a cosmetic containing the hexagonal boron nitride powder.
六方晶窒化ホウ素は黒鉛類似の層状構造を有し、滑り性、熱伝導性、絶縁性、化学的安定性、耐熱衝撃性などの特性に優れ、これらの特性を活かして化粧料（化粧品ともいう）原料、固体潤滑剤や離型剤、樹脂やゴムの充填材、耐熱性を有する絶縁性焼結体などに応用されている。 Hexagonal boron nitride has a layered structure similar to graphite, and has excellent properties such as slipperiness, thermal conductivity, insulation, chemical stability, and thermal shock resistance. Utilizing these properties, cosmetics (also called cosmetics ) Applied to raw materials, solid lubricants and mold release agents, fillers of resins and rubbers, heat-resistant insulating sinters, etc.
化粧料原料用の六方晶窒化ホウ素粉末については、これまでは安全性、衛生性の観点から開発をなされてきた。特に溶出ホウ素量については、医薬部外品原料規格２００６で規格が定められており、所定の手順で六方晶窒化ホウ素粉末を水に接触させた際に、許容できるホウ素量（以降、「溶出ホウ素量」という）は窒化ホウ素１ｇに対して２０μｇ以下（すなわち２０ｐｐｍ以下）と規定されており、該規定を超える六方晶窒化ホウ素粉末は、これを原料として配合した化粧料の肌への刺激性を高める可能性があった。そのため、水溶性ホウ素化合物を低減する手段が様々に開示されてきた。 Hexagonal boron nitride powder used as a raw material for cosmetics has been developed from the viewpoint of safety and hygiene. Particularly, regarding the amount of eluted boron, the standard is defined in the Quasi-drug raw material standard 2006, and when the hexagonal boron nitride powder is brought into contact with water by a predetermined procedure, the allowable amount of boron (hereinafter, “eluted boron”). Amount) is specified to be 20 μg or less (that is, 20 ppm or less) with respect to 1 g of boron nitride, and a hexagonal boron nitride powder exceeding the specified amount causes the skin irritancy of the cosmetic compounded with this as a raw material. There was a possibility to raise. Therefore, various means for reducing the water-soluble boron compound have been disclosed.
特許文献１には、六方晶窒化ホウ素を低級アルコールやアセトン等の水可溶性有機溶媒若しくはその水溶液、または界面活性剤水溶液中で攪拌洗浄し、低温かつ低酸素雰囲気下で乾燥する方法が、特許文献２には、六方晶窒化ホウ素粉末を水または熱水に分散させて水可溶性ホウ素化合物を洗浄除去し、乾燥させた後、アルコールを配合若しくはアルコール中に浸漬し、然る後再度乾燥させる方法が、さらに特許文献３には、六方晶窒化ホウ素粉末を、酸水溶液中で洗浄し、乾燥した後、炭素と接触させないようにして窒素雰囲気下１８００〜１９５０℃で１〜５時間熱処理する方法が開示されている。 Patent Document 1 discloses a method in which hexagonal boron nitride is washed by stirring in a water-soluble organic solvent such as lower alcohol or acetone or an aqueous solution thereof, or a surfactant aqueous solution, and dried under a low temperature and low oxygen atmosphere. In 2, there is a method in which a hexagonal boron nitride powder is dispersed in water or hot water to remove a water-soluble boron compound by washing, dried, and then blended with alcohol or immersed in alcohol, and then dried again. Further, Patent Document 3 discloses a method in which a hexagonal boron nitride powder is washed in an aqueous acid solution, dried, and then heat-treated at 1800 to 1950° C. for 1 to 5 hours in a nitrogen atmosphere without being brought into contact with carbon. Has been done.
一方で、化粧料原料用に六方晶窒化ホウ素粉末を配合する目的として、滑り性、伸び性、及び光沢性等の付与がある。特に、六方晶窒化ホウ素粉末の滑り性は、同様の機能を有するタルク粉末やマイカ粉末に比べて優れており、滑り性の改善は化粧料にとって重要な因子である。しかし特許文献１〜３に開示される六方晶窒化ホウ素粉末では滑り性の改善はなされておらず、結果として滑り性において十分に満足のいくものではなかった。 On the other hand, for the purpose of blending the hexagonal boron nitride powder as a raw material for cosmetics, it is necessary to impart slipperiness, extensibility and gloss. In particular, the hexagonal boron nitride powder is superior in slipperiness to talc powder and mica powder having similar functions, and the improvement of slipperiness is an important factor for cosmetics. However, the hexagonal boron nitride powders disclosed in Patent Documents 1 to 3 have not been improved in slidability, and as a result, slidability was not sufficiently satisfactory.
滑り性を数値化する方法として摩擦力がある。摩擦力は、材料自体の滑り性に加え、相手材への加圧力によって変化する。化粧料の場合、相手材は皮膚であり、加圧力はクリーム状化粧料では２．０ｋＰａ程度、パウダーファンデーションでは２．５ｋＰａ程度と、化粧料の種類によって異なっているため、化粧料として必要な加圧力範囲において滑り性に優れた六方晶窒化ホウ素粉末が必要とされていた。 Friction force is a method to quantify the slipperiness. The frictional force changes depending on the sliding force of the material itself and the pressure applied to the mating material. In the case of cosmetics, the mating material is the skin, and the pressing force is about 2.0 kPa for creamy cosmetics and about 2.5 kPa for powder foundations. A hexagonal boron nitride powder having excellent slidability in the pressure range has been required.
滑り性に優れた化粧料用窒化ホウ素粉末として、特許文献４が開示されている。しかし特許文献４は扁平形状の一次粒子が積層した板状の凝集体であるため、上記記載の方法では満足のいく滑り性が得られなかった。 Patent Document 4 is disclosed as a boron nitride powder for cosmetics having excellent slipperiness. However, since Patent Document 4 is a plate-like aggregate in which flat primary particles are laminated, satisfactory slipperiness cannot be obtained by the method described above.
本発明は、化粧料として必要な加圧力範囲において滑り性に優れた六方晶窒化ホウ素粉末、並びに該六方晶窒化ホウ素粉末を含む化粧料を提供することを目的とする。 An object of the present invention is to provide a hexagonal boron nitride powder having excellent slidability in a pressure range required as a cosmetic, and a cosmetic containing the hexagonal boron nitride powder.
すなわち本発明は、平均粒子径が３μｍ以上２０μｍ以下である六方晶窒化ホウ素粉末において、パウダーレオメーターで測定された加圧力１．５ｋＰａ以上３．０ｋＰａ以下の範囲におけるせん断応力Ｓと加圧力Ｐの比の値ｒ（［数１］）が０．７０以下であり、黒鉛化指数（［数２］）が２．０以下であることを特徴とする六方晶窒化ホウ素粉末である。更に本発明においては、加圧力２．０ｋＰａにおけるせん断応力が１．４ｋＰａ以下、及び／又は加圧力３．０ｋＰａにおけるせん断応力が２．１ｋＰａ以下であることを特徴とする六方晶窒化ホウ素粉末を得ることができる。 That is, in the present invention, in the hexagonal boron nitride powder having an average particle size of 3 μm or more and 20 μm or less, the shear stress S and the pressing force P in the range of 1.5 kPa or more and 3.0 kPa or less of the pressing force measured by a powder rheometer. A hexagonal boron nitride powder having a ratio value r ([Numerical formula 1]) of 0.70 or less and a graphitization index ([Numerical formula 2]) of 2.0 or less. Furthermore, in the present invention, a hexagonal boron nitride powder having a shear stress at a pressure of 2.0 kPa of 1.4 kPa or less and/or a shear stress at a pressure of 3.0 kPa of 2.1 kPa or less is obtained. be able to.
［数１］ r＝Ｓ／Ｐ
［数２］ 黒鉛化指数＝（Ｓ１＋Ｓ２）／Ｓ３
Ｓ１：Ｘ線回折スペクトルにおける（１００）面のピーク面積
Ｓ２：Ｘ線回折スペクトルにおける（１０１）面のピーク面積
Ｓ３：Ｘ線回折スペクトルにおける（１０２）面のピーク面積
[Equation 1] r=S/P
[Equation 2] Graphitization index=(S1+S2)/S3
S1: Peak area of (100) plane in X-ray diffraction spectrum
S2: Peak area of (101) plane in X-ray diffraction spectrum
S3: Peak area of (102) plane in X-ray diffraction spectrum
本発明により、化粧料として必要な加圧力範囲において優れた滑り性を示す六方晶窒化ホウ素を提供することができ、更に該六方晶窒化ホウ素粉末を含む滑り性に優れた化粧料を提供することができる。 According to the present invention, it is possible to provide a hexagonal boron nitride exhibiting excellent slidability in a pressing force range required as a cosmetic, and further to provide a cosmetic excellent in slidability containing the hexagonal boron nitride powder. You can
＜六方晶窒化ホウ素粉末＞
本発明の一側面に係る六方晶窒化ホウ素粉末は、平均粒子径が３μｍ以上２０μｍ以下、パウダーレオメーターで測定された加圧力１．５ｋＰａ以上３．０ｋＰａ以下の範囲におけるせん断応力Ｓと加圧力Ｐの比の値ｒが０．７０以下、黒鉛化指数が２．０以下である。
<Hexagonal boron nitride powder>
The hexagonal boron nitride powder according to one aspect of the present invention has an average particle diameter of 3 μm or more and 20 μm or less and a shear stress S and a pressure P of 1.5 kPa or more and 3.0 kPa or less measured by a powder rheometer. The value r of the ratio is 0.70 or less and the graphitization index is 2.0 or less.
以下に、本発明に係る六方晶窒化ホウ素粉末を実施するためのより詳しい説明を示す。 The following is a more detailed description for carrying out the hexagonal boron nitride powder according to the present invention.
＜平均粒子径＞
本発明の六方晶窒化ホウ素粉末の平均粒子径は３μｍ以上２０μｍ以下、好ましくは４μｍ以上１８μｍ以下、更に好ましくは５μｍ以上１５μｍ以下である。３μｍ未満では滑り性が不十分となる。２０μｍを超えると、例えばこれを用いた化粧料の肌への感触にざらつきが発生したり、外観上のぎらつきが強くなるため、化粧料原料としては好ましくなくなる。なお本発明における平均粒子径は、レーザー回折散乱法による粒度分布測定において、体積基準の累積粒度分布の累積値５０％の粒子径である。一般に平均粒子径は測定方法により変わる可能性があり、本発明では、水２００ｍｌに、六方晶窒化ホウ素粉末６０ｍｇ及び２０質量％ヘキサメタリン酸水溶液２ｍｌを加え、ホモジナイザーにより３００Ｗの出力で１８０秒間分散処理させた後の分散液を用いて、粒度分布測定器により計測した値である。
<Average particle size>
The hexagonal boron nitride powder of the present invention has an average particle size of 3 μm or more and 20 μm or less, preferably 4 μm or more and 18 μm or less, and more preferably 5 μm or more and 15 μm or less. If it is less than 3 μm, the slipperiness is insufficient. If it exceeds 20 μm, for example, a cosmetic using the same may have a rough texture on the skin, or the appearance may be more glare, which is not preferable as a raw material for cosmetics. The average particle size in the present invention is a particle size of 50% of the cumulative value of the cumulative particle size distribution on a volume basis in the particle size distribution measurement by the laser diffraction scattering method. Generally, the average particle size may change depending on the measuring method. In the present invention, 60 mg of hexagonal boron nitride powder and 2 ml of 20 mass% hexametaphosphoric acid aqueous solution are added to 200 ml of water, and the mixture is dispersed by a homogenizer at an output of 300 W for 180 seconds. It is the value measured by the particle size distribution measuring device using the dispersion liquid after being heated.
＜せん断応力及び加圧力とせん断応力の比＞
本発明の六方晶窒化ホウ素粉末において［数１］で示される加圧力Ｐとせん断応力Ｓの比の値ｒは、加圧力１．５ｋＰａ以上３．０ｋＰａ以下の範囲において０．７０以下、好ましくは０．６５以下である。
加圧力１．５ｋＰａ以上３．０ｋＰａ以下は、上述の通り化粧料として必要な加圧力範囲であり、クリーム状化粧料では２．０ｋＰａ、パウダーファンデーションでは２．５ｋＰａと言われている。加圧力とせん断応力の比ｒが小さい程、幅広い加圧力範囲で滑り易く、化粧料として好適であると言える。逆にｒが０．７０を超えると滑り性が不十分であり、化粧料として好適ではない。
<Shear stress and ratio of applied pressure and shear stress>
In the hexagonal boron nitride powder of the present invention, the value r of the ratio of the pressing force P and the shear stress S represented by [Equation 1] is 0.70 or less, preferably in the range of pressing force 1.5 kPa or more and 3.0 kPa or less. It is 0.65 or less.
The pressing force of 1.5 kPa or more and 3.0 kPa or less is a pressing force range required as a cosmetic as described above, and is said to be 2.0 kPa for creamy cosmetics and 2.5 kPa for powder foundations. It can be said that the smaller the ratio r of the pressing force and the shear stress, the more slippery in a wide pressing range and the more suitable it is as a cosmetic. On the other hand, when r exceeds 0.70, the slipperiness is insufficient and it is not suitable as a cosmetic.
また本発明の六方晶窒化ホウ素粉末は、パウダーレオメーターで測定された加圧力２．０ｋＰａにおけるせん断応力が１．４ｋＰａ以下、好ましくは１．３ｋＰａ以下であり、更に加圧力３．０ｋＰａ以下におけるせん断応力が２．１ｋＰａ以下、好ましくは２．０ｋＰａ以下である。これらのせん断応力を超えると滑り性が不十分であり、化粧料として好適ではない。なお加圧力とせん断応力の関係の測定は、「パウダーレオメーター（マルバーン製）」を用いた「壁面摩擦試験」により行った。この試験においては表面粗さが規定された円形ディスク（直径４８ｍｍ）を用いて試料粉体と円形ディスクとの摩擦力をせん断応力として測定するが、より肌の状態に近づけるべく円形ディスクに人工皮革（出光テクノファイン製、サプラーレ）を貼り付けて測定を行った。 The hexagonal boron nitride powder of the present invention has a shear stress at a pressure of 2.0 kPa measured by a powder rheometer of 1.4 kPa or less, preferably 1.3 kPa or less, and further shearing at a pressure of 3.0 kPa or less. The stress is 2.1 kPa or less, preferably 2.0 kPa or less. If these shear stresses are exceeded, the slipperiness is insufficient and it is not suitable as a cosmetic. The measurement of the relationship between the pressing force and the shear stress was performed by a "wall surface friction test" using a "powder rheometer (made by Malvern)". In this test, the frictional force between the sample powder and the circular disc is measured as shear stress using a circular disc (diameter 48 mm) whose surface roughness is regulated. To make it closer to the skin condition, the circular disc is made of artificial leather. (Suprare made by Idemitsu Techno Fine Co., Ltd.) was attached and the measurement was performed.
＜黒鉛化指数＞
六方晶窒化ホウ素粉末は、黒鉛と類似の結晶構造を有しており、粉末Ｘ線回折測定を利用し、黒鉛と同様の方法で、その黒鉛化指数を算出することができる。即ち、黒鉛化指数は、Ｘ線回折スペクトルの（１００）面に由来するピークの面積Ｓ１、（１０１）面に由来するピークの面積Ｓ２、及び（１０２）面に由来するピークの面積Ｓ３の各値を、［数２］に代入することによって算出できることが示されており（Ｊ．Ｔｈｏｍａｓ，ｅｔ．ａｌ，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．８４，４６１９（１９６２））、これを六方晶窒化ホウ素に適用したものである。
<Graphization index>
The hexagonal boron nitride powder has a crystal structure similar to that of graphite, and its graphitization index can be calculated by a method similar to that of graphite using powder X-ray diffraction measurement. That is, the graphitization index is the area S1 of the peak derived from the (100) plane of the X-ray diffraction spectrum, the area S2 of the peak derived from the (101) plane, and the area S3 of the peak derived from the (102) plane. It has been shown that the value can be calculated by substituting it into [Equation 2] (J. Thomas, et. al, J. Am. Chem. Soc. 84, 4619 (1962)), and this is calculated as hexagonal boron nitride. It has been applied to.
なお、本発明では、Ｓ１は六方晶窒化ホウ素の（１００）面のＸ線回折スペクトルに相当するピークの面積（積分強度比）であり、具体的には２θ＝４０°以上４２．５°以下のピークの面積である。同様にＳ２は六方晶窒化ホウ素の（１０１）面のＸ線回折スペクトルに相当するピークの面積（積分強度比）であり、具体的には２θ＝４３°以上４５°以下のピーク面積である。Ｓ３は六方晶窒化ホウ素の（１０２）面のＸ線回折スペクトルに相当するピークの面積（積分強度比）であり、具体的には２θ＝４８°以上５２°以下のピークの面積である。なお、各ピークの面積を求めるにあたり、２θ＝３８°及び５４°における各値を直線で結んでベースラインを作成し、ベースラインを基準として各ピーク面積を算出した。 In the present invention, S1 is the area (integrated intensity ratio) of the peak corresponding to the X-ray diffraction spectrum of the (100) plane of hexagonal boron nitride, and specifically, 2θ=40° or more and 42.5° or less. Is the area of the peak. Similarly, S2 is an area (integrated intensity ratio) of a peak corresponding to the X-ray diffraction spectrum of the (101) plane of hexagonal boron nitride, and specifically, a peak area of 2θ=43° or more and 45° or less. S3 is the area of the peak (integrated intensity ratio) corresponding to the X-ray diffraction spectrum of the (102) plane of hexagonal boron nitride, and is specifically the area of the peak at 2θ=48° or more and 52° or less. In obtaining the area of each peak, a baseline was created by connecting the respective values at 2θ=38° and 54° with a straight line, and each peak area was calculated based on the baseline.
黒鉛化指数は六方晶窒化ホウ素の結晶性の指標となり、化粧料として用いた場合の滑り性に影響する。本発明の六方晶窒化ホウ素の黒鉛化指数は２．０以下、好ましくは１．８以下、更に好ましくは１．４以下である。黒鉛化指数が２．０を超えると、六方晶窒化ホウ素の結晶性が不十分となり、ひいては滑り性が不十分になる。 The graphitization index serves as an index of crystallinity of hexagonal boron nitride and affects the slipperiness when used as a cosmetic. The graphitization index of the hexagonal boron nitride of the present invention is 2.0 or less, preferably 1.8 or less, more preferably 1.4 or less. When the graphitization index exceeds 2.0, the crystallinity of the hexagonal boron nitride becomes insufficient, and the slipperiness becomes insufficient.
＜六方晶窒化ホウ素の製造方法＞
本発明の六方晶窒化ホウ素粉末の製造方法の例としては、ホウ素を含む化合物の粉末及び窒素を含む化合物の粉末（以下、ホウ素を含む化合物と窒素を含む化合物とを併せて出発原料ということもある）と、アルカリ金属化合物及び／又はアルカリ土類金属などの焼成時における出発原料の六方晶窒化ホウ素への変換を促進する焼結助剤の粉末と、本発明の目的を逸脱しない範囲において、必要に応じて出発原料や焼結助剤以外の、単体や化合物を含む混合粉末を、第一焼成条件として窒素、ヘリウム、アルゴン等の不活性雰囲気下、及び又はアンモニア雰囲気下で６００〜１３００℃で焼成して低結晶性六方晶窒化ホウ素となし、これを更に第二焼成条件として窒素、ヘリウム、アルゴン等の不活性雰囲気下、及び又はアンモニア雰囲気下で１６００〜２２００℃で焼成して高結晶性六方晶窒化ホウ素となし、これを洗浄液で洗浄することによる不純物除去処理を加えてから乾燥する工程を含む製造方法が挙げられる。ここで、焼結助剤の配合は、出発原料に配合しても良いし、低結晶性六方晶窒化ホウ素に配合しても良い。
<Method for producing hexagonal boron nitride>
As an example of the method for producing the hexagonal boron nitride powder of the present invention, a powder of a compound containing boron and a powder of a compound containing nitrogen (hereinafter, the compound containing boron and the compound containing nitrogen are also referred to as starting materials. A), a powder of a sintering aid that promotes conversion of a starting material into hexagonal boron nitride during firing of an alkali metal compound and/or an alkaline earth metal, and the like, within a range not departing from the object of the present invention, 600 to 1300° C. under an inert atmosphere of nitrogen, helium, argon or the like as the first firing condition, and/or an ammonia atmosphere, as a first firing condition, if necessary, a mixed powder containing a simple substance or a compound other than a starting material or a sintering aid. To form low crystalline hexagonal boron nitride, which is further crystallized as a second firing condition under an inert atmosphere of nitrogen, helium, argon or the like and/or under an ammonia atmosphere at 1600 to 2200° C. to obtain high crystallinity. There is a manufacturing method including a step of forming a crystalline hexagonal boron nitride, and adding an impurity removal treatment by washing this with a washing liquid, and then drying. Here, the sintering aid may be mixed in the starting material or in the low crystalline hexagonal boron nitride.
ここでホウ素を含む化合物としては、ホウ酸、酸化ホウ素、ホウ砂などが好ましく、特にホウ酸を好ましく用いることができる。また、窒素を含む化合物としては、シアンジアミド、メラミン、尿素などが好ましく、特にメラミンを好ましく選択することができる。出発原料中に含まれるホウ素原子と窒素原子のモル比率は、必ずしも５：５に固定する必要はなく、反応性や収率に応じて、ホウ素原子と窒素原子のモル比率を、好ましくは２：８〜８：２の範囲で、さらに好ましくは３：７〜７：３の範囲で適宜変えることが可能である。なお、低結晶性六方晶窒化ホウ素を製造するための出発原料として用いる各種化合物等は一種類に限定する必要はなく、複数種類の化合物等を同時に使用することもできる。 As the compound containing boron, boric acid, boron oxide, borax, etc. are preferable, and boric acid can be particularly preferably used. Further, as the nitrogen-containing compound, cyandiamide, melamine, urea and the like are preferable, and melamine can be particularly preferably selected. The molar ratio of the boron atom and the nitrogen atom contained in the starting material does not necessarily have to be fixed at 5:5, and the molar ratio of the boron atom and the nitrogen atom is preferably 2:5 depending on the reactivity and the yield. It can be appropriately changed within the range of 8 to 8:2, and more preferably within the range of 3:7 to 7:3. The various compounds and the like used as starting materials for producing the low crystalline hexagonal boron nitride do not have to be limited to one kind, and a plurality of kinds of compounds and the like can be used at the same time.
焼結助剤の好ましい具体例としては、リチウム、ナトリウム、カリウム等のアルカリ金属の酸化物又は炭酸塩、カルシウム、ストロンチウム等のアルカリ土類金属の酸化物又は炭酸塩を挙げることができる。焼結助剤の好ましい配合割合としては、出発原料１００重量部に対して焼結助剤０．９質量部以上２０質量部以下が好ましい。なお、焼結助剤として用いる各種化合物等は一種類に限定する必要はなく、複数種類の化合物等を同時に使用することもできる。また、出発原料や焼結助剤以外に配合できる単体や化合物の例としては、炭素などの還元性物質を挙げることができる。 Preferred specific examples of the sintering aid include oxides or carbonates of alkali metals such as lithium, sodium and potassium, and oxides or carbonates of alkaline earth metals such as calcium and strontium. The preferable mixing ratio of the sintering aid is 0.9 parts by mass or more and 20 parts by mass or less of 100 parts by weight of the starting material. It should be noted that it is not necessary to limit the variety of compounds used as the sintering aid to one type, and a plurality of types of compounds and the like can be used at the same time. In addition, as an example of a simple substance or a compound that can be blended in addition to the starting material and the sintering aid, a reducing substance such as carbon can be cited.
さらに黒鉛化指数、すなわち六方晶窒化ホウ素の結晶性は、焼結助剤の配合量、及び焼成温度によって変化する。出発原料の１００質量部に対する焼結助剤の配合割合は少なくとも０．９質量部以上、好ましくは１．０質量部以上、さらに好ましくは２．０質量部以上であることが望ましい。また、化粧料への適用を考慮すると、出発原料の１００質量部に対する焼結助剤の配合割合は多くとも２０質量部以下、好ましくは１５質量部以下、さらに好ましくは１２質量部以下であることが望ましい。焼結助剤の配合割合が上記の範囲未満であると、焼結に伴って進行するべき出発原料から六方晶窒化ホウ素への変換反応が進まずに、黒鉛化指数が２．０を超える値となりやすく、化粧料としての塗り伸び性が不十分となる。逆に、焼結助剤の配合割合が上記の範囲を超えると六方晶窒化ホウ素の結晶成長が進みすぎて微粉砕が困難になり、該粉末の平均粒子径が２０μｍを超える可能性が高く、このような六方晶窒化ホウ素粉末を原料として用いた化粧料では、外観上のぎらつきが強くなり、化粧料用原料として相応しくない。 Further, the graphitization index, that is, the crystallinity of hexagonal boron nitride changes depending on the blending amount of the sintering aid and the firing temperature. The mixing ratio of the sintering aid to 100 parts by mass of the starting material is at least 0.9 parts by mass or more, preferably 1.0 parts by mass or more, and more preferably 2.0 parts by mass or more. In consideration of application to cosmetics, the mixing ratio of the sintering aid to 100 parts by mass of the starting material is at most 20 parts by mass, preferably 15 parts by mass or less, more preferably 12 parts by mass or less. Is desirable. When the blending ratio of the sintering aid is less than the above range, the conversion reaction from the starting material to hexagonal boron nitride that should proceed with sintering does not proceed and the graphitization index exceeds 2.0. And the coating spreadability as a cosmetic becomes insufficient. On the other hand, if the mixing ratio of the sintering aid exceeds the above range, the crystal growth of hexagonal boron nitride will proceed too much and fine pulverization will be difficult, and the average particle diameter of the powder is likely to exceed 20 μm. A cosmetic using such a hexagonal boron nitride powder as a raw material has a strong external glare, and is not suitable as a raw material for a cosmetic.
本発明の発明者らは、化粧料における皮膚への必要な加圧力範囲において優れた滑り性を示す六方晶窒化ホウ素粉末を合成する方法について鋭意検討した結果、これを実現するためには、低結晶性六方晶窒化ホウ素の粉末に含まれる１００μｍ以上の粗粉量を特定量以下とすることが必要であることを見出し、本発明を完成させた。低結晶性六方晶窒化ホウ素の粉末に含まれる１００μｍ以上の粗粉量としては、多くとも４０体積％以下、好ましくは３０体積％以下、さらに好ましくは２０体積％以下であることが望ましい。低結晶性六方晶窒化ホウ素の粉末に含まれる１００μｍ以上の粗粉量が４０体積％を超えると、高結晶性六方晶窒化ホウ素合成時の結晶成長が不均一化するため、加圧力Ｐとせん断応力Ｓの比の値ｒが０．６５を超えるため、化粧料用原料として相応しくない。なお本発明における１００μｍ以上の粗粉量は、レーザー回折散乱法による粒度分布測定において、体積基準の累積粒度分布の粒子径１００μｍを超える体積割合である。本発明では、水２００ｍｌに、低結晶性六方晶窒化ホウ素の粉末６０ｍｇ及び２０質量％ヘキサメタリン酸水溶液２ｍｌを加えた混合液を、超音波分散処理を実施することなく、粒度分布測定器により計測した値である。ここで、超音波分散処理を実施しない理由は、超音波分散処理を行うと、低結晶性六方晶窒化ホウ素の粉末に含まれる粗粉が超音波によって粉砕され、粗粉量が正確に測定できなくなるためである。 The inventors of the present invention diligently studied a method of synthesizing a hexagonal boron nitride powder showing excellent slipperiness in a range of a pressure applied to the skin in cosmetics, and as a result, in order to achieve this, a low The inventors have found that it is necessary to set the amount of coarse powder of 100 μm or more contained in the crystalline hexagonal boron nitride powder to a specific amount or less, and have completed the present invention. The amount of coarse powder of 100 μm or more contained in the low crystalline hexagonal boron nitride powder is at most 40% by volume or less, preferably 30% by volume or less, and more preferably 20% by volume or less. When the amount of coarse powder of 100 μm or more contained in the low crystalline hexagonal boron nitride powder exceeds 40% by volume, the crystal growth during the synthesis of the highly crystalline hexagonal boron nitride becomes non-uniform, so that the pressing force P and the shearing force are increased. Since the value r of the ratio of the stress S exceeds 0.65 , it is not suitable as a raw material for cosmetics. In addition, the amount of coarse powder of 100 μm or more in the present invention is a volume ratio in which the particle size of the cumulative particle size distribution on a volume basis exceeds 100 μm in the particle size distribution measurement by the laser diffraction scattering method. In the present invention, a mixed solution obtained by adding 60 mg of low crystalline hexagonal boron nitride powder and 2 ml of 20% by mass aqueous hexametaphosphoric acid solution to 200 ml of water was measured by a particle size distribution analyzer without performing ultrasonic dispersion treatment. It is a value. Here, the reason why the ultrasonic dispersion treatment is not performed is that when the ultrasonic dispersion treatment is performed, the coarse powder contained in the low crystalline hexagonal boron nitride powder is pulverized by ultrasonic waves, and the coarse powder amount can be accurately measured. This is because it will disappear.
第一焼成条件で得られる低結晶性六方晶窒化ホウ素は、一般的にはブロック状の固形物の状態で取り出されるため、これを粉砕又は分級することにより、１００μｍ以上の粗粉量が４０体積％以下である低結晶性六方晶窒化ホウ素の粉末を得ることができる。粉砕機の一例を挙げれば、ボールミル、ハンマーミル、カッターミル、リングミル、ピンミル、振動ミル、ジェットミル、ビーズミルがある。分級機の一例を挙げれば、振動篩、沈降分級、気流式分級機がある。また、低結晶性六方晶窒化ホウ素粉末の生産性を高めるために、これらの粉砕機及び分級機を、第一焼成条件の焼成炉の出口に設置することもできる。 The low crystalline hexagonal boron nitride obtained under the first firing condition is generally taken out in the form of a block-like solid, so by pulverizing or classifying it, a coarse powder amount of 100 μm or more is 40 volume. % Hexagonal boron nitride powder can be obtained. Examples of the pulverizer include a ball mill, a hammer mill, a cutter mill, a ring mill, a pin mill, a vibration mill, a jet mill and a bead mill. Examples of the classifier include a vibrating screen, a sedimentation classifier, and an airflow classifier. Further, in order to improve the productivity of the low crystalline hexagonal boron nitride powder, these pulverizers and classifiers can be installed at the exit of the firing furnace under the first firing conditions.
該混合粉末を焼成するときの最高温度としては、第一焼成条件では、６００℃以上１３００℃以下の範囲の温度が好ましく、８００℃以上１２００℃以下の範囲の温度がより好ましく設定される。焼成温度の最高値が６００℃未満であると低結晶六方晶窒化ホウ素への変換が進み難くなり、原料であるホウ素を含む化合物の残留量が増加するため、結果として平均粒子径が３．０μｍ未満の値となりやすく、加圧力Ｐとせん断応力Ｓの比の値ｒが０．６５を超えるため、化粧料用原料として相応しくない。焼成温度の最高値が１３００℃を超えると、高結晶六方晶窒化ホウ素を合成するのに必要なＢ２Ｏ３等の酸化物が減少し、結果として黒鉛化指数が２．０を超える値となりやすく、化粧料としての塗り伸び性が不十分となるため好ましくない。第二焼成条件では、１６００℃以上２２００℃以下の範囲の温度が好ましく、１６５０℃以上１９００℃以下の範囲の温度がより好ましく設定される。焼成温度の最高値が１６００℃未満であると六方晶窒化ホウ素への変換が進み難くなるため黒鉛化指数が２．０を超える値となりやすく、加圧力Ｐとせん断応力Ｓの比の値ｒが０．６５を超えるため、化粧料用原料として相応しくない。焼成温度の最高値が２２００℃を超えると、六方晶窒化ホウ素の結晶成長が進みすぎ、化粧料用原材料として使用した場合に外観のぎらつきが強まるため、実用上好ましくない。 As the maximum temperature for firing the mixed powder, a temperature in the range of 600° C. to 1300° C. is preferable, and a temperature in the range of 800° C. to 1200° C. is more preferably set under the first firing conditions. If the maximum firing temperature is less than 600° C., conversion to low-crystal hexagonal boron nitride becomes difficult to proceed, and the residual amount of the compound containing boron as the raw material increases, resulting in an average particle diameter of 3.0 μm. The value r of the ratio of the pressing force P to the shear stress S exceeds 0.65, which is not suitable as a raw material for cosmetics. When the maximum firing temperature exceeds 1300° C., the amount of oxides such as B 2 O 3 necessary for synthesizing high crystal hexagonal boron nitride decreases, and as a result, the graphitization index exceeds 2.0. It is not preferred because it is easy and the coating spreadability as a cosmetic is insufficient. Under the second firing conditions, a temperature in the range of 1600° C. or higher and 2200° C. or lower is preferable, and a temperature in the range of 1650° C. or higher and 1900° C. or lower is more preferably set. If the maximum firing temperature is less than 1600° C., the conversion to hexagonal boron nitride is difficult to proceed, so the graphitization index tends to exceed 2.0, and the value r of the ratio of the pressing force P to the shear stress S is Since it exceeds 0.65 , it is not suitable as a raw material for cosmetics. If the maximum firing temperature exceeds 2200° C., the crystal growth of hexagonal boron nitride will proceed excessively and the glare of the appearance will increase when used as a raw material for cosmetics, which is not preferable in practice.
六方晶窒化ホウ素粉末の焼成温度は一定に保持しても、連続的または不連続的に変化させても良く、昇温冷却時の速度にも制限はないが、第一焼成条件では、焼成時間が短すぎると、低結晶六方晶窒化ホウ素への変換が進み難くなり、原料であるホウ素を含む化合物の残留量が増加するため、結果として平均粒子径が３．０μｍ未満の値となりやすいため、０．５時間以上が好ましく、１時間以上がより好ましい。第二焼成条件では、焼成時間が短すぎると焼成が不十分となり、黒鉛化指数が２．０を超える可能性があるため、２時間以上が好ましく、４時間以上がより好ましい。また、該粉末混合物を焼成する装置類については特に制限はないが、該粉末混合物を収納する容器には、例えば六方晶窒化ホウ素製の容器を用いることができ、加熱装置には、例えば電気ヒータを用いた焼成炉を用いることができる。 The firing temperature of the hexagonal boron nitride powder may be kept constant, or may be continuously or discontinuously changed, and there is no limitation on the rate at the time of temperature rising and cooling, but in the first firing condition, the firing time is Is too short, the conversion to low crystal hexagonal boron nitride becomes difficult to proceed, the residual amount of the compound containing boron as a raw material increases, and as a result, the average particle diameter tends to be a value of less than 3.0 μm, It is preferably 0.5 hours or longer, more preferably 1 hour or longer. In the second firing condition, if the firing time is too short, firing becomes insufficient and the graphitization index may exceed 2.0, so 2 hours or more is preferable, and 4 hours or more is more preferable. Further, there is no particular limitation on the apparatus for firing the powder mixture, but a container made of hexagonal boron nitride, for example, can be used as the container for storing the powder mixture, and the heating device can be, for example, an electric heater. It is possible to use a firing furnace using.
また、出発原料を混合して粉末混合物となしてから焼成が終了するまでの間に、本発明の目的を逸脱しない範囲内で、さらに加熱、冷却、加湿、乾燥、及び洗浄の操作を加えることも可能である。 Further, during the period from the mixing of the starting materials to form a powder mixture and the end of the firing, further heating, cooling, humidifying, drying, and washing operations may be added within a range not departing from the object of the present invention. Is also possible.
焼成が終了して得られた高結晶性六方晶窒化ホウ素を粉砕する装置に特に規定はないが、粉砕条件によっては得られた六方晶窒化ホウ素が微細化してしまい、上述の溶出ホウ素量が２０ｐｐｍを超えてしまう恐れがある。 The device for pulverizing the highly crystalline hexagonal boron nitride obtained after the calcination is not particularly specified, but the hexagonal boron nitride obtained becomes finer depending on the pulverization conditions, and the amount of eluted boron is 20 ppm. May exceed.
粉砕した高結晶性六方晶窒化ホウ素粉末中には、六方晶窒化ホウ素以外の不純物や水溶性ホウ素化合物（以降、まとめて不純物等という）が含まれている可能性があるため、洗浄液を用いた洗浄により不純物等を除去してから固液分離して乾燥し、最終的に本発明の六方晶窒化ホウ素粉末を得ることができる。ここでいう洗浄液とは、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のいずれかであることが望ましい。水は、例えば５〜９５℃の冷水、温水または熱水を用いることができ、この場合、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以下の水を使用することができる。酸性物質としては、例えば塩酸、硝酸等の無機酸を挙げることができる。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やアセトン等の水溶性の有機溶媒を好ましく使用することができる。高結晶性六方晶窒化ホウ素粉末と洗浄液とを接触させる方法にも特に制限はないが、高結晶性六方晶窒化ホウ素粉末を、洗浄液中に浸漬して撹拌したり、高結晶性六方晶窒化ホウ素粉末に、洗浄液をスプレーしたりして洗浄する方法等がある。 Since the pulverized highly crystalline hexagonal boron nitride powder may contain impurities other than hexagonal boron nitride and water-soluble boron compounds (hereinafter collectively referred to as impurities), a cleaning liquid was used. Impurities and the like are removed by washing, solid-liquid separation is performed, and drying is performed to finally obtain the hexagonal boron nitride powder of the present invention. The cleaning liquid here is preferably any one of water, an aqueous solution containing an acidic substance, an organic solvent, and a mixed liquid of an organic solvent and water. As the water, for example, cold water, hot water or hot water of 5 to 95° C. can be used, and in this case, water having an electric conductivity of 1 mS/m or less is used from the viewpoint of avoiding secondary contamination of impurities. You can Examples of the acidic substance include inorganic acids such as hydrochloric acid and nitric acid. As the organic solvent, for example, water-soluble organic solvents such as methanol, ethanol, propanol, isopropyl alcohol and acetone can be preferably used. The method of bringing the highly crystalline hexagonal boron nitride powder and the cleaning liquid into contact with each other is not particularly limited, but the highly crystalline hexagonal boron nitride powder is immersed in the cleaning liquid and stirred, or the highly crystalline hexagonal boron nitride powder is stirred. There is a method of washing the powder by spraying a washing liquid or the like.
洗浄終了後、固液分離してから乾燥する場合、固液分離の方法にも特に限定はなく、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、沈降分離機またはそれらの組み合わせた装置を用いることができる。 When the solid-liquid separation is followed by drying after the completion of washing, the solid-liquid separation method is not particularly limited, and examples thereof include decantation, a suction filter, a pressure filter, a rotary filter, a sedimentation separator or a combination thereof. A combination of devices can be used.
さらに固液分離後の高結晶性六方晶窒化ホウ素粉末の乾燥方法にも特に制限はないが、使用できる乾燥装置の一例を示せば、棚式乾燥機、流動層乾燥機、噴霧乾燥機、回転型乾燥機、ベルト式乾燥機またはそれらの組み合わせであり、乾燥機内の雰囲気温度は３０℃以上３００℃以下、好ましくは２００℃以下、乾燥機内の絶対圧力は１０−６ｋＰａＡ以上１０１．３ｋＰａＡ以下である。 Further, the method for drying the highly crystalline hexagonal boron nitride powder after solid-liquid separation is not particularly limited, but if an example of a drying device that can be used is shown, a shelf dryer, a fluidized bed dryer, a spray dryer, a rotary dryer A mold dryer, a belt dryer, or a combination thereof, the atmosphere temperature in the dryer is 30° C. or higher and 300° C. or lower, preferably 200° C. or lower, and the absolute pressure in the dryer is 10 −6 kPaA or higher and 101.3 kPaA or lower. is there.
洗浄、固液分離、乾燥はそれぞれ１回でも良いし、同じ方法または異なる方法を組み合わせて複数回実施しても構わない。 The washing, solid-liquid separation, and drying may be performed once, or may be performed multiple times by combining the same method or different methods.
＜本発明の六方晶窒化ホウ素粉末を用いた化粧料＞
本発明は別の一側面において、本発明の六方晶窒化ホウ素粉末を含む化粧料である。化粧料の一例を示せば、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、マスカラであるが、中でもファンデーション、アイシャドーに本発明の六方晶窒化ホウ素粉末が特に良く適合する。本発明の六方晶窒化ホウ素粉末の化粧料への好適な配合割合量は０．１質量％以上７０質量％以下である。
<Cosmetics using the hexagonal boron nitride powder of the present invention>
The present invention, in another aspect, is a cosmetic containing the hexagonal boron nitride powder of the present invention. Examples of cosmetics are foundations (powder foundation, liquid foundation, cream foundation), face powder, point makeup, eye shadow, eyeliner, manicure, lipstick, blusher, mascara. The inventive hexagonal boron nitride powder is particularly well suited. The preferred blending ratio of the hexagonal boron nitride powder of the present invention to cosmetics is 0.1% by mass or more and 70% by mass or less.
以下、本発明を実施例、比較例をあげて更に具体的に説明する。
＜実施例１＞
ホウ酸粉末（関東化学社製、純度９９．８質量％以上）２００ｇ、及びメラミン粉末（和光純薬社製、純度９９．０質量％以上）１８０ｇの各出発原料をそれぞれ秤量し、アルミナ製乳鉢を用いて１０分間混合した。作製した粉末混合物を恒温恒湿機（ＡＤＶＡＮＴＥＣ社製、ＡＧＸ−２２５）に入れ、８０℃、相対湿度９５％で１時間加湿し、その後、１２０℃で１時間乾燥した。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
<Example 1>
200 g of boric acid powder (manufactured by Kanto Chemical Co., Inc., purity of 99.8 mass% or more) and 180 g of melamine powder (manufactured by Wako Pure Chemical Industries, purity of 99.0 mass% or more) were weighed, and an alumina mortar was used. And mixed for 10 minutes. The produced powder mixture was placed in a thermo-hygrostat (ADVANTEC, AGX-225), humidified at 80° C. and 95% relative humidity for 1 hour, and then dried at 120° C. for 1 hour.
これを六方晶窒化ホウ素製の容器（内容積１．４Ｌ）に入れ、炉室内容積が１６Ｌの電気炉（東海高熱工業社製、ＴＶ−２００）内に配し、炉室内への窒素ガス流量を１６Ｌ（２５℃における体積）／分として、１０℃／分の割合で室温から昇温し、１０００℃で２時間保持したのち、加熱を止めて自然冷却させ、温度が１００℃以下まで下がった時点で電気炉を開放して、低結晶性窒化ホウ素（粉砕前）を回収した。 This was placed in a hexagonal boron nitride container (internal volume: 1.4 L), placed in an electric furnace (TV-200, manufactured by Tokai High Heat Industrial Co., Ltd.) having a furnace chamber volume of 16 L, and the nitrogen gas flow rate into the furnace chamber. Was 16 L (volume at 25° C.)/min, the temperature was raised from room temperature at a rate of 10° C./min, and the temperature was kept at 1000° C. for 2 hours, then the heating was stopped and the temperature was lowered to 100° C. or lower. At this point, the electric furnace was opened and the low crystalline boron nitride (before grinding) was recovered.
得られた低結晶性窒化ホウ素（粉砕前）を、ボールミルを用いて２４時間粉砕し、低結晶性六方晶窒化ホウ素の粉末となした。ボールミルは、内容積１Ｌの樹脂容器に、φ１５ｍｍのアルミナボール０．７ｋｇ及び低結晶性窒化ホウ素（粉砕前）を充填し、回転速度７５ｒｐｍで粉砕を行った。この低結晶性六方晶窒化ホウ素の粉末１００重量部に、炭酸ナトリウム（和光純薬社製、純度９９．５質量％以上）１０重量部を配合してアルミナ製乳鉢を用いて１０分間混合し、さらに上述の電気炉内に配し、炉室内への窒素ガス流量を１６Ｌ（２５℃における体積）／分として、１０℃／分の割合で昇温し、焼成温度の最高値である１８５０℃まで到達させてから４時間温度を保持した。その後、加熱を止めて自然冷却させ、温度が１００℃以下まで下がった時点で電気炉を開放して、高結晶性六方晶窒化ホウ素（粉砕前）を回収した。これをアルミナ製乳鉢で３分間粉砕し、高結晶性六方晶窒化ホウ素の粉末となした。 The obtained low crystalline boron nitride (before pulverization) was pulverized with a ball mill for 24 hours to obtain a low crystalline hexagonal boron nitride powder. In the ball mill, a resin container having an internal volume of 1 L was filled with 0.7 kg of φ15 mm alumina balls and low crystalline boron nitride (before crushing), and crushed at a rotation speed of 75 rpm. 100 parts by weight of this low crystalline hexagonal boron nitride powder was mixed with 10 parts by weight of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5% by mass or more) and mixed for 10 minutes using an alumina mortar, Further, it is placed in the above-mentioned electric furnace, and the nitrogen gas flow rate into the furnace chamber is set to 16 L (volume at 25° C.)/min and the temperature is raised at a rate of 10° C./min until the maximum firing temperature of 1850° C. After reaching the temperature, the temperature was maintained for 4 hours. Then, the heating was stopped and the mixture was naturally cooled, and when the temperature dropped to 100° C. or lower, the electric furnace was opened to recover the highly crystalline hexagonal boron nitride (before pulverization). This was pulverized in an alumina mortar for 3 minutes to obtain a highly crystalline hexagonal boron nitride powder.
さらに該高結晶性六方晶窒化ホウ素の粉末中に含まれる不純物を除くため、５質量％希硝酸５００ｇあたり３０ｇの割合で該粉末を投入し、室温で６０分攪拌した後、吸引ろ過により固液分離し、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。洗浄後の粉末は乾燥機で１７０℃で１２時間乾燥し、実施例１の六方晶窒化ホウ素粉末を得た。 Further, in order to remove impurities contained in the powder of the highly crystalline hexagonal boron nitride, the powder was added at a ratio of 30 g per 500 g of 5% by mass dilute nitric acid, stirred at room temperature for 60 minutes, and then solid-liquid by suction filtration. Separation was performed and water (electrical conductivity 1 mS/m) was replaced and washed until the filtrate became neutral. The washed powder was dried at 170° C. for 12 hours with a drier to obtain the hexagonal boron nitride powder of Example 1.
＜１００μｍ以上の粗粉量＞
実施例１で作製した低結晶性六方晶窒化ホウ素粉末の分散液を上述した方法で作製し、粒度分布測定機（日機装社製、ＭＴ３３００ＥＸ型）で六方晶窒化ホウ素粉末の平均粒子径を測定した。水の屈折率には１．３３を用い、窒化ホウ素粉末の屈折率は１．８０として、一回当たりの測定時間は３０秒とした。
<Amount of coarse powder of 100 μm or more>
The dispersion liquid of the low crystalline hexagonal boron nitride powder produced in Example 1 was produced by the method described above, and the average particle diameter of the hexagonal boron nitride powder was measured with a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., MT3300EX type). .. The refractive index of water was 1.33, the refractive index of the boron nitride powder was 1.80, and the measurement time per measurement was 30 seconds.
＜平均粒子径＞
実施例１で作製した六方晶窒化ホウ素粉末の分散液を上述した方法で作製し、粒度分布測定機（日機装社製、ＭＴ３３００ＥＸ型）で六方晶窒化ホウ素粉末の平均粒子径を測定した。水の屈折率には１．３３を用い、窒化ホウ素粉末の屈折率は１．８０として、一回当たりの測定時間は３０秒とした。
<Average particle size>
The dispersion liquid of the hexagonal boron nitride powder produced in Example 1 was produced by the method described above, and the average particle diameter of the hexagonal boron nitride powder was measured with a particle size distribution measuring instrument (manufactured by Nikkiso Co., Ltd., MT3300EX type). The refractive index of water was 1.33, the refractive index of the boron nitride powder was 1.80, and the measurement time per measurement was 30 seconds.
＜せん断応力＞
実施例１で作製した六方晶窒化ホウ素粉末のせん断応力を「パウダーレオメーター（マルバーン製、ＦＴ−４型」を用いて測定した。測定は「壁面摩擦試験」に基づき行い、円形ディスクに人工皮革（出光テクノファイン製、サプラーレ）を貼り付け、加圧１．５ｋＰａ（Ｐ１）、２．０ｋＰａ（Ｐ２）、３．０ｋＰａ（Ｐ３）の各加圧力においてせん断応力（Ｓ１〜Ｓ３）を測定、各加圧力における加圧力とせん断応力との比率（ｒ１〜ｒ３）を求めた。
<Shear stress>
The shear stress of the hexagonal boron nitride powder produced in Example 1 was measured using a "powder rheometer (FT-4 type manufactured by Malvern). The measurement was performed based on the "wall friction test", and artificial leather was formed on a circular disk. (Suprare made by Idemitsu Techno Fine Co., Ltd.) is attached, and the shear stress (S1 to S3) is measured at each pressure of 1.5 kPa (P1), 2.0 kPa (P2) and 3.0 kPa (P3). The ratio (r1 to r3) of the pressing force and the shear stress in the pressing force was obtained.
＜黒鉛化指数＞
実施例１で作製した六方晶窒化ホウ素粉末の黒鉛化指数を、高出力粉末Ｘ線回折装置（ブルカー・エイエックスエス社製、Ｄ８ＡＤＶＡＮＣＥ Ｓｕｐｅｒ Ｓｐｅｅｄ）を用いて測定した。六方晶窒化ホウ素粉末を１００ｋＮでプレス成形し、１０×１５×３ｍｍのサンプルを被検体とし、Ｘ線源はＣｕＫα線を用い、管電圧は４５ｋＶ、管電流は３６０ｍＡの条件とした。
<Graphization index>
The graphitization index of the hexagonal boron nitride powder produced in Example 1 was measured using a high power powder X-ray diffractometer (D8ADVANCE Super Speed, manufactured by Bruker AXS KK). Hexagonal boron nitride powder was press-molded at 100 kN, a sample of 10×15×3 mm was used as a test object, CuKα rays were used as an X-ray source, a tube voltage was 45 kV, and a tube current was 360 mA.
＜実施例２〜１１、比較例１〜７＞
実施例１の焼結助剤の出発原料に対する質量割合、第一焼成条件の焼成温度の最高値、焼成時間、ボールミルによる粉砕時間、第二焼成条件の焼成温度の最高値、焼成時間を変更して、実施例２〜１１、比較例１〜７の六方晶窒化ホウ素粉末を作製した。
<Examples 2 to 11, Comparative Examples 1 to 7>
The mass ratio of the sintering aid of Example 1 to the starting material, the maximum firing temperature under the first firing conditions, the firing time, the grinding time with a ball mill, the maximum firing temperature under the second firing conditions, and the firing time were changed. Thus, the hexagonal boron nitride powders of Examples 2-11 and Comparative Examples 1-7 were produced.
＜実施例１２＞
焼結助剤に炭酸カルシウム（関東化学社製、純度９９．５質量％以上）を用いた以外は、実施例１と同じ条件で行い、実施例１２の六方晶窒化ホウ素粉末を作製した。
<Example 12>
A hexagonal boron nitride powder of Example 12 was produced under the same conditions as in Example 1 except that calcium carbonate (manufactured by Kanto Chemical Co., Inc., purity: 99.5 mass% or more) was used as a sintering aid.
＜比較例８＞
焼結助剤を配合割合しなかった以外は、実施例１と同じ条件で行い、比較例８の六方晶窒化ホウ素粉末を作製した。
<Comparative Example 8>
A hexagonal boron nitride powder of Comparative Example 8 was produced under the same conditions as in Example 1 except that the sintering aid was not mixed.
本発明の実施により、従来に比べて化粧料として必要な加圧力範囲において滑り性に優れた六方晶窒化ホウ素粉末、並びに該六方晶窒化ホウ素粉末を含む化粧料を提供することが出来るので、ファンデーション、アイシャドー等の化粧料の原料として好適に用いられる。
By carrying out the present invention, it is possible to provide a hexagonal boron nitride powder having excellent slipperiness in a pressing force range required as a cosmetic material as compared with conventional ones, and a cosmetic material containing the hexagonal boron nitride powder, and thus a foundation. It is preferably used as a raw material for cosmetics such as eye shadows.
Claims (6)
［数１］ ｒ＝Ｓ／Ｐ
［数２］ 黒鉛化指数＝（Ｓ１＋Ｓ２）／Ｓ３
Ｓ１：Ｘ線回折スペクトルにおける（１００）面のピーク面積
Ｓ２：Ｘ線回折スペクトルにおける（１０１）面のピーク面積
Ｓ３：Ｘ線回折スペクトルにおける（１０２）面のピーク面積 In the hexagonal boron nitride powder having an average particle diameter of 3 μm or more and 8.9 μm or less, the ratio of the shear stress S in the range of the pressing force of 2.0 kPa or more and 3.0 kPa or less and the pressing force P measured by a powder rheometer A hexagonal boron nitride powder having a value r ([Numerical formula 1]) of 0.70 or less and a graphitization index ([Numerical formula 2]) of 1.7 or less.
[Equation 1] r=S/P
[Equation 2] Graphitization index=(S1+S2)/S3
S1: Peak area of (100) plane in X-ray diffraction spectrum S2: Peak area of (101) plane in X-ray diffraction spectrum S3: Peak area of (102) plane in X-ray diffraction spectrum
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