JP7002196B2 - Hexagonal boron nitride powder and cosmetics - Google Patents
Hexagonal boron nitride powder and cosmetics Download PDFInfo
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本発明は六方晶窒化ホウ素粉末に関する。また、本発明は該六方晶窒化ホウ素粉末を含む化粧料に関する。 The present invention relates to hexagonal boron nitride powder. The present invention also relates to 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、潤滑性、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、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 lubricity, thermal conductivity, insulation, chemical stability, and heat impact resistance. Taking advantage of these properties, cosmetics (also called cosmetics) ) It is applied to raw materials, solid lubricants, mold release agents, resin and rubber fillers, heat-resistant insulating sintered bodies, and the like.
特に化粧料原料用の六方晶窒化ホウ素粉末については、安全性、衛生性の観点から医薬部外品原料規格2006(以降、「外原規2006」という)にその規格が定められており、この中で、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、許容できる溶出ホウ素量は、濃度基準で20mg/L以下と規定されている。水に溶出するホウ素(以降、「水溶性ホウ素化合物」という。)が、該規定を超えるように含まれ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る。 In particular, regarding hexagonal boron nitride powder for cosmetic raw materials, the standard is defined in the Pharmaceutical Non-Pharmaceutical Products Raw Material Standard 2006 (hereinafter referred to as "Outer Regulations 2006") from the viewpoint of safety and hygiene. In the above, when the hexagonal boron nitride powder is brought into contact with water by a predetermined procedure, the allowable amount of eluted boron is specified to be 20 mg / L or less on a concentration basis. Hexagonal boron nitride powder containing boron eluted in water (hereinafter referred to as "water-soluble boron compound") in excess of the specified value makes the cosmetics containing this as a raw material irritating to the skin. May increase.
六方晶窒化ホウ素粉末から水溶性ホウ素化合物を低減する手段として、特許文献1には、六方晶窒化ホウ素粉末を低級アルコールやアセトン等の水可溶性有機溶媒また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、アルコールを添加し、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。 As a means for reducing the water-soluble boron compound from the hexagonal boron nitride powder, Patent Document 1 states that the hexagonal boron nitride powder is stirred and washed in a water-soluble organic solvent such as lower alcohol or acetone, an aqueous solution thereof, or an aqueous solution of a surfactant. In Patent Document 2, hexagonal boron nitride powder is dispersed in water or hot water to wash and remove the water-soluble boron compound, dried, and then alcohol is added. A method of adding or immersing in alcohol and then drying again is described in Patent Document 3 in which the hexagonal boron nitride powder is washed with an aqueous acid solution, dried, and then kept out of contact with carbon. , Disclosed is a method of heat treatment at 1800 to 1950 ° C. for 1 to 5 hours under a nitrogen atmosphere.
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、隠ぺい性、光沢性の付与等がある。六方晶窒化ホウ素は主にファンデーションに用いられており、塗り伸び性、カバー力(隠ぺい力)が特に重要な因子である。これらの因子は六方晶窒化ホウ素の粒子形態、具体的には平均粒子径やアスペクト比(長径/厚さ)が影響し、一例として特許文献4が挙げられる。 The purpose of blending hexagonal boron nitride powder for cosmetic raw materials is to impart slipperiness, extensibility, hiding property, glossiness and the like. Hexagonal boron nitride is mainly used in foundations, and its coatability and covering power (concealing power) are particularly important factors. These factors are affected by the particle morphology of hexagonal boron nitride, specifically, the average particle diameter and the aspect ratio (major diameter / thickness), and Patent Document 4 is given as an example.
しかしながら、特許文献1及び特許文献2に開示される方法では、洗浄処理で用いる界面活性剤や有機溶剤が六方晶窒化ホウ素粉末に微量残留した場合に、肌への刺激性が発現する可能性を否定できない。また、これらの技術は六方晶窒化ホウ素粉末中に存在していた水溶性ホウ素化合物を、洗浄して予め除去することを主眼としており、例えば六方晶窒化ホウ素粉末を保管している間に、水溶性ホウ素化合物が副生する傾向の大きさに着目した方法ではない。そのため、長期にわたる保管や使用を想定したような、高温かつ高湿度雰囲気中に、六方晶窒化ホウ素粉末を一定期間置いた試験を実施すると、該六方晶窒化ホウ素粉末と雰囲気中の水分とが反応して水溶性ホウ素化合物の副生が進行し、「外原規2006」の規格を逸脱してしまう現象が見られ、実用的な耐久性に関する課題は残存していた。 However, in the methods disclosed in Patent Document 1 and Patent Document 2, when a trace amount of the surfactant or organic solvent used in the cleaning treatment remains in the hexagonal boron nitride powder, there is a possibility that skin irritation may be exhibited. I can't deny it. In addition, these techniques focus on cleaning and preliminarily removing the water-soluble boron compound that was present in the hexagonal boron nitride powder. For example, while the hexagonal boron nitride powder is stored, it is water-soluble. It is not a method that focuses on the magnitude of the tendency of sex boron compounds to be produced as a by-product. Therefore, when a test in which the hexagonal boron nitride powder is placed for a certain period of time in a high temperature and high humidity atmosphere assuming long-term storage and use, the hexagonal boron nitride powder reacts with the moisture in the atmosphere. As a result, the by-product of the water-soluble boron compound progressed, and a phenomenon was observed in which the standard of "Outer Regulations 2006" was deviated, and the problem of practical durability remained.
また、特許文献3に示される方法は、窒化ホウ素粉末の耐加水分解性を向上させる効果があるが、長期保管性に対しては未だ改善の余地が残されている。また、高温での再焼成が必要になるため製造工程が複雑になり、六方晶窒化ホウ素粉末が高額になる問題があった Further, the method shown in Patent Document 3 has an effect of improving the hydrolysis resistance of the boron nitride powder, but there is still room for improvement in the long-term storage property. In addition, since re-baking at a high temperature is required, the manufacturing process becomes complicated, and there is a problem that the hexagonal boron nitride powder becomes expensive.
さらに特許文献4に示される六方晶窒化ホウ素粉末はアスペクト比(長径/厚さ)が5~20と記載されている。長径に対する厚さの比率が小さいため鱗片粒子が厚みを増したものとなり、これら六方晶窒化ホウ素粉末を用いたファンデーションなどの化粧料は塗り伸び性、カバー力(隠ぺい力)が十分に発揮されない。 Further, the hexagonal boron nitride powder shown in Patent Document 4 is described as having an aspect ratio (major axis / thickness) of 5 to 20. Since the ratio of the thickness to the major axis is small, the scale particles become thicker, and cosmetics such as foundations using these hexagonal boron nitride powders do not sufficiently exhibit the spreadability and covering power (concealing power).
六方晶窒化ホウ素の耐久性、及び塗り伸び性を向上させるためには、上述に加えて六方晶窒化ホウ素の結晶性を向上させる必要がある。しかし化粧料用窒化ホウ素において、結晶性に関する知見は今まで見られなかった。 In addition to the above, it is necessary to improve the crystallinity of hexagonal boron nitride in order to improve the durability and coatability of hexagonal boron nitride. However, no findings regarding crystallinity have been found in boron nitride for cosmetics.
上記を鑑み、本発明は、従来に比べて塗り伸び、隠ぺい力に優れた化粧料用の窒化ホウ素粉末を提供する。 In view of the above, the present invention provides a boron nitride powder for cosmetics, which is superior in spreading and hiding power as compared with the conventional one.
(1)アスペクト比(長径/厚さ)が20を超え、かつ平均粒子径が3~20μm、比表面積が1~10m2/g、一次粒子の粉末X線回折法による黒鉛化指数(Graphitization Index)が2.0以下、タップ密度が0.5g/cm3以下であることを特徴とする六方晶窒化ホウ素粉末。
(2)医薬部外品原料規格2006に準拠して測定される溶出ホウ素が20mg/L以下であることを特徴とする(1)に記載の六方晶窒化ホウ素粉末。
(3)(1)または(2)に記載の六方晶窒化ホウ素粉末を含む化粧料。
(1) The aspect ratio (major axis / thickness) exceeds 20, the average particle size is 3 to 20 μm, the specific surface area is 1 to 10 m 2 / g, and the graphitization index of the primary particles by powder X-ray diffraction method (Graphitation Index). ) Is 2.0 or less, and the tap density is 0.5 g / cm 3 or less.
(2) The hexagonal boron nitride powder according to (1), wherein the eluted boron measured in accordance with the quasi-drug raw material standard 2006 is 20 mg / L or less.
(3) A cosmetic containing the hexagonal boron nitride powder according to (1) or (2).
本発明により、従来に比べて塗り伸び、隠ぺい力に優れた化粧料用の六方晶窒化ホウ素粉末、及び六方晶窒化ホウ素粉末を含む化粧料を得ることができるという効果を奏する。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a cosmetic containing hexagonal boron nitride powder and hexagonal boron nitride powder for cosmetics, which are superior in spreading and hiding power as compared with the conventional invention.
<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、アスペクト比(長径/厚さ)が20を超え、かつ平均粒子径が3~20μm、比表面積が1~10m2/g、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 aspect ratio (major axis / thickness) of more than 20, an average particle size of 3 to 20 μm, a specific surface area of 1 to 10 m 2 / g, and a graphitization index. It 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。 Hereinafter, a more detailed description for carrying out the hexagonal boron nitride powder according to the present invention will be shown.
<アスペクト比>
アスペクト比はある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。六方晶窒化ホウ素はいわゆる「鱗片形状」の粒子であり、最も短い箇所(短径)は鱗片粒子の厚さで表すことができる。よって本発明の六方晶窒化ホウ素粉末におけるアスペクト比は、(長径)/(厚さ)で示すこととする。アスペクト比は20を超える必要があり、望ましくは21~30、更に好ましくは24~28である。アスペクト比が20以下では、長径が小さいため隠ぺい力が不十分となる、もしくは厚さが大きいため塗り伸び性が不十分となる。
<Aspect ratio>
The aspect ratio is expressed by the ratio ((major diameter) / (minor diameter)) of the longest part (major diameter) and the shortest part (minor diameter) of a certain particle. Hexagonal boron nitride is a so-called "scale-shaped" particle, and the shortest part (minor axis) can be represented by the thickness of the scale particle. Therefore, the aspect ratio of the hexagonal boron nitride powder of the present invention is indicated by (major axis) / (thickness). The aspect ratio needs to be greater than 20, preferably 21-30, more preferably 24-28. When the aspect ratio is 20 or less, the hiding power is insufficient because the major axis is small, or the coating extensibility is insufficient because the thickness is large.
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、例えば電子顕微鏡により撮影された粒子画像をそのまま解析する方法では誤差が生じ易く(例えば粒子が傾いていると誤差が生じる)、正確な測定が困難である。そこで本発明の六方晶窒化ホウ素におけるアスペクト比の測定方法は、以下の通り行った(Non-Oxide Technical and Engineering Ceramics, 83-96, 1986,Springer)。
窒化ホウ素粉末をプレス成型し、樹脂包埋後に断面ミリング加工を行うことで、窒化ホウ素粒子の断面を得た。プレス成型により窒化ホウ素粒子が一方向に配向した状態が得られ、粒子傾きによる測定誤差を抑えられる。この断面を走査型電子顕微鏡、例えば「JSM-6010LA」(日本電子社製)にて撮影し、得られた粒子像を画像解析ソフトウェア、例えば「Mac-View」(マウンテック社製)に取り込む。
次いで、得られた写真から粒子の長辺(=長径)と短辺(=厚さ)を測定し長辺短辺比(長辺/短辺)を算出し、粒子100個に対する測定結果を得た。
得られた長径短径比より累積分布を作成し、累積相対度数の95%に相当する長径/厚さを求め、これをアスペクト比とした。
When measuring the aspect ratio of "scaly" particles such as hexagonal boron nitride, an error is likely to occur in the method of analyzing the particle image taken by an electron microscope as it is (for example, if the particle is tilted, an error will occur. Occurs), accurate measurement is difficult. Therefore, the method for measuring the aspect ratio of hexagonal boron nitride of the present invention was carried out as follows (Non-Oxide Technical and Engineering Ceramics, 83-96, 1986, Springer).
The boron nitride powder was press-molded, embedded in a resin, and then cross-section milled to obtain a cross-section of the boron nitride particles. By press molding, the boron nitride particles are oriented in one direction, and the measurement error due to the particle inclination can be suppressed. This cross section is photographed with a scanning electron microscope, for example, "JSM-6010LA" (manufactured by JEOL Ltd.), and the obtained particle image is taken into image analysis software, for example, "Mac-View" (manufactured by Mountech).
Next, the long side (= major axis) and short side (= thickness) of the particles are measured from the obtained photograph, the long side short side ratio (long side / short side) is calculated, and the measurement result for 100 particles is obtained. rice field.
A cumulative distribution was created from the obtained major axis / minor axis ratio, and the major axis / thickness corresponding to 95% of the cumulative relative frequency was obtained, and this was used as the aspect ratio.
<平均粒子径>
本発明の六方晶窒化ホウ素の平均粒子径は3~20μm、好ましくは5~15μm、更に好ましくは6~12μmである。平均粒子径が3μm未満では、塗り伸び性及び隠ぺい力が不十分となる。平均粒子径が20μmを超えると塗り伸び性や隠ぺい力には問題がないが、外観上のぎらつきが強くなったりするため、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条件により変わる可能性があり、本発明では、六方晶窒化ホウ素粉末60mgを、15gの0.2質量%ヘキサメタリン酸水溶液に加え、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、粒度分布測定機により計測した値である。
<Average particle size>
The average particle size of the hexagonal boron nitride of the present invention is 3 to 20 μm, preferably 5 to 15 μm, and more preferably 6 to 12 μm. If the average particle size is less than 3 μm, the spreadability and hiding power will be insufficient. If the average particle size exceeds 20 μm, there is no problem in the spreadability and the hiding power, but the glare on the appearance becomes strong, 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 volume-based cumulative particle size distribution in the particle size distribution measurement by the laser diffraction / scattering method. In general, the average particle size may change depending on the measurement conditions. In the present invention, 60 mg of hexagonal boron nitride powder is added to 15 g of a 0.2 mass% hexamethaphosphate aqueous solution and dispersed with a homogenizer at an output of 300 W for 180 seconds. It is a value measured by a particle size distribution measuring machine using the dispersion liquid after that.
<比表面積>
本発明の六方晶窒化ホウ素粉末の比表面積は1~10m2/g、好ましくは1~5m2/g、更に好ましくは2~3m2/gである。比表面積が1m2/g未満では粒子径が大きくなり、塗り伸び性や隠ぺい力には問題がないが、外観上のぎらつきが強くなったりするため、化粧料原料としては好ましくなくなる。比表面積が10を超えると、塗り伸び性及び隠ぺい力が不十分となる上に、後述の溶出ホウ素量が20mg/Lを超えてしまう。比表面積は、一般に市販されているガス吸着現象を利用した測定装置を用い、BET1点法により算出された値を用いることができる。
<Specific surface area>
The specific surface area of the hexagonal boron nitride powder of the present invention is 1 to 10 m 2 / g, preferably 1 to 5 m 2 / g, and more preferably 2 to 3 m 2 / g. If the specific surface area is less than 1 m 2 / g, the particle size becomes large and there is no problem in coatability and hiding power, but the appearance becomes more glaring, which is not preferable as a raw material for cosmetics. If the specific surface area exceeds 10, the spreadability and hiding power will be insufficient, and the amount of eluted boron, which will be described later, will exceed 20 mg / L. As the specific surface area, a commercially available measuring device using a gas adsorption phenomenon can be used, and a value calculated by the BET 1-point method can be used.
<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1)に代入することによって算出できることが示され(J.Thomas,et.al,J.Am.Chem.Soc.84,4619(1962))ており、これを六方晶窒化ホウ素に適用したものである。
<Graphitization index>
Hexagonal boron nitride powder has a crystal structure similar to that of graphite, and its graphitization index can be calculated by the same method as graphite by using powder X-ray diffraction measurement. That is, the graphitization index is each of the peak area S1 derived from the (100) plane, the peak area S2 derived from the (101) plane, and the peak area S3 derived from the (102) plane of the X-ray diffraction spectrum. It has been shown that the value can be calculated by substituting the value into (Equation 1) (J. Thomas, et. Al, J. Am. Chem. Soc. 84, 4619 (1962)), which is hexagonal boron nitride. It is 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度以上42.5度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度以上45度以下のピークの面積である。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度以上52度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度及び54度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 of the peak corresponding to the X-ray diffraction spectrum of the (100) plane of hexagonal boron nitride (integral intensity ratio), and specifically, 2θ = 40 degrees or more and 42.5 degrees or less. The area of the peak of. Similarly, S2 is the area of the peak corresponding to the X-ray diffraction spectrum of the (101) plane of hexagonal boron nitride (integral intensity ratio), specifically, the area of the peak of 2θ = 43 degrees or more and 45 degrees or less. .. S3 is the area of the peak corresponding to the X-ray diffraction spectrum of the (102) plane of hexagonal boron nitride (integral intensity ratio), and specifically, the area of the peak of 2θ = 48 degrees or more and 52 degrees or less. In finding the area of each peak, a baseline was created by connecting the values at 2θ = 38 degrees and 54 degrees with a straight line, and each peak area was calculated with reference to 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塗り伸び性に影響する。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1.5以下、更に好ましくは1.3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化が不十分となり、塗り伸び性が不十分となる。 The graphitization index is an index of the crystallinity of hexagonal boron nitride and affects the coatability when used as a cosmetic. The graphitization index of hexagonal boron nitride of the present invention is 2.0 or less, preferably 1.5 or less, and more preferably 1.3 or less. When the graphitization index exceeds 2.0, the crystallization of hexagonal boron nitride becomes insufficient and the coatability becomes insufficient.
<溶出ホウ素>
溶出ホウ素は肌への刺激性を示すため、所定量に低減する必要がある。溶出ホウ素は医薬部外品原料規格2006に準拠した方法で行い、その値は20mg/L以下である必要がある。なお好ましい値は15mg/L以下、更に好ましくは10mg/L以下である。溶出ホウ素が20mg/Lを超えると、肌への刺激性を示す恐れがある。
<Eluted boron>
Since the eluted boron is irritating to the skin, it is necessary to reduce it to a predetermined amount. Eluted boron should be prepared by a method conforming to the quasi-drug raw material standard 2006, and the value should be 20 mg / L or less. A preferable value is 15 mg / L or less, and more preferably 10 mg / L or less. If the eluted boron exceeds 20 mg / L, it may be irritating to the skin.
<タップ密度>
本発明に係る六方晶窒化ホウ素粉末のタップ密度は0.5g/cm3以下、好ましくは0.3g/cm3以下、更に好ましくは0.25g/cm3以下である。本発明でいうタップ密度とは、タップ密度測定器(例:ホソカワミクロン社製、パウダーテスターPT-E型)を用い、100cm3の専用容器に六方晶窒化ホウ素粉末を仮充填してから、タッピングタイム180秒、タッピング回数180回、タップリフト18mmの条件で容器をタッピングして衝撃で固めた後、容器上部の余分な六方晶窒化ホウ素粉末をブレードで擦りきり、数2の式に測定した各質量値を代入することにより求めたものである。
<Tap density>
The tap density of the hexagonal boron nitride powder according to the present invention is 0.5 g / cm 3 or less, preferably 0.3 g / cm 3 or less, and more preferably 0.25 g / cm 3 or less. The tap density as used in the present invention refers to the tapping time after temporarily filling a 100 cm 3 dedicated container with hexagonal boron nitride powder using a tap density measuring device (eg, powder tester PT-E type manufactured by Hosokawa Micron). After tapping the container under the conditions of 180 seconds, 180 tapping times, and 18 mm tap lift and hardening by impact, the excess hexagonal boron nitride powder on the upper part of the container was scraped off with a blade, and each mass measured by the formula 2 was measured. It was obtained by assigning a value.
タップ密度の値が小さい六方晶窒化ホウ素粉末は感触がふわっとしており、肌に塗ったときの感触が軽くなる特徴がある。タップ密度が0.5g/cm3を超えると、肌に塗ったときの感触が重くなり、化粧料として好ましくはない。 Hexagonal boron nitride powder, which has a small tap density value, has a fluffy feel and is characterized by a light feel when applied to the skin. If the tap density exceeds 0.5 g / cm 3 , the feel when applied to the skin becomes heavy, which is not preferable as a cosmetic.
<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)の合計100質量部と、0.9質量部以上20質量部以下のアルカリ金属化合物など、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、窒素、ヘリウム、アルゴン、アンモニア等の不活性雰囲気下で焼成して、粗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。
<Manufacturing method of hexagonal boron nitride>
As an example of the method for producing a hexagonal boron nitride powder of the present invention, a powder of a compound containing boron and a powder of a compound containing nitrogen (hereinafter, a compound containing boron and a compound containing nitrogen may be used as a starting material together. A total of 100 parts by mass and a powder of a sintering aid that promotes the conversion of the starting material to hexagonal boron nitride during firing, such as an alkali metal compound of 0.9 parts by mass or more and 20 parts by mass or less, and this book. To the extent that it does not deviate from the object of the invention, if necessary, a mixed powder containing a simple substance or a compound other than the starting material and the sintering aid is calcined in an inert atmosphere such as nitrogen, helium, argon or ammonia. Examples thereof include a production method including a step of forming a crude hexagonal boron nitride, adding an impurity removing treatment by washing the compound with a cleaning liquid, and then drying the compound.
ここでホウ素を含む化合物としては、ホウ酸、酸化ホウ素、ホウ砂などを好ましく、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、尿素などを好ましく、特にメラミンを好ましく選択することができる。さらに焼結助剤の好ましい具体例としては、炭酸リチウム、炭酸ナトリウムなどの炭酸塩を挙げることができる。また、出発原料や焼結助剤以外に添加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。なお、粗六方晶窒化ホウ素を製造するための出発原料や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。 Here, as the compound containing boron, boric acid, boron oxide, borax and the like 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. Further, preferred specific examples of the sintering aid include carbonates such as lithium carbonate and sodium carbonate. Further, as an example of a simple substance or a compound that can be added other than the starting material and the sintering aid, a reducing substance such as carbon can be mentioned. The starting material for producing crude hexagonal boron nitride and various compounds used as sintering aids need not be limited to one type, and a plurality of types of compounds and the like can be used at the same time. Further, 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 set according to the reactivity and the yield. It can be appropriately changed in the range of 2: 8 to 8: 2, more preferably in the range of 3: 7 to 7: 3.
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、粗六方晶窒化ホウ素粉末合成時の焼結助剤の配合量、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1.1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0.9質量部未満であると、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20質量部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, varies depending on the blending amount of the sintering aid and the firing temperature at the time of synthesizing the crude hexagonal boron nitride powder. The mixing ratio of the sintering aid to 100 parts by mass of the starting material is preferably at least 0.9 parts by mass or more, preferably 1.0 part by mass or more, and more preferably 1.1 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, and more preferably 12 parts by mass or less. Is desirable. When the blending ratio of the sintering aid is less than 0.9 parts by mass, the conversion reaction from the starting material to hexagonal boron nitride, which should proceed with sintering, does not proceed, and the graphitization index becomes 2.0. The value tends to exceed the value, and the spreadability as a cosmetic is insufficient. On the contrary, if the blending ratio of the sintering aid exceeds 20 parts by mass, the crystal growth of hexagonal boron nitride progresses too much and fine pulverization becomes difficult, and there is a high possibility that the average particle size of the powder exceeds 20 μm. Cosmetics using such hexagonal boron nitride powder as a raw material have a strong appearance of glare and are not suitable as a raw material for cosmetics.
該混合粉末を焼成するときの最高温度としては、1600℃以上2200℃以下の範囲の温度が好ましく、1650℃以上1800℃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、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。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るため微粉砕が困難になり、化粧料用原材料として実用上好ましくない。 As the maximum temperature when firing the mixed powder, 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 1800 ° 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 spreadability as a cosmetic is insufficient. Not preferable. If the maximum firing temperature exceeds 2200 ° C., the crystal growth of hexagonal boron nitride progresses too much, making fine pulverization difficult, which is not practically preferable as a raw material for cosmetics.
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、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 changed continuously or discontinuously, and the speed at the time of heating and cooling is not limited, but if the firing time is too short, the firing will be performed. 2 hours or more is preferable, and 4 hours or more is more preferable, because it becomes insufficient and the graphitization index may exceed 2.0. The device for firing the powder mixture is not particularly limited, but a container made of, for example, hexagonal boron nitride can be used as the container for storing the powder mixture, and an electric heater, for example, can be used as the heating device. A firing furnace using the above can be used.
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, from the time when the starting materials are mixed to form a powder mixture until the end of firing, further heating, cooling, humidifying, drying, and washing operations are added within a range not deviating from the object of the present invention. Is also possible.
焼成が終了して得られた粗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の比表面積が上昇し、塗り伸び性及び隠ぺい力が不十分となる上に、後述の溶出ホウ素量が20mg/Lを超えてしまう恐れがある。 The device for crushing the crude hexagonal boron nitride obtained after firing is not particularly specified, but the specific surface area of the obtained hexagonal boron nitride increases depending on the crushing conditions, and the coatability and hiding power are poor. In addition to being sufficient, the amount of boron nitride described below may exceed 20 mg / L.
粉砕した粗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。粗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、粗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、粗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。 The crushed crude hexagonal boron nitride powder may contain impurities other than hexagonal boron nitride and water-soluble boron compounds (hereinafter collectively referred to as impurities, etc.). After removing impurities and the like, the hexagonal boron nitride powder of the present invention can be finally obtained by solid-liquid separation and drying. The cleaning liquid referred to here is preferably water, an aqueous solution containing an acidic substance, an organic solvent, or a mixed liquid of an organic solvent and water. As the water, for example, cold water, hot water or hot water at 5 to 95 ° C. can be used, and in this case, water having an electric conductivity of 1 mS / m or less should be used from the viewpoint of avoiding secondary contamination of impurities. Can be done. Examples of the acidic substance include inorganic acids such as hydrochloric acid and nitric acid. As the organic solvent, for example, a water-soluble organic solvent such as methanol, ethanol, propanol, isopropyl alcohol or acetone can be preferably used. The method of contacting the crude hexagonal boron nitride powder with the cleaning liquid is not particularly limited, but the crude hexagonal boron nitride powder is immersed in the cleaning liquid and stirred, or the cleaning liquid is sprayed on the crude hexagonal boron nitride powder. There is a method of cleaning by rubbing.
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。 In the case of solid-liquid separation and then drying after cleaning, the method of solid-liquid separation is not particularly limited, and for example, decantation, suction filter, pressure filter, rotary filter, sedimentation separator or theirs. Combined devices can be used.
さらに固液分離後の粗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、乾燥機の設定温度は30℃以上250℃以下、好ましくは200℃以下、乾燥機内の圧力は10-6kPaA以上101.3kPaA以下、好ましくは5kPaA以下である。 Further, the method for drying the crude hexagonal boron nitride powder after solid-liquid separation is not particularly limited, but an example of a drying device that can be used is a shelf dryer, a fluidized bed dryer, a spray dryer, and a rotary dryer. A machine, a belt dryer, or a combination thereof. The set temperature of the dryer is 30 ° C. or higher and 250 ° C. or lower, preferably 200 ° C. or lower, and the pressure inside the dryer is 10-6 kPaA or higher and 101.3 kPaA or lower, preferably 5 kPaA. It is as follows.
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。 Washing, solid-liquid separation, and drying may be performed once, or the same method or a combination of different methods may be performed multiple times.
<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添加量は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>
In another aspect, the present invention is a cosmetic containing the hexagonal boron nitride powder of the present invention. Examples of cosmetics are foundations (powder foundations, liquid foundations, cream foundations), face powders, point makeups, eye shadows, eye liners, manicures, lipsticks, blushers, and mascara, but especially foundations and eye shadows. The hexagonal boron nitride powder of the invention is particularly well suited. A suitable amount of the hexagonal boron nitride powder of the present invention to be added 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)100g、及びメラミン粉末(和光純薬社製、純度99.0質量%以上)90g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。
これを六方晶窒化ホウ素製の容器(容積約500cm3)に入れ、炉室内容積が約16000cm3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た。
得られた焼成品100gに、炭酸ナトリウム(和光純薬社製、純度99.5質量%以上)を3g秤量し、アルミナ製乳鉢を用いて10分間混合した。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1700℃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、粗六方晶窒化ホウ素(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、粗六方晶窒化ホウ素の粉末となした。
さらに該粗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120℃で3時間一旦乾燥した後、実施例1の六方晶窒化ホウ素粉末を得た。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
<Example 1>
Weigh 100 g of boric acid powder (manufactured by Kanto Chemical Co., Inc., purity 99.8% by mass or more) and 90 g of melamine powder (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0% by mass or more), and weigh each of them into an alumina mortar. Was mixed for 10 minutes using. The prepared powder mixture was placed in a constant temperature and humidity chamber (AGX-225 manufactured by ADVANTEC), humidified at 80 ° C. and 95% relative humidity for 1 hour, and then dried at 120 ° C. for 1 hour.
This is placed in a container made of hexagonal boron nitride (volume approx. 500 cm 3 ), placed in an electric furnace (Tokai Kogyo Kogyo Co., Ltd., TV-200) with a furnace chamber volume of approximately 16000 cm 3 , and nitrogen gas into the furnace chamber. Set the flow rate to 16 L (volume at 25 ° C) / min, raise the temperature from room temperature at a rate of 10 ° C / min, hold at 1000 ° C for 2 hours, then stop heating and let it cool naturally, and the temperature drops to 100 ° C or less. At that point, the electric furnace was opened.
To 100 g of the obtained calcined product, 3 g of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5% by mass or more) was weighed 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 to 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 to reach the maximum firing temperature of 1700 ° C. The temperature was maintained for 4 hours after reaching. 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 and the crude hexagonal boron nitride (before pulverization) was recovered. This was pulverized in an alumina mortar for 3 minutes to obtain a powder of crude hexagonal boron nitride.
Further, in order to remove impurities contained in the crude hexagonal boron nitride powder, the powder was added at a ratio of 30 g per 500 g of 5 mass% dilute nitrate, stirred at room temperature for 60 minutes, and then solid-liquid separated by suction filtration. Water (electrical conductivity 1 mS / m) was replaced and washed until the filtrate became neutral. The washed powder was once dried at 120 ° C. for 3 hours in a dryer to obtain the hexagonal boron nitride powder of Example 1.
<アスペクト比>
実施例1で作製した六方晶窒化ホウ素粉末をプレス成型し、樹脂包埋後に断面ミリング加工を行うことで、窒化ホウ素粒子の断面を得た。この断面を走査型電子顕微鏡(日本電子社製、JSM-6010LA)にて倍率5000倍で撮影し、得られた粒子像を画像解析ソフトウェア(マウンテック社製、Mac-View)に取り込んだ。次いで、得られた写真から粒子の長辺(=長径)と短辺(=短径)を測定し長辺短辺比(長辺/短辺)を算出し、粒子100個に対する測定結果を得た。得られた長径短径比より累積分布を作成し、累積相対度数の95%に相当する長径短径比の値を求め、これをアスペクト比とした。
<Aspect ratio>
The hexagonal boron nitride powder produced in Example 1 was press-molded, embedded in a resin, and then cross-section milled to obtain a cross-section of the boron nitride particles. This cross section was photographed with a scanning electron microscope (JSM-6010LA, manufactured by JEOL Ltd.) at a magnification of 5000 times, and the obtained particle image was incorporated into image analysis software (Mac-View, manufactured by Mountech). Next, the long side (= major axis) and short side (= minor axis) of the particles are measured from the obtained photograph, the long side short side ratio (long side / short side) is calculated, and the measurement result for 100 particles is obtained. rice field. A cumulative distribution was created from the obtained major axis / minor axis ratio, and the value of the major axis / minor axis ratio corresponding to 95% of the cumulative relative frequency was obtained, and this was used as the aspect ratio.
<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 of hexagonal boron nitride powder prepared in Example 1 was prepared by the method described above, and the average particle size of the hexagonal boron nitride powder was measured with a particle size distribution measuring machine (MT3300EX type manufactured by Nikkiso Co., Ltd.). 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.
<比表面積>
実施例1で作製した六方晶窒化ホウ素粉末の比表面積を、比表面積測定装置(ユアサアイオニクス社製、カンターソーブ)を用いて、BET1点法により測定した。なお測定に際しては、試料1gを300℃、15分間乾燥脱気してから測定に供した。
<Specific surface area>
The specific surface area of the hexagonal boron nitride powder produced in Example 1 was measured by the BET 1-point method using a specific surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Cantersorb). In the measurement, 1 g of the sample was dried and degassed at 300 ° C. for 15 minutes before being subjected to the measurement.
<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。
<Graphitization index>
The graphitization index of the hexagonal boron nitride powder prepared in Example 1 was measured using a high-power powder X-ray diffractometer (D8ADVANCE Super Speed, manufactured by Bruker AXS). Hexagonal boron nitride powder was press-molded at 100 kN, a sample of 10 × 15 × 3 mm was used as a subject, CuKα ray was used as an X-ray source, a tube voltage was 45 kV, and a tube current was 360 mA.
<溶出ホウ素>
実施例1で作製した六方晶窒化ホウ素粉末の、製造直後、及び長期保管後の水に溶出するホウ素の量は、基本的に「外原規2006」に基づく方法で抽出し、ICP発光分光分析装置で測定した。
即ち、製造直後の六方晶窒化ホウ素粉末2.5gをフッ素系樹脂製ビーカーにとり、エタノール10mLを加えてよくかき混ぜ、更に水40mLを加えてよくかき混ぜた後、フッ素系樹脂製時計皿をのせ、50℃で1時間加温した。冷却後、該ビーカーの内容物をろ過したろ液と、少量の水による残留物の洗液とを合わせた回収液を採取した。
該回収液を、孔径0.22μmのメンブレンフィルターでろ過して「石英」製ビーカーにとり、この中に硫酸(47.5質量%)2mL を加えた。さらにホットプレート上で10分間煮沸し、冷後、この液をポリエチレン製メスフラスコに入れ、更にビーカーを少量の水で洗い、この水洗液も当該ポリエチレン製メスフラスコに移し、さらに水を追加して正確に100mL とし、これを試料溶液とした。試料溶液のホウ素量をICP発光分光分析装置 (島津製作所製、ICPE-9000)で測定した。
<Eluted boron>
The amount of boron eluted in water immediately after production and after long-term storage of the hexagonal boron nitride powder prepared in Example 1 is basically extracted by a method based on "Outer Regulations 2006" and analyzed by ICP emission spectroscopy. Measured with the device.
That is, take 2.5 g of hexagonal boron nitride powder immediately after production in a fluorine-based resin beaker, add 10 mL of ethanol and stir well, add 40 mL of water and stir well, then put a fluorine-based resin watch glass on it and put it on 50. It was heated at ° C for 1 hour. After cooling, a recovered liquid obtained by filtering the contents of the beaker and washing the residue with a small amount of water was collected.
The recovered liquid was filtered through a membrane filter having a pore size of 0.22 μm and placed in a “quartz” beaker, and 2 mL of sulfuric acid (47.5% by mass) was added thereto. Boil on a hot plate for 10 minutes, cool, put this solution in a polyethylene volumetric flask, wash the beaker with a small amount of water, transfer this water wash solution to the polyethylene volumetric flask, and add more water. The volume was exactly 100 mL, which was used as the sample solution. The amount of boron in the sample solution was measured with an ICP emission spectrophotometer (ICPE-9000, manufactured by Shimadzu Corporation).
<タップ密度>
実施例1で作製した六方晶窒化ホウ素粉末のタップ密度は、タップ密度測定器(ホソカワミクロン社製、パウダーテスター PT-E型)を用いて測定した。即ち、100cm3の専用容器に六方晶窒化ホウ素粉末を仮充填してから、タッピングタイム180秒、タッピング回数180回、タップリフト18mmの条件で容器をタッピングして衝撃で固めた後に余剰分を擦りきりして測定した、擦りきり後の容器含む全体質量を基に算出した値である。
<Tap density>
The tap density of the hexagonal boron nitride powder prepared in Example 1 was measured using a tap density measuring device (powder tester PT-E type manufactured by Hosokawa Micron Co., Ltd.). That is, after temporarily filling a 100 cm 3 dedicated container with hexagonal boron nitride powder, the container is tapped under the conditions of tapping time 180 seconds, tapping frequency 180 times, and tap lift 18 mm, and then the surplus is rubbed after being hardened by impact. It is a value calculated based on the total mass including the container after scraping, which was measured by cutting.
<塗り伸び>
実施例1で作製した六方晶窒化ホウ素粉末にタルク(ヤマグチマイカ製「EX-15」)、顔料(ヤマグチマイカ製「LY-S」)、マイカ(三信鉱工製「セリサイトFSN」)、流動パラフィン(カネダ製「ハイコールM-352」)を用いて、化粧料(ファンデーション)を作製した。配合量を以下に示す。
(成分) (配合量(質量%))
窒化ホウ素 35.0
タルク 8.0
顔料 8.0
マイカ 35.0
流動パラフィン 14.0
この化粧料について10名の被験者に1ヶ月間使用してもらい、次の評価基準にて評価。
○:塗り伸び良好(3点)
△:塗り伸び普通(2点)
×:塗り伸び不良(1点)
全被験者の評価結果の平均値を求めた。また使用した被験者が気になった点をその他に記載した。なお気になった点がないものについては横線(-)とした。
<Painting>
Talc ("EX-15" manufactured by Yamaguchi Mica), pigment ("LY-S" manufactured by Yamaguchi Mica), mica ("Serisite FSN" manufactured by Sanshin Mining Co., Ltd.), flow on the hexagonal boron nitride powder prepared in Example 1. A cosmetic (foundation) was prepared using paraffin (“Hicol M-352” manufactured by Kaneda). The blending amount is shown below.
(Ingredients) (Mixing amount (% by mass))
Boron Nitride 35.0
Talc 8.0
Pigment 8.0
Mica 35.0
Liquid paraffin 14.0
We asked 10 subjects to use this cosmetic for one month and evaluated it according to the following evaluation criteria.
◯: Good coating spread (3 points)
△: Normal coating (2 points)
×: Poor coating spread (1 point)
The average value of the evaluation results of all subjects was calculated. In addition, the points that the subject who used it was interested in were described in other points. Horizontal lines (-) are used for items that are not of concern.
<隠ぺい力評価>
JIS K 5101-4:2004 顔料試験方法-第4部:隠ぺい力-隠ぺい率試験紙法に準拠して、実施例1で作製した六方晶窒化ホウ素粉末50gを流動パラフィン100gに分散させた後、隠ぺい率試験紙に塗布した。測色色差計(日本電色工業製「ZE 6000」)を用いて、隠ぺい率試験紙の白色部と黒色部との明度比から隠ぺい率を求めた。
<Evaluation of hiding power>
After dispersing 50 g of the hexagonal boron nitride powder prepared in Example 1 in 100 g of liquid paraffin in accordance with JIS K 5101-4: 2004 Pigment Test Method-Part 4: Hiding Power-Hiding Rate Test Paper Method. It was applied to the concealment rate test paper. Using a colorimeter (“ZE 6000” manufactured by Nippon Denshoku Kogyo Co., Ltd.), the hiding rate was calculated from the brightness ratio between the white part and the black part of the hiding rate test paper.
<実施例2~6、比較例1~6>
実施例1の焼結助剤の出発原料に対する質量割合、焼成温度の最高値、焼成時間を変更して、実施例2~6、比較例1~6の六方晶窒化ホウ素粉末を作製した。
<Examples 2 to 6, Comparative Examples 1 to 6>
Hexagonal boron nitride powders of Examples 2 to 6 and Comparative Examples 1 to 6 were prepared by changing the mass ratio of the sintering aid of Example 1 to the starting material, the maximum value of the firing temperature, and the firing time.
<比較例7>
焼結助剤を添加しなかった以外は、実施例1と同じ条件で行い、比較例7の六方晶窒化ホウ素粉末を作製した。
<Comparative Example 7>
The same conditions as in Example 1 were carried out except that a sintering aid was not added, to prepare a hexagonal boron nitride powder of Comparative Example 7.
<比較例8、9>
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又は実施例3と同じ条件で行い、それぞれ比較例8、比較例9の六方晶窒化ホウ素粉末を作製した。
<Comparative Examples 8 and 9>
The same conditions as in Example 1 or Example 3 were carried out except that calcium carbonate (manufactured by Kanto Chemical Co., Inc., purity 99.5% by mass or more) was used as the sintering aid, and the hexagons of Comparative Example 8 and Comparative Example 9, respectively. A boron nitride powder was prepared.
本発明の実施により、従来に比べて塗り伸び、隠ぺい力に優れた化粧料用の窒化ホウ素粉末を提供することができるので、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 implementing the present invention, it is possible to provide a boron nitride powder for cosmetics, which is superior in spreading and hiding power as compared with the conventional one, and is therefore suitably used as a raw material for cosmetics such as foundations and eye shadows.
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